Process and systems for obtaining 1,3-butanediol from fermentation broths

Abstract

To provide bioderived 1,3-butanediol compositions, and systems and methods for producing such bioderived 1,3-butanediol compositions.SOLUTION: In one aspect, provided herein is bioderived 1,3-butylene glycol (1,3-BG), where the bioderived 1,3-BG includes detectable levels of one or more compounds selected from 3-hydroxy-butanal, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one, 1,2-propanediol, 1,3-propanediol or 2,3-butanediol.SELECTED DRAWING: None

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application is filed on the same date as the "Process and Systems for Obtaining This application claims the benefit of U.S. Provisional Patent Application No. 62 / 480,270, filed March 31, 2017, entitled "1,3-Butanediol from Fermentation Broths," the entire contents of which are incorporated herein by reference.

[0002] Reference is made to the following provisional and international applications, which are incorporated herein by reference in their entireties: (1) “3-HYDROXYBUTYRYL-COA DEHYDROGENASE VARIANTS AND METHODS,” filed on March 31, 2017; No. 62 / 480,208 (Attorney Docket No. 12956-409-888), entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE" filed on March 31, 2017; (2) U.S. Provisional Patent Application No. 62 / 480,194 (Attorney Docket No. 12956-408-888), entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE" filed on the same date as this application; and (4) International Patent Application No. __, entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE," filed on even date herewith, Attorney Docket No. 12956-409-228.

[0003] The present disclosure relates generally to compositions produced by biosynthetic methods, as well as methods and systems for producing such compositions. [Background technology]

[0004] 1,3 - BG (also known as BG, 1,3 - butanediol, 1,3 - BDO, 13 - BDO, 1,3 - butylene glycol, or butylene glycol) is a four - carbon diol that has conventionally been produced in chemical processes via the hydration of petroleum - derived acetylene (“petro - BG”). The resulting acetaldehyde is then converted to 3 - hydroxybutyraldehyde, which is subsequently reduced to form 1,3 - BG. 1,3 - BG is used in many industrial processes, for example, as an organic solvent for food flavorings and as a reagent for producing polyurethane and polyester resins. 1,3 - BG is generally of low toxicity and low irritation properties, and thus also finds further use in the cosmetics industry. In this specification, 1,3 - BG is particularly useful as an odorless cosmetic - grade ingredient.

[0005] Cosmetic - grade petro - BG, as well as methods for producing and storing cosmetic - grade petro - BG, are available in the cosmetics industry, but there is still a need for bio - based 1,3 - BG (“bio - BG”) for cosmetic and food applications, as well as methods and systems for producing such bio - BG. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0006] In one aspect, bio - based 1,3 - butylene glycol (1,3 - BG) is provided herein, whereby the bio - based 1,3 - BG comprises one or more compounds at detectable levels selected from 3 - hydroxy - butanal, 4 - hydroxy - 2 - butanone, 4-(3 - hydroxybutoxy)butan - 2 - one, 4 - ((4 - hydroxybutan - 2 - yl)oxy)-butan - 2 - one, 1,2 - propanediol, 1,3 - propanediol, or 2,3 - butanediol.

[0007] In some embodiments, the bioderived 1,3-BG comprises detectable levels of 3-hydroxy-butanol, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one or 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one.

[0008] In some embodiments, the bioderived 1,3-BG comprises one or more compounds at levels higher than petro-BG, selected from 3-hydroxy-butanol, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one or 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one.

[0009] In some embodiments, the chiral purity of the bioderived 1,3-BG is 95% or higher, 96% or higher, 97% or higher, 98% or higher, 99.0% or higher, 99.1% or higher, 99.2% or higher, 99.3% or higher, 99.4% or higher, 99.5% or higher, 99.6% or higher, 99.7% or higher, 99.8% or higher, or 99.9% or higher.

[0010] In some embodiments, the bioderived 1,3-BG has a chemical purity of 99.0% or higher, 99.1% or higher, 99.2% or higher, 99.3% or higher, 99.4% or higher, 99.5% or higher, 99.6% or higher, 99.7% or higher, 99.8% or higher, or 99.9% or higher.

[0011] In some embodiments, the bioderived 1,3-BG has more R-enantiomers than S-enantiomers.

[0012] In some embodiments, the bio-derived 1,3-BG has a chiral purity of 95% or higher and a chemical purity of 99.0% or higher.

[0013] In some embodiments, the bio-derived 1,3-BG has a chiral purity of 99.0% or higher and a chemical purity of 99.0% or higher.

[0014] In some embodiments, the bio-derived 1,3-BG has a chiral purity of 99.5% or higher and a chemical purity of 99.0% or higher.

[0015] In some embodiments, the bio-derived 1,3-BG is of industrial grade or cosmetic grade.

[0016] In some embodiments, the bio-derived 1,3-BG contains the compound at a level of 5 ppm or higher, 10 ppm or higher, 20 ppm or higher, 30 ppm or higher, 40 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, or 2,000 ppm or higher.

[0017] In some embodiments, the bio-derived 1,3-BG contains a detectable level of the compound characterized by the mass spectrum according to FIG. 3 or FIG. 4.

[0018] In some embodiments, the bio-derived 1,3-BG contains a detectable compound as a peak eluting at a relative retention time between 0.97 and 0.99 in the GC-MS chromatogram, where the relative retention time of 1,3-BG is 1.0.

[0019] In some embodiments, the bio-derived 1,3-BG contains compounds detectable in a GC-MS chromatogram as peaks eluting at relative retention times between 0.94 and 0.96, where the relative retention time of 1,3-BG is 1.0.

[0020] In some embodiments, the bio-derived 1,3-BG does not contain any detectable levels of one or more contaminants of petro-BG that are detectable in a GC-MS chromatogram as peaks eluting at relative retention times between 0.8 and 0.95, where the relative retention time of 1,3-BG is 1.0.

[0021] In some embodiments, the bio-derived 1,3-BG contains one or more contaminants at levels that are at least 2-fold, at least 3-fold, at least 4-fold, at least 5-fold, at least 6-fold, at least 7-fold, at least 8-fold, at least 9-fold, or at least 10-fold lower than detectable levels of petro-BG, which are detectable in a GC-MS chromatogram as peaks eluting at relative retention times between 0.8 and 0.95, where the relative retention time of 1,3-BG is 1.0.

[0022] In some embodiments, the chemical purity of the bio-derived 1,3-BG is 99% or higher, the total level of heavy substances is 0.8% or less, and the total level of light substances is 0.2% or less.

[0023] In some embodiments, the UV absorbance of the bio-derived 1,3-BG between 220 nm and 260 nm is at least 2-fold, at least 3-fold, at least 4-fold, at least 5-fold, at least 6-fold, at least 7-fold, at least 8-fold, at least 9-fold, or at least 10-fold lower than the UV absorbance of petro-BG.

[0024] In some embodiments, the bio-derived 1,3-BG does not contain detectable levels of 1,4-(4-methyl-1,3-dioxan-2-yl)propan-2-one.

[0025] In some embodiments, the bio-derived 1,3-BG contains 1-4-(4-methyl-1,3-dioxan-2-yl) propane-2-one at a level that is at least 2-fold, at least 3-fold, at least 4-fold, at least 5-fold, at least 6-fold, at least 7-fold, at least 8-fold, at least 9-fold, or at least 10-fold lower than petro-BG.

[0026] In some embodiments, the detectable level is analyzed by gas chromatography coupled mass spectrometry or liquid chromatography coupled mass spectrometry.

[0027] In some embodiments, the bio-derived 1,3-BG has a chiral purity of 55% or higher.

[0028] In one aspect, a method for purifying bio-derived 1,3-BG is provided herein, the method comprising: (a) subjecting a first bio-derived 1,3-BG-containing product stream to a first column distillation procedure to remove materials having a boiling point higher than that of bio-derived 1,3-BG as a first high-boiling material stream, thereby generating a second bio-derived 1,3-BG-containing product stream; (b) subjecting the second bio-derived 1,3-BG-containing product stream to a second column distillation procedure to remove materials having a boiling point lower than that of bio-derived 1,3-BG, thereby generating a third bio-derived 1,3-BG-containing product stream; and (c) subjecting the third bio-derived 1,3-BG-containing product stream to a third column distillation procedure to remove materials having a boiling point higher than that of bio-derived 1,3-BG as a second high-boiling material stream, thereby generating a purified bio-derived 1,3-BG product.

[0029] In some embodiments, the method further comprises subjecting a crude bio-derived 1,3-BG mixture to a dehydration column distillation procedure to remove materials having a boiling point lower than that of bio-derived 1,3-BG from the crude bio-derived 1,3-BG mixture, thereby generating the first bio-derived 1,3-BG-containing product stream of (a).

[0030] In some embodiments, the method further comprises subjecting the crude bioderived 1,3-BG to polishing ion exchange to produce the first bioderived 1,3-BG-containing product stream of (a).

[0031] In some embodiments, the purified bioderived 1,3-BG product comprises one or more compounds at detectable levels selected from the group consisting of 3-hydroxy-butan-al, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one, 1,2-propanediol, 1,3-propanediol, and 2,3-butanediol.

[0032] In some embodiments, the purified bioderived 1,3-BG product does not contain 1-4-(4-methyl-1,3-dioxan-2-yl)propan-2-one at detectable levels or contains it only at low levels.

[0033] In some embodiments, the method further comprises adding a base to the bioderived 1,3-BG-containing product stream either before or after any one of (a), (b), or (c).

[0034] In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream after (a).

[0035] In some embodiments, the method further comprises treating the bioderived 1,3-BG-containing product stream with a hydrogenation reaction either before or after any one of (a), (b), or (c).

[0036] In some embodiments, the second bioderived 1,3-BG-containing product stream is treated with a hydrogenation reaction before performing (b).

[0037] In some embodiments, due to the hydrogenation reaction, the concentration of 3-hydroxy-butanol or 4-hydroxy-2-butanone in the second bio-derived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0038] In some embodiments, due to the hydrogenation reaction, the UV absorbance at 270 nm or 220 nm of the second bio-derived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0039] In some embodiments, the purified bio-derived 1,3-BG product is collected as the distillate of the third column distillation procedure.

[0040] In some embodiments, the method further includes contacting the distillate of the third column distillation procedure with activated carbon to produce the purified bio-derived 1,3-BG product.

[0041] In some embodiments, the method further includes contacting the second bio-derived 1,3-BG-containing product stream with activated carbon before performing step (c).

[0042] In some embodiments, due to the contact with activated carbon, the concentration of 3-hydroxy-butanol or 4-hydroxy-2-butanone in the second bio-derived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0043] In some embodiments, the method further includes contacting the second bioderived 1,3-BG-containing product stream with sodium borohydride (NaBH4) before performing step (c).

[0044] In some embodiments, due to the contact with NaBH4, the UV absorbance of the second bioderived 1,3-BG-containing product stream at 270 nm or 220 nm is reduced by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0045] In some embodiments, the bioderived 1,3-BG has a chiral purity of 55% or higher.

[0046] In some embodiments, the purified bioderived 1,3-BG product has a chemical purity of 99.0% or higher.

[0047] In another aspect, provided herein is a system for purifying bioderived 1,3-BG, comprising: a first distillation column that receives a first bioderived 1,3-BG-containing product stream and generates a first material stream having a boiling point higher than that of 1,3-BG and a second bioderived 1,3-BG-containing product stream; a second distillation column that receives the second bioderived 1,3-BG-containing product stream and generates a material stream having a boiling point lower than that of 1,3-BG and a third bioderived 1,3-BG-containing product stream; and a third distillation column that receives the third 1,3-BG-containing product stream at a feed point and generates a second material stream having a boiling point higher than that of 1,3-BG and a fourth bioderived 1,3-BG-containing product stream comprising a purified bioderived 1,3-BG product.

[0048] In some embodiments, the fourth bioderived 1,3-BG-containing product stream consists essentially of the bioderived 1,3-BG provided herein.

[0049] In some embodiments, the system includes a polishing column that receives a crude bioderived 1,3-BG mixture and produces a crude bioderived 1,3-BG mixture with a reduced salt content.

[0050] In some embodiments, the polishing column is an ion exchange chromatography column.

[0051] In some embodiments, the system includes a dehydration column that receives a crude bioderived 1,3-BG mixture and produces a material stream having a boiling point lower than that of 1,3-BG and a first bioderived 1,3-BG-containing product stream.

[0052] In some embodiments, the bioderived 1,3-BG is produced by the methods provided herein or by the systems provided herein. In embodiments of the present invention, for example, the following items are provided. (Item 1) Bioderived 1,3-butylene glycol (1,3-BG) comprising one or more compounds at a detectable level selected from the group consisting of 3-hydroxy-butanol, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one, 1,2-propanediol, 1,3-propanediol, and 2,3-butanediol. (Item 2) The bioderived 1,3-BG according to Item 1, comprising 3-hydroxy-butanol, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, and 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one at a detectable level. (Item 3) The bioderived 1,3-BG according to Item 1 or 2, comprising one or more compounds at a level higher than that of petro-BG selected from the group consisting of 3-hydroxy-butanol, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, and 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one. (Item 4) The chirality purity of the bio-derived 1,3-BG is 95% or higher, 96% or higher, 97% or higher, 98% or higher, 99.0% or higher, 99.1% or higher, 99.2% or higher, 99.3% or higher, 99.4% or higher, 99.5% or higher, 99.6% or higher, 99.7% or higher, 99.8% or higher, or 99.9% or higher, and the bio-derived 1,3-BG according to any one of Items 1 to 3. (Item 5) The bio-derived 1,3-BG according to Item 4, having a chemical purity of 99.0% or higher, 99.1% or higher, 99.2% or higher, 99.3% or higher, 99.4% or higher, 99.5% or higher, 99.6% or higher, 99.7% or higher, 99.8% or higher, or 99.9% or higher. (Item 6) The bio-derived 1,3-BG according to any one of Items 1 to 5, containing more R-enantiomers than S-enantiomers. (Item 7) The bio-derived 1,3-BG according to Item 6, having a chirality purity of 95% or higher and a chemical purity of 99.0% or higher. (Item 8) The bio-derived 1,3-BG according to Item 7, having a chirality purity of 99.0% or higher and a chemical purity of 99.0% or higher. (Item 9) The bio-derived 1,3-BG according to Item 7, having a chirality purity of 99.5% or higher and a chemical purity of 99.0% or higher. (Item 10) The bio-derived 1,3-BG according to any one of Items 1 to 9, which is of industrial grade or cosmetic grade. (Item 11) The bio-derived 1,3-BG according to any one of items 1 to 10, containing the compound at a level of 5 ppm or higher, 10 ppm or higher, 20 ppm or higher, 30 ppm or higher, 40 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, or 2,000 ppm or higher. (Item 12) The bio-derived 1,3-BG according to any one of items 1 to 11, containing a detectable level of a compound characterized by the mass spectrum according to FIG. 3 or FIG. 4. (Item 13) The bio-derived 1,3-BG according to any one of items 1 to 12, containing a compound detectable as a peak eluting at a relative retention time between 0.97 and 0.99 in a GC-MS chromatogram, where the relative retention time of 1,3-BG is 1.0. (Item 14) The bio-derived 1,3-BG according to any one of items 1 to 13, containing a compound detectable as a peak eluting at a relative retention time between 0.94 and 0.96 in a GC-MS chromatogram, where the relative retention time of 1,3-BG is 1.0. (Item 15) The bio-derived 1,3-BG according to any one of items 1 to 14, not containing one or more contaminating substances at a detectable level of petro-BG, detectable as a peak eluting at a relative retention time between 0.8 and 0.95 in a GC-MS chromatogram, where the relative retention time of 1,3-BG is 1.0. (Item 16) One or more contaminating substances that are detectable in the GC-MS chromatogram as peaks eluting at a relative retention time between 0.8 and 0.95, and are at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, or at least 10 times lower than petro-BG, wherein the relative retention time of 1,3-BG is 1.0, the bio-derived 1,3-BG according to any one of items 1 to 15. (Item 17) The total purity of the bio-derived 1,3-BG is 99% or higher, the total level of heavy substances is 0.8% or less, and the total level of light substances is 0.2% or less, the bio-derived 1,3-BG according to any one of items 1 to 16. (Item 18) The UV absorbance of the bio-derived 1,3-BG between 220 nm and 260 nm is at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, or at least 10 times lower than the UV absorbance of petro-BG, the bio-derived 1,3-BG according to any one of items 1 to 17. (Item 19) The bio-derived 1,3-BG according to any one of items 1 to 18, not containing detectable levels of 1-4-(4-methyl-1,3-dioxan-2-yl)propan-2-one. (Item 20) The bio-derived 1,3-BG according to any one of items 1 to 19, containing 1-4-(4-methyl-1,3-dioxan-2-yl)propan-2-one at a level that is at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, or at least 10 times lower than petro-BG. (Item 21) The bio-derived 1,3-BG according to any one of items 1 to 20, wherein the detectable level is analyzed by gas chromatography coupled with mass spectrometry or liquid chromatography coupled with mass spectrometry. (Item 22) Biologically-derived 1,3-BG according to any one of items 1 to 21, having a chiral purity of 55% or higher. (Item 23) A method for purifying biologically-derived 1,3-BG, (a) subjecting a first biologically-derived 1,3-BG-containing product stream to a first column distillation procedure to remove materials having a boiling point higher than that of biologically-derived 1,3-BG as a first high-boiling material stream, thereby generating a second biologically-derived 1,3-BG-containing product stream; (b) subjecting the second biologically-derived 1,3-BG-containing product stream to a second column distillation procedure to remove materials having a boiling point lower than that of biologically-derived 1,3-BG, thereby generating a third biologically-derived 1,3-BG-containing product stream; (c) subjecting the third biologically-derived 1,3-BG-containing product stream to a third column distillation procedure to remove materials having a boiling point higher than that of biologically-derived 1,3-BG as a second high-boiling material stream, thereby generating a purified biologically-derived 1,3-BG product. A method comprising the above steps. (Item 24) The method according to item 23, further comprising subjecting a crude biologically-derived 1,3-BG mixture to a dehydration column distillation procedure to remove materials having a boiling point lower than that of biologically-derived 1,3-BG from the crude biologically-derived 1,3-BG mixture, thereby generating the first biologically-derived 1,3-BG-containing product stream of (a). (Item 25) The method according to item 23 or 24, further comprising subjecting crude biologically-derived 1,3-BG to refined ion exchange to generate the first biologically-derived 1,3-BG-containing product stream of (a). (Item 26) The method according to item 25, wherein the purified biologically-derived 1,3-BG product contains one or more compounds at a detectable level selected from the group consisting of 3-hydroxy-butan-al, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one, 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one, 1,2-propanediol, 1,3-propanediol, and 2,3-butanediol. (Item 27) The method according to item 25, wherein the purified bio-derived 1,3-BG product contains 1-4-(4-methyl-1,3-dioxan-2-yl)propan-2-one at undetectable levels or at low levels only. (Item 28) The method according to item 25, further comprising the step of adding a base to the bio-derived 1,3-BG-containing product stream either before or after any one of (a), (b), or (c). (Item 29) The method according to item 28, wherein the base is added to the bio-derived 1,3-BG-containing product stream after (a). (Item 30) The method according to item 25, further comprising the step of treating the bio-derived 1,3-BG-containing product stream by a hydrogenation reaction either before or after any one of (a), (b), or (c). (Item 31) The method according to item 25, wherein the second bio-derived 1,3-BG-containing product stream is treated by a hydrogenation reaction before performing (b). (Item 32) By the hydrogenation reaction, the concentration of 3-hydroxy-butan-al or 4-hydroxy-2-butanone in the second bio-derived 1,3-BG-containing product stream is reduced by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more. The method according to item 31. (Item 33) By the hydrogenation reaction, the UV absorbance at 270 nm or 220 nm of the second bio-derived 1,3-BG-containing product stream is reduced by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more. The method according to item 32. (Item 34) The method according to item 25, wherein the purified bio-derived 1,3-BG product is collected as the distillate of the third column distillation procedure. (Item 35) (c) further includes contacting the distillate of the third column distillation procedure with activated carbon to produce the purified bio-derived 1,3-BG product, the method according to item 25. (Item 36) The method according to item 25, further including, before performing step (c), contacting the second bio-derived 1,3-BG-containing product stream with activated carbon. (Item 37) By the contact with activated carbon, the concentration of 3-hydroxy-butan-al or 4-hydroxy-2-butanone in the second bio-derived 1,3-BG-containing product stream is reduced by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more, the method according to item 25 or 36. (Item 38) The method according to item 25 or 37, further including, before performing step (c), contacting the second bio-derived 1,3-BG-containing product stream with sodium borohydride (NaBH4). (Item 39) By the contact with NaBH4, the UV absorbance of the second bio-derived 1,3-BG-containing product stream at 270 nm or 220 nm is reduced by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more, the method according to item 38. (Item 40) The method according to any one of items 23 to 39, wherein the bio-derived 1,3-BG has a chiral purity of 55% or higher. (Item 41) The method according to any one of items 23 to 40, wherein the purified bio-derived 1,3-BG product has a chemical purity of 99.0% or higher. (Item 42) A system for purifying bio-derived 1,3-BG, comprising A first distillation column that receives a first biological-derived 1,3-BG-containing product stream and produces a first material stream having a boiling point higher than that of 1,3-BG and a second biological-derived 1,3-BG-containing product stream; A second distillation column that receives the second biological-derived 1,3-BG-containing product stream and produces a material stream having a boiling point lower than that of 1,3-BG and a third biological-derived 1,3-BG-containing product stream; and A third distillation column that receives the third 1,3-BG-containing product stream at a supply point and produces a second material stream having a boiling point higher than that of 1,3-BG and a fourth biological-derived 1,3-BG-containing product stream containing a purified biological-derived 1,3-BG product A system comprising. (Item 43) The system according to item 42, wherein the fourth biological-derived 1,3-BG-containing product stream consists essentially of the biological-derived 1,3-BG according to any one of items 1 to 15. (Item 44) The system according to item 42 or 43, comprising a refining column that receives a crude biological-derived 1,3-BG mixture and produces a crude biological-derived 1,3-BG mixture with a reduced salt content. (Item 45) The system according to item 44, wherein the refining column is an ion exchange chromatography column. (Item 46) The system according to any one of items 42 to 45, comprising a dehydration column that receives a crude biological-derived 1,3-BG mixture and produces a material stream having a boiling point lower than that of 1,3-BG and the first biological-derived 1,3-BG-containing product stream. (Item 47) Biological-derived 1,3-BG produced by the method according to any one of items 23 to 39 or by the system according to any one of items 42 to 46.

Brief Description of the Drawings

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Mode for Carrying Out the Invention

[0072] Commercially, 1,3-BG is typically produced by chemically converting acetaldehyde (derived from petroleum or ethanol) to 3-hydroxybutyraldehyde and then reducing it to form petroleum-derived 1,3-BG (“petro-BG”). This chemically produced petro-BG typically forms a racemic mixture of equimolar ratios of the R- and S-enantiomers of 1,3-BG. Methods for isolating each chiral form from petro-BG using 1,3-BG racemates have been disclosed. However, such isolation methods have generally proven to be very inefficient (e.g., enzymatic conversion of racemates) or very costly and difficult to scale up for industrial-scale production (e.g., chiral chromatography).

[0073] The Applicant recognizes that there is still a need for high-purity biologically derived 1,3-BG (“bio-BG”) for use in the cosmetics and food industries. In particular, the Applicant has confirmed that the R-enantiomer of 1,3-BG is required for food, nutraceuticals, pharmaceuticals, and other applications, where the R-enantiomer is generally considered to be more physiologically effective than the S-enantiomer in applications in humans and animals (e.g., livestock or companion animals). In particular, the Applicant has confirmed the need for the R-enantiomer of 1,3-BG having an improved purity profile compared to, for example, typical commercially available petro-BG racemic preparations. A method capable of economically and effectively producing the R-enantiomer of 1,3-BG is needed to produce 1,3-BG on an industrial scale for use in the cosmetics and other industries, such as food or pharmaceutical industries.

[0074] This disclosure is further based in part on the recognition that petro-BG and bio-BG have different odor characteristics and that the different odors of petro-BG and bio-BG are due to the different impurities normally present in petro-BG and bio-BG preparations.

[0075] The present disclosure is further based in part on the recognition that chemically highly pure (e.g., total purity) bio-derived 1,3-BG and bio-derived 1,3-BG enriched or of high chiral purity R-enantiomer may have generally different or favorable odor characteristics or improved physiological properties (e.g., observable in in vitro assays or in vivo) compared to racemic 1,3-BG mixtures or petro-BG (e.g., cosmetic grade or industrial grade).

[0076] Purified bio-BG products, as well as methods and systems for producing such purified bio-BG products, are provided herein.

[0077] In one aspect, bio-derived 1,3-butylene glycol (1,3-BG) (“bio-BG”) is provided. In some embodiments, the bio-derived 1,3-BG has an odor different from that of chemically derived 1,3-BG, such as 1,3-BG derived from the processing of petroleum or acetaldehyde. In some embodiments, the bio-derived 1,3-BG does not have the characteristic off-odor typically found in industrial grade bio-BG. In some embodiments, the bio-derived 1,3-BG has an improved odor compared to petro-BG, as determined, for example, by sensory testing by trained odor panelists. In some embodiments, the improved odor of the bio-BG is characterized as “sweet,” for example, by trained odor panelists. In some embodiments, the bio-derived 1,3-BG is of cosmetic grade. In some embodiments, the cosmetic grade bio-derived 1,3-BG has improved odor characteristics (e.g., a “sweet” odor) compared to petro-BG. In another aspect, a system for purifying bio-derived 1,3-BG is provided herein. In another aspect, a method for purifying bio-derived 1,3-BG is provided herein.

[0078] In some embodiments, the bio-derived 1,3-BG is a racemate or a mixture of the R- and S-enantiomers of 1,3-BG (e.g., CAS No. 107-88-0).

[0079] In some embodiments, the 1,3-BG racemate is an equimolar mixture of the R- and S-enantiomers of 1,3-BG.

[0080] In some embodiments, the 1,3-BG racemate has more R-enantiomers than the S-enantiomer of 1,3-BG. In some embodiments, the 1,3-BG racemate consists essentially of only the R-enantiomer (e.g., >95%, >96%, >97%, >98%, >99%, >99.1%, >99.2%, >99.3%, >99.4%, >99.5%, >99.6%, >99.7%, >99.8%, or >99.9% R-enantiomers). In some embodiments, the biologically-derived 1,3-BG consists essentially of only the R-enantiomer (e.g., 100% enantiomer; CAS No. 6290-03-5), and the S-enantiomer cannot be detected, for example, by GC-MS or LC-MS. In some embodiments, the 1,3-BG racemate is enriched in the R-enantiomer, i.e., it contains more R-enantiomers than S-enantiomers. For example, the 1,3-BG racemate can contain 55% or more R-enantiomers and 45% or less S-enantiomers. For example, the 1,3-BG racemate can contain 60% or more R-enantiomers and 40% or less S-enantiomers. For example, the 1,3-BG racemate can contain 65% or more R-enantiomers and 35% or less S-enantiomers. For example, the 1,3-BG racemate can contain 70% or more R-enantiomers and 30% or less S-enantiomers. For example, the 1,3-BG racemate can contain 75% or more R-enantiomers and 25% or less S-enantiomers. For example, the 1,3-BG racemate can contain 80% or more R-enantiomers and 20% or less S-enantiomers. For example, the 1,3-BG racemate can contain 85% or more R-enantiomers and 15% or less S-enantiomers. For example, the 1,3-BG racemate can contain 90% or more R-enantiomers and 10% or less S-enantiomers. For example, the 1,3-BG racemate can contain 95% or more R-enantiomers and 5% or less S-enantiomers.

[0081] In some preferred embodiments, the bio-derived 1,3-BG is enriched in the R-enantiomer. Thus, even if not explicitly defined, in each case of this disclosure referring to the bio-derived 1,3-BG provided herein, or alternative terms such as bio 1,3-butylene glycol, bio1,3-BG, bio-BG, bio13-BDO, bio1,3-BDO, bio-butylene glycol, or bio1,3-butanediol, the explicitly preferred embodiment is the R-enantiomer. Particularly preferred compositions are of high chiral purity, ≧99% and chemically of high purity, for example ≧99% of the R-enantiomer, and optionally contain certain impurities present at preferred levels or less as described in more detail elsewhere herein. Further compositions provided herein are enriched in the R-enantiomer, for example, containing ≧55% of the R-enantiomer, ≧60% of the R-enantiomer, ≧65% of the R-enantiomer, ≧70% of the R-enantiomer, ≧75% of the R-enantiomer, ≧80% of the R-enantiomer, ≧85% of the R-enantiomer, ≧90% of the R-enantiomer, or ≧95% of the R-enantiomer, and can be of chemically high purity, for example ≧99%, and optionally contain certain impurities present at preferred levels or less as described in more detail elsewhere herein.

[0082] Biologically-derived 1,3-BG, particularly preferably an R-enantiomeric composition, preferably those with high chemical purity and high chiral purity (e.g., ≥95% chemical purity and ≥99% chiral purity, or more preferably ≥99% or >99.5% chemical purity and >99.5% chiral purity) are provided herein, and compositions that are enriched in the R-enantiomer and have high chemical purity and high chiral purity (e.g., ≥95% chemical purity and ≥50% chiral purity, or ≥95% chemical purity and ≥55% chiral purity) can find use in food, dietary supplements, pharmaceuticals, cosmetics, and industrial applications. For example, biologically-derived 1,3-BG can be enzymatically reacted with an acid using lipase, either in vivo or in vitro, to convert the biologically-derived 1,3-BG into an ester. Such esters can have uses in dietary supplements, medicine, and food. In particular, such biologically-derived 1,3-BG esters are advantageous when the chiral ester form containing the R-enantiomer of 1,3-BG is a preferred energy source for humans and animals, and thus when the R-enantiomer of biologically-derived 1,3-BG, or biologically-derived 1,3-BG enriched in the R-enantiomer, is used to form the ester (e.g., as compared to the use of the S-enantiomer, or a racemic mixture of petro-BG prepared, for example, from petroleum or ethanol through a chemical synthesis route of acetaldehyde). Examples include the (R)-3-hydroxybutyl-R-1,3-butanediol monoester of a ketoester, and the (R)-3-hydroxybutyrate glycerol monoester or diester, and the ketoester (R)-3-hydroxybutyl-R-1,3-butanediol monoester has been recognized as generally safe (GRAS approved) by the US Food and Drug Administration (FDA). The ketoester may be delivered orally and releases R-1,3-butylene glycol that can be used in vivo, for example, in the human body.For example, reference is made to WO2013150153(“Ketone Bodies and Ketone Body Esters for Maintaining or Improving Muscle Power Output.”), the entire content of which is incorporated herein by reference. Accordingly, the present disclosure of highly chiral pure and chemically highly pure R-enantiomer compositions of 1,3-BG is particularly useful for applications in the food and pharmaceutical industries. Biologically derived 1,3-BG (e.g., the R-enantiomer of biologically derived 1,3-BG, or biologically derived 1,3-BG enriched in the R-enantiomer) has further food-related applications, including use as a food ingredient, flavoring agent, solvent or solubilizer for flavoring agents, stabilizer, emulsifier, and antibacterial agent, and preservative. Biologically derived 1,3-BG (e.g., the R-enantiomer of biologically derived 1,3-BG, or biologically derived 1,3-BG enriched in the R-enantiomer) can also be used as a parenteral drug solvent in the pharmaceutical industry. Furthermore, biologically derived 1,3-BG (e.g., the R-enantiomer of biologically derived 1,3-BG, or biologically derived 1,3-BG enriched in the R-enantiomer) has been found to be used as a component such as a skin softening agent, humectant, additive capable of preventing crystallization of insoluble components, solubilizer for poorly water-soluble components such as fragrances, and antibacterial agent and preservative in cosmetics. For example, biologically derived 1,3-BG (e.g., the R-enantiomer of biologically derived 1,3-BG, or biologically derived 1,3-BG enriched in the R-enantiomer) can be used particularly as a humectant in hairsprays and setting lotions. Biologically derived 1,3-BG (e.g., the R-enantiomer of biologically derived 1,3-BG, or biologically derived 1,3-BG enriched in the R-enantiomer) can reduce the loss of fragrance from essential oils, protect against spoilage by microorganisms, and be used as a solvent for benzoates. Biologically derived 1,3-BG can be used, for example, at concentrations ranging from 0.1% or less to 50% or higher.Biologically-derived 1,3-BG (e.g., the R-enantiomer of biologically-derived 1,3-BG, or biologically-derived 1,3-BG enriched in the R-enantiomer) can be used in hair and bath products, eye and facial makeup, fragrances, personal cleansing products, and shaving and skin care preparations. For example, see Cosmetic Ingredient Review Board Report: 「Final Report on the Safety Assessment of Butylene Glycol, Hexylene Glycol,Ethoxy diglycol,and。 Dipropylene Glycol」, Journal of the American College of Toxicology, Volume 4, Number 5, 1985 (the 「Report」). This Report, which is hereby incorporated by reference in its entirety, provides the concentrations of butylene glycol in specific uses and cosmetics. For example, see Report, Table 2 (「Product Formulation Data」). Although the Report describes the use of the petro-BG racemate, biologically-derived 1,3-BG, particularly the R-enantiomer enriched preparation provided herein, is expected to be a superior product to the petro-BG racemate due to at least an improved purity profile and favorable odor characteristics.

[0083] As used herein, the term "crude bioderived 1,3-BG mixture" means a mixture of bioderived 1,3-BG, about 50% to 90% thereof, and water, 50% to 1%, and one or more other impurities derived from the fermentation process, or including these. In some embodiments, the crude bioderived 1,3-BG mixture is about 75% to 85% or more of 1,3-BG, 1% to 25% water, and one or more other impurities derived from the fermentation process. In some embodiments, the crude bioderived 1,3-BG mixture is about 80% to 85% of 1,3-BG, 1% to 20% water, and one or more other impurities derived from the fermentation process. The crude bioderived 1,3-BG mixture can be, or can include, a mixture containing partially purified bioderived 1,3-BG, e.g., bioderived 1,3-BG that has been partially purified using one or more methods.

[0084] As used herein, the term "bioderived 1,3-BG-containing product stream" means a material that concludes a procedure and includes a majority of the bioderived 1,3-BG for which the procedure was conducted.

[0085] As used herein, the term "bioderived 1,3-BG product" means a mixture that contains bioderived 1,3-BG and for which at least one procedure has been conducted to increase the content of bioderived 1,3-BG or to decrease the content of impurities. The term bioderived 1,3-BG product can include a crude bioderived 1,3-BG mixture or partially purified bioderived 1,3-BG, but the bioderived 1,3-BG and water content of the bioderived 1,3-BG product can be higher or lower than that of the crude bioderived 1,3-BG mixture or the partially purified bioderived 1,3-BG.

[0086] As used herein, the term "biologically-derived 1,3-BG in fermentation broth" means a fermentation broth containing biologically-derived 1,3-BG, which is produced by culturing a non-naturally occurring microorganism capable of producing biologically-derived 1,3-BG in a suitable culture medium. The terms "biologically-derived 1,3-BG" and "bio-BG" are used interchangeably herein.

[0087] As used herein, the term "biologically derived" means that which is produced from or synthesized by a biological organism and can be considered a renewable resource because it can be produced by a biological organism. Such biological organisms, particularly microbial organisms for use in the compositions, systems, and methods provided and disclosed herein, can utilize raw materials or biomass such as sugars or carbohydrates, preferably dextrose or glucose, obtained from agricultural, plant, bacterial, or animal sources; or other renewable sources such as synthesis gas (CO, CO2 and / or H2). Coal products can also be used as a carbon source for biological organisms to synthesize bio-based products such as those provided herein. Alternatively, biological organisms can utilize carbon in the atmosphere. As used herein, the term "bio-based" means a product as described above that is wholly or partially composed of biologically derived compounds provided herein. Bio-based or biologically derived products are in contrast to petroleum-derived products, which are derived from petroleum or petrochemical raw materials or are chemically synthesized. Preferred microbial pathways to biologically derived 1,3-BG are described, for example, in WO2010127319A2, the entire content of which is incorporated herein by reference. In particular, WO2010127319A2 describes biosynthetic pathways including 3-hydroxybutyryl-CoA dehydrogenase, such as the pathway from acetoacetyl-CoA to 1,3-butanediol (see, for example, Figure 2, step H). In one embodiment, 3-hydroxybutyryl-CoA dehydrogenase is modified to have specificity for the R enantiomer.Also mentioned in the following provisional applications, which are hereby incorporated by reference in their entirety: (1) U.S. Patent Provisional Application No. 62 / 480,208, filed March 31, 2017, entitled "3-HYDROXYBUTYRYL-COA DEHYDROGENASE VARIANTS AND METHODS OF USE" (Attorney Docket No. 12956-409-888); (2) U.S. Patent Provisional Application No. 62 / 480,194, filed March 31, 2017, entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE" (Attorney Docket No. 12956-408-888); (3) International Patent Application No. _, filed on the same date as this application, entitled "3-HYDROXYBUTYRYL-COA DEHYDROGENASE VARIANTS AND METHODS OF USE" (Attorney Docket No. 12956-409-228); and (4) International Patent Application No. _, filed on the same date as this application, entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE" (Attorney Docket No. 12956-408-228).

[0088] As used herein, the term "detectable level" means the level of an analyte (e.g., 1,3 - BG or an impurity in a 1,3 - BG product) that can be detected using an analytical method above the background observed using the analytical method in the absence of the analyte. The analytical method can include detection by an analytical device or instrument, e.g., GC - MS, LC - MS, or sensory detection by an individual, e.g., olfactory detection or characterization of an analyte by a trained person or a group of trained persons. The detectable level can be qualitative (e.g., the analyte is determined to be "present" or "absent" in the sample) or quantitative (e.g., the analyte is determined to be present in the sample at, e.g., 100 ppm on a weight basis). In some embodiments, an analyte is at a detectable level if it produces a signal intensity that is 2σ - or higher or 3σ - or higher above the background noise observed in the absence of the analyte, e.g., the background noise observed in a GC - MS assay or an LC - MS assay (e.g., total ion current (TIC) or extracted ion current (XIC)).

[0089] As used herein, the term "low level" means that the analyte is present at a level close to the detection limit of the analytical method, e.g., less than 5σ, less than 4σ, or less than 3σ, above the background noise observed using the analytical method in the absence of the analyte.

[0090] As used herein, the term "light matter" refers to compounds in a 1,3 - BG sample (e.g., a bio - BG or petro - BG sample) that elute with a retention time earlier than 1,3 - BG in, for example, a GC - MS chromatogram or an LC - MS chromatogram.

[0091] As used herein, the term "heavy matter" refers to compounds in a 1,3 - BG sample (e.g., a bio - BG or petro - BG sample) that elute with a retention time later than 1,3 - BG in, for example, a GC - MS chromatogram or an LC - MS chromatogram.

[0092] As used herein, the term "purity" refers to either, or both, chemical purity or chiral purity.

[0093] As used herein, the term "chiral purity" means, for example, the fraction of enantiomers (e.g., R-enantiomer or S-enantiomer) in a racemic mixture of 1,3-BG. For example, in a bio-derived 1,3-BG with a chiral purity of 99%, 99% of the 1,3-BG molecules may be the R-enantiomer and 1% of the 1,3-BG molecules may be the S-enantiomer, or vice versa. A bio-derived 1,3-BG with a chiral purity of 99% can have any chemical purity. For example, a bio-derived 1,3-BG with a chiral purity of 99% can have a chemical purity of 95% (e.g., on a weight basis). A bio-derived 1,3-BG with a chiral purity of 99%, i.e., a chemical purity of 95%, may contain, for example, 95% 1,3-BG (e.g., on a weight basis) of the R-enantiomer and / or S-enantiomer 1,3-BG, as well as 5% of other contaminating substances such as "heavy bio-BG" and "light bio-BG", which may also be referred to as "heavy matter" or "light matter", respectively.

[0094] As used herein, the term "chemical purity" means, for example, the fraction of 1,3-BG in a 1,3-BG composition (e.g., on a weight basis). For example, 1,3-BG with a chemical purity of 95% can have 95% 1,3-BG (e.g., on a weight basis) and 5% of other contaminating substances such as "heavy matter" or "light matter". 1,3-BG with a chemical purity of 95% can have any chiral purity. For example, 1,3-BG with a chemical purity of 95% can have a chiral purity of 99%, e.g., having 99% 1,3-BG in the R-enantiomeric form and 1% 1,3-BG in the S-enantiomeric form.

[0095] In some embodiments, the bio-derived 1,3-BG has a purity level (e.g., chemical or chiral purity, or both chemical and chiral purity) of at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% on a weight / weight basis. In some embodiments, the bio-derived 1,3-BG has a purity level (e.g., chemical or chiral purity, or both chemical and chiral purity) of at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%. In some embodiments, the bio-derived 1,3-BG has a purity level (e.g., chemical or chiral purity, or both chemical and chiral purity) of at least 99.0%, at least 99.1%, at least 99.2%, at least 99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, or at least 99.9%.

[0096] In some embodiments, the bioderived 1,3-BG has a chemical purity of 99.0% (e.g., 99.1, 99.2, 99.3, 99.4, 99.5, 99.6, 99.7, 99.8, 99.9% or higher). In some embodiments, the bioderived 1,3-BG has less than 0.5% water. In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 55.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 60.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 65.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 70.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 75.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 80.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 85.0% or higher (e.g., R-enantiomer). In some embodiments, the chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 90.0% or higher (e.g., R-enantiomer).

[0097] In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 95.0% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 96.0% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 97.0% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 98.0% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.0% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.1% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.2% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.3% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.4% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.5% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.6% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.7% or higher (e.g., the R-enantiomer).In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.8% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 99.9% or higher (e.g., the R-enantiomer). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher consists essentially of only the R-enantiomer, and the S-enantiomer is not detectable, for example, by GC-MS or LC-MS. In another embodiment, chemically pure 1,3-BG that is 99.0% or higher is enriched in the R-enantiomer, for example, containing 45% or less of the S-enantiomer, 40% or less of the S-enantiomer, 35% or less of the S-enantiomer, 30% or less of the S-enantiomer, 25% or less of the S-enantiomer, 20% or less of the S-enantiomer, 15% or less of the S-enantiomer, 10% or less of the S-enantiomer, or 5% or less of the S-enantiomer.

[0098] In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 95% or higher (e.g., 96% or higher, 97% or higher, 98% or higher, 99.0% or higher, 99.1% or higher, 99.2% or higher; e.g., the R-enantiomer), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of 1 ppm to 1000 ppm (e.g., in the range of 1 ppm to 900 ppm, in the range of 1 ppm to 800 ppm, in the range of 1 ppm to 700 ppm, in the range of 1 ppm to 600 ppm, in the range of 1 ppm to 500 ppm, in the range of 1 ppm to 400 ppm, in the range of 1 to 300 ppm, in the range of 1 to 200 ppm, in the range of 1 to 100 ppm, in the range of 1 to 90 ppm, in the range of 1 to 80 ppm, in the range of 1 to 70 ppm, in the range of 1 to 60 ppm, in the range of 1 to 50 ppm, in the range of 1 to 40 ppm, in the range of 1 to 30 ppm, in the range of 1 to 20 ppm, or in the range of 1 to 10 ppm). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 95% or higher (e.g., 96% or higher, 97% or higher, 98% or higher, 99.0% or higher, 99.1 or higher, 99.2% or higher), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of 1 ppm to 400 ppm. In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 95% or higher (e.g., 96% or higher, 97% or higher, 98% or higher, 99.0% or higher, 99.1 or higher, 99.2% or higher), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of 1 ppm to less than 400 ppm.

[0099] In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 55% or higher (e.g., 60% or higher, 70% or higher, 75% or higher, 80% or higher, 85% or higher, 90% or higher; e.g., the R-enantiomer), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of 1 ppm to 1000 ppm (e.g., in the range of 1 ppm to 900 ppm, in the range of 1 ppm to 800 ppm, in the range of 1 ppm to 700 ppm, in the range of 1 ppm to 600 ppm, in the range of 1 ppm to 500 ppm, in the range of 1 ppm to 400 ppm, between 1 and 300 ppm, between 1 and 200 ppm, between 1 and 100 ppm, between 1 and 90 ppm, between 1 and 80 ppm, between 1 and 70 ppm, between 1 and 60 ppm, between 1 and 50 ppm, between 1 and 40 ppm, between 1 and 30 ppm, between 1 and 20 ppm, or between 1 and 10 ppm). In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 55% or higher (e.g., 60% or higher, 70% or higher, 75% or higher, 80% or higher, 85% or higher, 90% or higher; e.g., the R-enantiomer), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of 1 ppm to 400 ppm. In some embodiments, chemically pure 1,3-BG that is 99.0% or higher has a chiral purity of 55% or higher (e.g., 60% or higher, 70% or higher, 75% or higher, 80% or higher, 85% or higher, 90% or higher; e.g., the R-enantiomer), and has one or both of 3-hydroxy-butanals and 4-hydroxy-2-butanones in the range of less than 1 ppm to 400 ppm.

[0100] In some embodiments, the bio-derived 1,3-BG has a higher purity level (e.g., chemical or chiral purity, or both chemical and chiral purity) than industrial-grade or cosmetic-grade bio-BG. In some embodiments, the bio-derived 1,3-BG has a purity level that is approximately the same (e.g., a purity level within ±0.5%) as industrial-grade or cosmetic-grade bio-BG. In some embodiments, the bio-derived 1,3-BG has a lower purity level than industrial-grade or cosmetic-grade bio-BG.

[0101] In some embodiments, the bio-derived 1,3-BG has a higher purity (e.g., chemical or chiral purity, or both chemical and chiral purity) than industrial-grade or cosmetic-grade petro-BG. In some embodiments, the bio-derived 1,3-BG has a purity level that is approximately the same (e.g., a purity level within ±0.5%) as industrial-grade or cosmetic-grade petro-BG. In some embodiments, the bio-derived 1,3-BG has a lower purity level than industrial-grade or cosmetic-grade petro-BG.

[0102] In some embodiments, the bio-derived 1,3-BG has more R-enantiomers than S-enantiomers, and thus is enriched in R-enantiomers. In some embodiments, the bio-derived 1,3-BG having a higher level of R-enantiomers than S-enantiomers has, for example, a chiral purity level of at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% on a weight / weight basis. In some embodiments, the bio-derived 1,3-BG having a higher level of R-enantiomers than S-enantiomers has a chiral purity level of at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%. In some embodiments, the bio-derived 1,3-BG having a higher level of R-enantiomers than S-enantiomers has a chiral purity level of at least 99.0%, at least 99.1%, at least 99.2%, at least 99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, or at least 99.9%.

[0103] In some embodiments, the bio-derived 1,3-BG has more S-enantiomers than R-enantiomers, and thus is enriched in S-enantiomers. In some embodiments, the bio-derived 1,3-BG having a higher level of S-enantiomers than R-enantiomers has, for example, a chiral purity level of at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% on a weight / weight basis. In some embodiments, the bio-derived 1,3-BG having a higher level of S-enantiomers than R-enantiomers has a chiral purity level of at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%. In some embodiments, the bio-derived 1,3-BG having a higher level of S-enantiomers than R-enantiomers has a chiral purity level of at least 99.0%, at least 99.1%, at least 99.2%, at least 99.3%, at least 99.4%, at least 99.5%, at least 99.6%, at least 99.7%, at least 99.8%, or at least 99.9%.

[0104] In some embodiments, the bio-derived 1,3-BG has a higher chiral purity level (e.g., a higher level of R-enantiomers) than industrial-grade or cosmetic-grade bio-BG. In some embodiments, the bio-derived 1,3-BG has a chiral purity level (e.g., R-enantiomer level) that is approximately the same as that of industrial-grade or cosmetic-grade bio-BG (e.g., within ±0.5% of the chiral purity level, e.g., R-enantiomer level).

[0105] In some embodiments, the bio-derived 1,3-BG has a higher chiral purity level (e.g., a higher level of R-enantiomers) than industrial-grade or cosmetic-grade petro-BG. In some embodiments, the bio-derived 1,3-BG has a chiral purity level (e.g., a higher level of R-enantiomers) that is approximately the same as that of industrial-grade or cosmetic-grade petro-BG (e.g., within ±0.5% of the purity level).

[0106] In some embodiments, the bio-derived 1,3-BG has one or more contaminating substances at detectable levels, which cannot be detected in petro-BG or are present at higher or lower levels in bio-derived 1,3-BG compared to petro-BG (e.g., industrial grade or cosmetic grade). In some embodiments, the contaminant levels in bio-derived 1,3-BG are detectable, for example, by a perceptual analysis performed by a trained person. In some embodiments, the contaminant levels are detectable in bio-derived by their relative signal intensities in a GC-MS chromatogram or an LC-MS chromatogram (e.g., total ion current (TIC), extracted ion current (XIC)). In some embodiments, the bio-derived 1,3-BG has one or more contaminating substances at detectable levels, which cannot be detected in industrial petro-BG or are present at higher or lower levels in bio-derived 1,3-BG compared to industrial grade petro-BG. In some embodiments, the bio-derived 1,3-BG has one or more contaminating substances at detectable levels, which cannot be detected in cosmetic grade petro-BG or are present at higher or lower levels in bio-BG compared to cosmetic grade petro-BG.

[0107] In some embodiments, the bio-derived 1,3-BG has two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more contaminating substances at detectable levels, which cannot be detected in petro-BG (e.g., cosmetic grade or industrial grade petro-BG) or are present at higher levels in bio-derived 1,3-BG compared to petro-BG.

[0108] In some embodiments, the bio-derived 1,3-BG has two or more, three or more, four or more, five or more, six or more, seven or more, eight or more, nine or more, or ten or more detectable levels of contaminants, which are present at low levels in the bio-derived 1,3-BG compared to petro-BG.

[0109] In some embodiments, the bio-derived 1,3-BG has levels of one or more contaminants that are at least two times, at least three times, at least four times, at least five times, at least six times, at least seven times, at least eight times, at least nine times, at least ten times, at least twelve times, at least fifteen times, at least twenty times, at least thirty times, at least forty times, at least fifty times, at least sixty times, at least seventy times, at least eighty times, at least ninety times, at least one hundred times, at least one hundred and fifty times, at least two hundred times, at least three hundred times, at least four hundred times, at least five hundred times, at least six hundred times, at least seven hundred times, at least eight hundred times, at least nine hundred times, or at least one thousand times higher (e.g., in weight / weight percent) than the concentration of contaminants in petro-BG (e.g., industrial grade or cosmetic grade petro-BG).

[0110] In some embodiments, the concentration of the contaminant in the bio-derived 1,3-BG is at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, at least 10 times, at least 12 times, at least 15 times, at least 20 times, at least 30 times, at least 40 times, at least 50 times, at least 60 times, at least 70 times, at least 80 times, at least 90 times, at least 100 times, at least 150 times, at least 200 times, at least 300 times, at least 400 times, at least 500 times, at least 600 times, at least 700 times, at least 800 times, at least 900 times, or at least 1,000 times lower than the concentration of the contaminant in petro-BG (e.g., industrial grade or cosmetic grade petro-BG), i.e., the level of one or more contaminants is present at such a low concentration (e.g., in weight / weight percent).

[0111] In some embodiments, the level of the detectable contaminant in the bio-derived 1,3-BG that is not detectable in petro-BG or is present at a higher level in the bio-derived 1,3-BG compared to petro-BG is less than 10,000 ppm, less than 9,000 ppm, less than 8,000 ppm, less than 7,000 ppm, less than 6,000 ppm, less than 5,000 ppm, less than 4,000 ppm, less than 3,000 ppm, less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm in the bio-derived 1,3-BG.

[0112] In some embodiments, the level of detectable contaminants in bio-based 1,3-BG that are present at lower levels in bio-based 1,3-BG compared to petro-BG is less than 10,000 ppm, less than 9,000 ppm, less than 8,000 ppm, less than 7,000 ppm, less than 6,000 ppm, less than 5,000 ppm, less than 4,000 ppm, less than 3,000 ppm, less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm in bio-based 1,3-BG.

[0113] In some embodiments, the level of detectable contaminants in bio-based 1,3-BG that are not detectable in petro-BG or are present at higher levels in bio-based 1,3-BG compared to petro-BG is 25 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, 2,000 ppm or higher, 3,000 ppm or higher, 4,000 ppm or higher, 5,000 ppm or higher, 6,000 ppm or higher, 7,000 ppm or higher, 8,000 ppm or higher, 9,000 ppm or higher, 10,000 ppm or higher in bio-based 1,3-BG.

[0114] In some embodiments, the level of detectable contaminants in bio-based 1,3-BG that are present at lower levels in bio-based 1,3-BG compared to petro-BG is 25 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, 2,000 ppm or higher, 3,000 ppm or higher, 4,000 ppm or higher, 5,000 ppm or higher, 6,000 ppm or higher, 7,000 ppm or higher, 8,000 ppm or higher, 9,000 ppm or higher, 10,000 ppm or higher in bio-based 1,3-BG.

[0115] In some embodiments, the level of detectable contaminants in bio-based 1,3-BG that are not detectable in petro-BG or are present at higher levels in bio-based 1,3-BG compared to petro-BG is less than 25 ppm, less than 50 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, or at undetectable levels in petro-BG (e.g., cosmetic grade or industrial grade).

[0116] In some embodiments, the level of detectable contaminants in bio-based 1,3-BG that are present at lower levels in bio-based 1,3-BG compared to petro-BG is less than 25 ppm, less than 50 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, or at undetectable levels in petro-BG (e.g., cosmetic grade or industrial grade).

[0117] In some embodiments, the contaminant is present in bio-based 1,3-BG at a level of 25 ppm or higher (e.g., 25 ppm or higher, 50 ppm or higher, 100 ppm, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, 2,000 ppm or higher, 3,000 ppm or higher, 4,000 ppm or higher, 5,000 ppm or higher, 6,000 ppm or higher, 7,000 ppm or higher, 8,000 ppm or higher, 9,000 ppm or higher, or 10,000 ppm or higher), and the contaminant is present in petro-BG (e.g., industrial grade or cosmetic grade) at a level of less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, or at undetectable levels.

[0118] In some embodiments, the contaminant is present in petro - BG at a level of 25 ppm or higher (e.g., 25 ppm or higher, 50 ppm or higher, 100 ppm, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, 2,000 ppm or higher, 3,000 ppm or higher, 4,000 ppm or higher, 5,000 ppm or higher, 6,000 ppm or higher, 7,000 ppm or higher, 8,000 ppm or higher, 9,000 ppm or higher, or 10,000 ppm or higher), and the contaminant is present in bio - derived 1,3 - BG (e.g., industrial grade or cosmetic grade) at a level less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, or at a non - detectable level.

[0119] In some embodiments, the level of the contaminant in bio - derived 1,3 - BG that is not detectable in petro - BG or is present at a higher level in bio - derived 1,3 - BG compared to petro - BG is less than 10,000 ppm, less than 9,000 ppm, less than 8,000 ppm, less than 7,000 ppm, less than 6,000 ppm, less than 5,000 ppm, less than 4,000 ppm, less than 3,000 ppm, less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm.

[0120] In some embodiments, the level of contaminants in bio-based 1,3-BG that are present at lower levels in bio-based 1,3-BG compared to petro-BG is less than 10,000 ppm, less than 9,000 ppm, less than 8,000 ppm, less than 7,000 ppm, less than 6,000 ppm, less than 5,000 ppm, less than 4,000 ppm, less than 3,000 ppm, less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm.

[0121] In some embodiments, detectable contaminants in bio-based 1,3-BG that are not detectable in petro-BG (e.g., industrial grade or cosmetic grade), or are present at high levels in bio-based 1,3-BG compared to petro-BG, or are present at low levels in bio-based 1,3-BG compared to petro-BG, may include 3-hydroxy-butan-al, 4-hydroxy-2-butanone, 4-(3-hydroxybutoxy)butan-2-one (proposed structure, also referred to herein as 3-hydroxy-butyl-3-oxo-butane ether (proposed structure) or "Compound 7"; see also Table 5) and 4-((4-hydroxybutan-2-yl)oxy)-butan-2-one (proposed structure, also referred to herein as 2-methyl-3-hydroxy-propyl-3-oxo-butane ether (proposed structure) or "Compound 9"; see also Table 5), or combinations thereof.

[0122] In some embodiments, an impurity detectable in bio-based 1,3-BG that cannot be detected in petro-BG (e.g., industrial grade or cosmetic grade), or is present at high levels in bio-based 1,3-BG compared to petro-BG, or is present at low levels in bio-based 1,3-BG compared to petro-BG, can be 3-hydroxy-butan-al. For example, see FIGS. 1 and 2. In some embodiments, the bio-based 1,3-BG has a 3-hydroxy-butan-al level of less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm. In some embodiments, the bio-based 1,3-BG has a 3-hydroxy-butan-al level of 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, or 1,000 ppm or higher.

[0123] In some embodiments, an impurity detectable in bio-based 1,3-BG that cannot be detected in petro-BG (e.g., industrial grade or cosmetic grade), or is present at high levels in bio-based 1,3-BG compared to petro-BG, or is present at low levels in bio-based 1,3-BG compared to petro-BG, can be 4-hydroxy-2-butanone. For example, see FIGS. 1 and 2. In some embodiments, the bio-based 1,3-BG has a 4-hydroxy-2-butanone level of less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm. In some embodiments, the bio-based 1,3-BG has a 4-hydroxy-2-butanone level of 25 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, or 1,000 ppm or higher.

[0124] In some embodiments, an impurity detectable in bio-based 1,3-BG that cannot be detected in petro-BG (e.g., industrial grade or cosmetic grade), or that is present at high levels in bio-based 1,3-BG compared to petro-BG, or that is present at low levels in bio-based 1,3-BG compared to petro-BG, may be Compound 7. For example, see Figure 2. In some embodiments, bio-based 1,3-BG has a Compound 7 level of less than 2,000 ppm, less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm. In some embodiments, bio-based 1,3-BG has a Compound 7 level of 25 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, 1,500 ppm or higher, or 2,000 ppm or higher.

[0125] In some embodiments, an impurity detectable in bio-based 1,3-BG that cannot be detected in petro-BG (e.g., industrial grade or cosmetic grade), or that is present at high levels in bio-based 1,3-BG compared to petro-BG, or that is present at low levels in bio-based 1,3-BG compared to petro-BG, may be a compound characterized by the mass spectrum according to Figure 3. In Figure 3, the proposed explanations for certain mass fragments are not intended to be limiting.

[0126] In some embodiments, contaminants that are detectable in bio-derived 1,3-BG, not detectable in petro-BG (e.g., industrial grade or cosmetic grade), present at high levels in bio-derived 1,3-BG compared to petro-BG, or present at low concentrations in bio-derived 1,3-BG compared to petro-BG, are detectable in a GC-MS chromatogram (e.g., total ion current (TIC)) as peaks eluting at a relative retention time between 0.97 and 0.99 (e.g., 0.97; 0.98; 0.99) when the relative retention time of 1,3-BG is set to 1.0. See, for example, FIG. 2 (RT Compound 7 = 12.05 minutes; RT 1,3-BG = 11.85 minutes; see also Table 5).

[0127] In some embodiments, a contaminant that is detectable in bio-derived 1,3-BG, not detectable in petro-BG (e.g., industrial grade or cosmetic grade), present at high levels in bio-derived 1,3-BG compared to petro-BG, or present at low levels in bio-derived 1,3-BG compared to petro-BG, can be Compound 9. See, for example, FIG. 2. In some embodiments, bio-derived 1,3-BG has a Compound 9 level of less than 1,500 ppm, less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, or less than 25 ppm. In some embodiments, bio-derived 1,3-BG has a Compound 9 level of 25 ppm or higher, 50 ppm or higher, 100 ppm or higher, 200 ppm or higher, 300 ppm or higher, 400 ppm or higher, 500 ppm or higher, 600 ppm or higher, 700 ppm or higher, 800 ppm or higher, 900 ppm or higher, 1,000 ppm or higher, or 1,500 ppm or higher.

[0128] In some embodiments, contaminants that are detectable in bio-based 1,3-BG and not detectable in petro-BG (e.g., industrial grade or cosmetic grade), or are present at high levels in bio-based 1,3-BG compared to petro-BG, or are present at low levels in bio-based 1,3-BG compared to petro-BG, may include compounds characterized by the mass spectrum according to FIG. 4. In FIG. 4, the proposed explanations for certain mass fragments are not intended to be limiting.

[0129] In some embodiments, contaminants that are detectable in bio-based 1,3-BG and not detectable in petro-BG (e.g., industrial grade or cosmetic grade), or are present at high levels in bio-based 1,3-BG compared to petro-BG, or are present at low levels in bio-based 1,3-BG compared to petro-BG, are detectable in a GC-MS chromatogram (e.g., total ion current (TIC)) as peaks eluting at a relative retention time between 0.94 and 0.96 (e.g., 0.94; 0.95; 0.96) when the relative retention time of 1,3-BG is set to 1.0. See, for example, FIG. 2 (RT Compound 9 = 12.51 minutes; RT 1,3-BG = 11.85 minutes; see also Table 5).

[0130] In some embodiments, contaminants that are detectable in bio-based 1,3-BG and not detectable in petro-BG (e.g., industrial grade or cosmetic grade), or are present at high levels in bio-based 1,3-BG compared to petro-BG, or are present at low levels in bio-based 1,3-BG compared to petro-BG, are detectable in an LC-MS chromatogram (e.g., extracted ion current (XIC)) as peaks eluting at a relative retention time between 0.45 and 0.55 (e.g., 0.94; 0.95; 0.96) when the relative retention time of 1,3-BG is set to 1.0. See, for example, FIG. 8A (RT Compound = 6.0 minutes to 6.7 minutes; RT 1,3-BG = 3.08 minutes; see also Table 5).

[0131] In some embodiments, contaminants that are detectable in bio-derived 1,3-BG, undetectable in petro-BG (e.g., industrial grade or cosmetic grade), or present at high levels in bio-derived 1,3-BG compared to petro-BG, or present at low levels in bio-derived 1,3-BG compared to petro-BG, are C8H 16 O3 and have an elemental composition and a molecular weight of 160. See, for example, FIG. 8B. In FIG. 8B, the proposed explanations of certain mass fragments are not intended to be limiting.

[0132] In some embodiments, contaminants that are detectable in bio-derived 1,3-BG, undetectable in petro-BG (e.g., industrial grade or cosmetic grade), or present at high levels in bio-derived 1,3-BG compared to petro-BG are characterized by the mass spectrum according to FIG. 8B.

[0133] In some embodiments, in the bio-derived 1,3-BG provided herein, fewer "heavy" contaminant substances are detectable by GC-MS compared to petro-BG (e.g., industrial grade or cosmetic grade), while the "heavy" contaminant substances elute at a relative retention time between 0.8 and 0.95 when the relative retention time of 1,3-BG is set to 1.0. See, for example, FIG. 2.

[0134] In some embodiments, the bio-derived 1,3-BG has overall lower levels of "heavy" contaminating substances than petro-BG (e.g., industrial grade or cosmetic grade). In some embodiments, the bio-derived 1,3-BG has overall lower levels of "light" contaminating substances than petro-BG. In some embodiments, the bio-derived 1,3-BG has overall lower levels of both "heavy" and "light" contaminating substances than petro-BG. In some embodiments, the total purity of the bio-derived 1,3-BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher), and the total level of heavy contaminating substances is 1.0% or less (e.g., 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or less). In some embodiments, the total purity of the bio-derived 1,3-BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher), and the total level of light contaminating substances is 1.0% or less (e.g., 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or less). In some embodiments, the total purity of the bio-derived 1,3-BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher), the total level of heavy contaminating substances is 0.8% or less (e.g., 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or less), and the total level of light contaminating substances is 0.2% or less (e.g., 0.2%, 0.1%, 0.0%). See, for example, Table 3.

[0135] Preferably, in all embodiments herein, the light and heavy impurities present in bio - BG are at lower total levels, or each is at a lower level, than those in industrial or cosmetic grade petro - BG.

[0136] In some embodiments, the total chiral purity (e.g., R - enantiomer level) of bio - derived 1,3 - BG is 55% or higher (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or higher). In some embodiments, the total chiral purity (e.g., R - enantiomer level) of bio - derived 1,3 - BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher), preferably 99.5% or higher. In preferred embodiments, the total chiral purity (e.g., R - enantiomer level) of bio - derived 1,3 - BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher), preferably 99.5% or higher, and the total chemical purity of bio - derived 1,3 - BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher). In some embodiments, the total chiral purity (e.g., R - enantiomer level) of bio - derived 1,3 - BG is 55% or higher (e.g., 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or higher), and the total chemical purity of bio - derived 1,3 - BG is 99% or higher (e.g., 99.0%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or higher).

[0137] In some embodiments, the bio-derived 1,3-BG has a UV absorbance between 220 nm and 260 nm that is at least 2 times, at least 3 times, at least 4 times, at least 5 times, at least 6 times, at least 7 times, at least 8 times, at least 9 times, or at least 10 times lower than the UV absorbance of petro-BG (e.g., cosmetic grade or industrial grade).

[0138] In some embodiments, the bio-derived 1,3-BG does not have a detectable level of 1,4-(4-methyl-1,3-dioxan-2-yl)propan-2-one, or has a lower level of 1,4-(4-methyl-1,3-dioxan-2-yl)propan-2-one than petro-BG, as determined by, for example, LC-MS (e.g., extracted ion current (XIC)). See, for example, Table 6, FIGS. 9A and 9B. In FIG. 9B, the proposed explanations for certain mass fragments are not intended to be limiting.

[0139] In some embodiments, the bio-derived 1,3-BG does not have, at a detectable level, contaminants eluting in the LC-MS chromatogram with a relative retention time between 0.40 and 0.43 when the relative retention time of 1,3-BG is set to 1.0, or has a lower level than petro-BG. See, for example, FIG. 9A (RT compound = 7.31 min to 7.33 min; RT 1,3-BG = 3.05 min; see also Table 6).

[0140] In some embodiments, the bio-derived 1,3-BG does not have, at a detectable level, contaminants having an elemental composition of C8H 14 O3 and a molecular weight of 158, or has a lower level than petro-BG. See, for example, FIG. 9B.

[0141] In some embodiments, the bio-derived 1,3-BG does not have, at a detectable level, contaminants characterized by the mass spectrum according to FIG. 9B, or has a lower level than petro-BG.

[0142] In some embodiments, the level of contaminating substances that cannot be detected in bio-derived 1,3-BG or are present at a lower level than petro-BG in bio-derived 1,3-BG is at least 2-fold, at least 3-fold, at least 4-fold, at least 5-fold, at least 6-fold, at least 7-fold, at least 8-fold, at least 9-fold, or at least 10-fold lower than petro-BG in bio-derived 1,3-BG.

[0143] In some embodiments, bio-derived 1,3-BG does not have, or has only at low levels, compounds characterized as having a "sharp", "fecal", "oily", "sweet", or "moldy" odor as observed in cosmetic-grade petro-BG and as determined, for example, by a sensory odor panel composed of trained individuals. See, for example, Example 3. In some embodiments, the compounds observed in cosmetic-grade petro-BG correspond to the compounds identified between 17.60 minutes and 25.40 minutes in the GCMS-O analysis shown in FIG. 11.

[0144] In some embodiments, the odor of the bio-derived 1,3-BG provided herein is predominantly classified by the majority of the members of the sensory odor panel as mildly sweet, oily, fruity, or combinations thereof.

[0145] In some embodiments, the odor of the bio-derived 1,3-BG provided herein is not predominantly classified by the majority of the members of the sensory odor panel as oily, paint-like, glue-like, or combinations thereof.

[0146] In some embodiments, it is observed at a retention time (RT) longer than that of 1,3-BG by GC-MS analysis that the fraction containing the compounds responsible for the odor in bio-derived 1,3-BG is less than that in cosmetic-grade petro-BG. See, for example, Example 3.

[0147] In some embodiments, the cosmetic-grade petro-BG includes GC fractions having a sweet (e.g., 5 or more fractions), musty (e.g., 4 or more fractions), fruity (e.g., 1 or more fractions), oily (e.g., 3 or more fractions), citrusy (e.g., 1 or more fractions), soil (e.g., 1 or more fractions), aldehyde (e.g., 1 or more fractions), sharp (e.g., 1 or more fractions), or fecal (e.g., 1 or more fractions) odor, or combinations thereof.

[0148] In some embodiments, the bio-based 1,3-BG includes GC fractions having a sweet (e.g., 6 or fewer fractions), musty (e.g., 6 or fewer fractions), oily (e.g., 4 or fewer fractions), aldehyde (e.g., 1 or fewer fractions), sharp (e.g., 2 or fewer fractions), buttery (e.g., 1 or fewer fractions), solvent (e.g., 1 or fewer fractions), or unknown (e.g., 1 or fewer fractions) odor, or combinations thereof.

[0149] In some embodiments, the bio-based 1,3-BG does not include GC fractions having a fecal, soil, or citrusy odor, or combinations thereof.

[0150] In some embodiments, the bio-based 1,3-BG includes GC fractions having a buttery or solvent odor, or combinations thereof, which are not present in the cosmetic-grade petro-BG.

[0151] In some embodiments, the bio-based 1,3-BG includes GC fractions having a fecal, musty, or sharp odor, or combinations thereof, and having a GC retention time longer than that of 1,3-BG.

[0152] In some embodiments, the bio-derived 1,3-BG can have detectable levels of compounds such as acetaldehyde, 4-hydroxy-2-butanone, 3-buten-2-one (methyl vinyl ketone), diacetyl, 2-butenal (crotonaldehyde), 1-hydroxy-2-propanone, 3-hydroxy-2-butanone (acetoin), 3-hydroxy-butyraldehyde (3-hydroxy-butyl aldehyde), 2,3-butanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-2-propyl-1,3-dioxepane, or combinations thereof. See also Tables 1 and 7. In some embodiments, the compound levels are detectable, for example, by olfactory analysis by a trained person. In some embodiments, the compound levels are detectable by mass and relative signal intensity (e.g., total ion current (TIC)) in a GC-MS chromatogram. In some embodiments, the detectable level of the compound is less than 1,000 ppm, less than 900 ppm, less than 800 ppm, less than 700 ppm, less than 600 ppm, less than 500 ppm, less than 400 ppm, less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, or less than 1 ppm, as determined, for example, by gas chromatography coupled mass spectrometry (GCMS). In some embodiments, the detectable level of the compound is less than the odor threshold of the compound.

[0153] At least the following volatile substance compounds in the bio-derived 1,3-BG were detected only in the gas headspace using an absorbent. Therefore, although not wishing to be bound by theory, the following exemplary compounds are thought to be present at levels below 1 ppm: acetaldehyde, 3-buten-2-one (methyl vinyl ketone), diacetyl, 2-butenal (crotonaldehyde), 3-hydroxy-2-butanone (acetoin), or combinations thereof. At least the following exemplary compounds can be specific to bio-derived 1,3-BG: 4-hydroxy-2-butanone, diacetyl, 1-hydroxy-2-propanone, 2,3-butanediol, 1,2-propanediol, or 1,3-propanediol, or combinations thereof.

Table 1-1

Table 1-2

[0154] In some embodiments, the levels of acetaldehyde, 4-hydroxy-2-butanone, 3-buten-2-one (methyl vinyl ketone), diacetyl, 2-butenal (crotonaldehyde), 1-hydroxy-2-propanone, 3-hydroxy-2-butanone (acetoin), 3-hydroxy-butenal (3-hydroxy-butyl aldehyde), 2,3-butanediol, 1,2-propanediol, 1,3-propanediol, 1,3-dioxepane, 2-methyl-2-propyl, 2-methyl-2-propyl-1,3-dioxepane, or combinations thereof cannot be detected in bio-derived 1,3-BG, for example by GC-MS.

[0155] In some embodiments, the bio-derived 1,3-BG has a detectable level of 3-hydroxybutanal or 4-hydroxy-2-butanone. In some embodiments, the bio-derived 1,3-BG has, for example, less than 200 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm of 3-hydroxybutanal or 4-hydroxy-2-butanone as determined by GC-MS. In some embodiments, the bio-derived 1,3-BG has 3-hydroxybutanal or 4-hydroxy-2-butanone less than the odor threshold of 3-hydroxybutanal or 4-hydroxy-2-butanone.

[0156] In some embodiments, the bio-derived 1,3-BG has a detectable level of 3-hydroxybutanal. In some embodiments, the bio-derived 1,3-BG has, for example, less than 200 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm of 3-hydroxybutanal as determined by GC-MS. In some embodiments, the level of 3-hydroxybutanal is not detectable in the bio-derived 1,3-BG by, for example, GC-MS. In some embodiments, the bio-derived 1,3-BG has 3-hydroxybutanal less than the odor threshold of 3-hydroxybutanal. In some embodiments, the bio-derived 1,3-BG has less than 40 ppm of 3-hydroxybutanal.

[0157] In some embodiments, the bio-derived 1,3-BG has a detectable level of 4-hydroxy-2-butanone. In some embodiments, the bio-derived 1,3-BG has, for example, less than 200 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm of 4-hydroxy-2-butanone as determined by GC-MS. In some embodiments, the level of 4-hydroxy-2-butanone is not detectable in the bio-derived 1,3-BG by, for example, GC-MS. In some embodiments, the bio-derived 1,3-BG has less 4-hydroxy-2-butanone than the odor threshold of 4-hydroxy-2-butanone.

[0158] In some embodiments, the bio-derived 1,3-BG has a detectable level of 1-hydroxy-2-propanone. In some embodiments, the bio-derived 1,3-BG has, for example, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, or less than 1 ppm of 1-hydroxy-2-propanone as determined by GC-MS. See, for example, Table 1. In some embodiments, the level of 1-hydroxy-2-propanone is not detectable in the bio-derived 1,3-BG by, for example, GC-MS.

[0159] In some embodiments, the biogenic 1,3-BG has a detectable level of 1,2-propanediol. In some embodiments, the biogenic 1,3-BG has, for example, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, or less than 1 ppm of 1,2-propanediol as determined by, for example, GC-MS. See, for example, Table 1. In some embodiments, the level of 1,2-propanediol is not detectable in the biogenic 1,3-BG by, for example, GC-MS.

[0160] In some embodiments, the biogenic 1,3-BG has a detectable level of 1,3-propanediol. In some embodiments, the biogenic 1,3-BG has, for example, less than 200 ppm, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, or less than 10 ppm of 4-hydroxy-2-butanone 1,3-propanediol as determined by, for example, GC-MS. In some embodiments, the level of 1,3-propanediol is not detectable in the biogenic 1,3-BG by, for example, GC-MS.

[0161] In some embodiments, the biogenic 1,3-BG has a detectable level of 2,3-butanediol. In some embodiments, the biogenic 1,3-BG has, for example, less than 100 ppm, less than 90 ppm, less than 80 ppm, less than 70 ppm, less than 60 ppm, less than 50 ppm, less than 40 ppm, less than 30 ppm, less than 20 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, less than 3 ppm, less than 2 ppm, or less than 1 ppm of 2,3-butanediol as determined by, for example, GC-MS. In some embodiments, the level of 2,3-butanediol is not detectable in the biogenic 1,3-BG by, for example, GC-MS.

[0162] In another aspect, a method for purifying a biologically-derived 1,3-BG is provided herein.

[0163] In some embodiments, a method for purifying a biologically-derived 1,3-BG can include culturing a non-naturally-occurring microorganism to produce the biologically-derived 1,3-BG in a fermentation broth and performing one or more of the following procedures on the fermentation broth: microfiltration, ultrafiltration, nanofiltration, primary ion exchange, evaporation, polishing ion exchange, column distillation, hydrogenation, activated carbon filtration or adsorption, base addition, sodium borohydride (NaBH4) treatment, and wiped-film evaporation.

[0164] In some embodiments, a method for purifying a biologically-derived 1,3-BG includes (i) microfiltration, followed by (ii) nanofiltration, followed by (iii) primary ion exchange, followed by (iv) evaporation, followed by (v) polishing ion exchange, followed by (vi) distillation. In some embodiments, base addition is performed as a step after ion exchange and before or during the distillation step. In some embodiments, distillation includes activated carbon treatment. In some embodiments, activated carbon treatment is performed during the distillation process. In some embodiments, carbon treatment is performed at the end of the distillation process. In some embodiments, sodium borohydride treatment is performed after distillation in (v).

[0165] In some embodiments, a method for purifying a bioderived 1,3-BG can include the step of distilling a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG. The distillation can be performed using the distillation system provided herein to produce a purified bioderived 1,3-BG product. The purified bioderived 1,3-BG product can be or can include bioderived 1,3-BG (1,3-BDO) that is greater than 90%, 92%, 94%, 96%, 97%, 98%, 99%, 99.5%, 99.7% or 99.9% by weight / weight. The distillation system can include or can be composed of one or more distillation columns that can be used to remove materials having a boiling point higher or lower than 1,3-BG by generating a stream of materials having a boiling point higher or lower than 1,3-BG. Examples of distillation columns can include, or can include, random packings, structured packings, plates, random and structured packings, random packings and plates, or structured packings and plates. As is known in the art, many types and configurations of distillation columns are available. The recovery rate of bioderived 1,3-BG in the purified bioderived 1,3-BG (1,3-BDO) product can be calculated as a percentage by dividing the amount of bioderived 1,3-BG (1,3-BDO) in the purified bioderived 1,3-BG product by the amount of bioderived 1,3-BG or the target compound in the purified crude bioderived 1,3-BG mixture.

[0166] What should be considered in distillation is to reduce or minimize the amount of heat that the bio-derived 1,3-BG or the target compound product receives during the distillation process. Impurities or even bio-derived 1,3-BG may undergo heat or chemical decomposition while being heated during distillation. Operating the distillation column under reduced pressure (less than atmospheric pressure) or in a vacuum reduces the boiling temperature of the mixture within the distillation column, enabling operation of the distillation column at a lower temperature. Any column described in the various embodiments provided herein can be operated under reduced pressure. A common vacuum system can be used with some or all of the distillation columns to achieve reduced pressure, or each column may have its own vacuum system. All combinations and permutations of the above-exemplified vacuum equipment configurations are within the scope of the compositions, systems, and methods provided and described herein. The pressure of the distillation column can be measured at the top or condenser, the bottom or base, or anywhere in between. The pressure at the top of the distillation column may differ from the pressure at the base of the distillation column, and this pressure difference indicates the pressure drop across the entire distillation column. Different distillation columns of the same embodiment can be operated at different pressures. The pressure within the column can be ambient pressure, less than ambient pressure, or, for example, less than 500 mmHg, 200 mmHg, 100 mmHg, 50 mmHg, 40 mmHg, 30 mmHg, 20 mmHg, 15 mmHg, 10 mmHg, or 5 mmHg.

[0167] It should be understood that the step of removing high or low boiling point materials by distillation using a distillation column is not expected to be 100% effective, and there may still be residual amounts of high or low boiling point materials present in the product stream after the distillation procedure. When it is described that a material is removed by the distillation procedure, removal can mean that more than 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5% or 99.9% of the material is removed from the feed port to the distillation column by distillation.

[0168] The mixture to be refined can be fed to a distillation column, and depending on the operating conditions, high-boiling or low-boiling materials can be removed from the mixture. For example, when removing low-boiling materials, the low-boiling materials are boiled and removed from the top of the distillation column, and the product-containing stream with the low-boiling materials removed is discharged from the bottom of the distillation column. This bottom stream can be fed to the next distillation column, where high-boiling materials are removed from the product-containing stream. In the next distillation column, the product-containing stream is boiled and discharged from the top of the distillation column, and the high-boiling materials are removed from the bottom of the distillation column, thus obtaining a purer product-containing stream. In another example, both high-boiling and low-boiling materials can be removed from the product-containing stream. In this case, the low-boiling materials are boiled and removed through the top of the column, the high-boiling materials are removed from the bottom of the column, and the product is discharged through a side-draw, whereby the material is withdrawn from the column at an intermediate position between the top and bottom of the distillation column.

[0169] In the systems and methods provided herein that include a distillation column, the distillation column has several stages. In some embodiments, the disclosed system or method has a distillation column that includes from 3 to 80 stages. For example, the distillation column can have from 3 to 25 stages, from 25 to 50 stages, or from 50 to 80 stages. In some embodiments, the distillation column has from 8 to 28 stages, such as from 14 to 18 stages. In some embodiments, the distillation column has 4 stages, 8 stages, 10 stages, 11 stages, 17 stages, 22 stages, 18 stages, 23 stages, 30 stages, or 67 stages.

[0170] In some embodiments, the method comprises: (a) subjecting a first biomass-derived 1,3-BG-containing product stream to a first column distillation procedure to remove materials having a boiling point higher than that of biomass-derived 1,3-BG as a first high-boiling stream, thereby producing a second 1,3-BG-containing product stream; (b) subjecting the second biomass-derived 1,3-BG-containing product stream to a second column distillation procedure to remove materials having a boiling point lower than that of biomass-derived 1,3-BG, thereby producing a third biomass-derived 1,3-BG-containing product stream; and (c) subjecting the third biomass-derived 1,3-BG-containing product stream to a third column distillation procedure to remove materials having a boiling point higher than that of biomass-derived 1,3-BG as a second high-boiling stream, thereby producing a fourth biomass-derived 1,3-BG-containing product stream comprising a purified biomass-derived 1,3-BG product. In some embodiments, the purified biomass-derived 1,3-BG product is the biomass-derived 1,3-BG provided herein.

[0171] In some embodiments, the method comprises subjecting a crude biomass-derived 1,3-BG mixture or a partially purified biomass-derived 1,3-BG to refinement to produce the first biomass-derived 1,3-BG-containing product stream of (a). In some embodiments, the refinement involves, for example, ion exchange chromatography or contact with activated carbon.

[0172] Purification is a procedure for reducing or removing all residual salts and / or other impurities in a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG. Purification may include contacting the crude bioderived 1,3-BG (1,3-BDO) or the partially purified bioderived 1,3-BG with one or several materials that can react with or adsorb the impurities in the crude bioderived 1,3-BG mixture or the partially purified bioderived 1,3-BG. Materials used in purification may include ion exchange resins, activated carbon, or adsorbent resins such as, for example, DOWEX™ 22, DOWEX™ 88, OPTIPORE™ L493, AMBERLITE™ XAD761, or AMBERLITE™ FPX66, or mixtures of these resins such as a mixture of DOWEX™ 22 and DOWEX™ 88.

[0173] In some embodiments, purification is or includes purification ion exchange. Using purification ion exchange, all residual salts, color bodies, and color precursors can be removed and then further purified. Purification ion exchange can include anion exchange, cation exchange, both cation exchange and anion exchange, or can be cation-anion mixed bed exchange including both cation exchange resin and anion exchange resin, or can include these. In certain embodiments, purification ion exchange is, or includes, anion exchange followed by cation exchange, cation exchange followed by anion exchange, or cation-anion mixed bed exchange. In certain embodiments, purification ion exchange is or includes anion exchange. Purification ion exchange is, or includes, both strong cation and strong anion exchange, or other strong anion exchange other than purification cation exchange or purification anion exchange, or includes this. In some embodiments, purification ion exchange is performed after a water removal step such as evaporation and before subsequent distillation.

[0174] In some embodiments, the method comprises subjecting a crude bio-derived 1,3-BG mixture or a partially purified bio-derived 1,3-BG to a dehydration column distillation procedure to remove materials having a boiling point lower than that of the bio-derived 1,3-BG from the crude bio-derived 1,3-BG mixture or the partially purified bio-derived 1,3-BG to produce a first bio-derived 1,3-BG-containing product stream of (a).

[0175] In some embodiments, the method comprises subjecting a crude bio-derived 1,3-BG mixture or a partially purified bio-derived 1,3-BG to refining, subjecting the resulting crude bio-derived 1,3-BG mixture or the partially purified bio-derived 1,3-BG to a dehydration column distillation procedure to reduce or remove materials having a boiling point lower than that of the bio-derived 1,3-BG from the resulting crude bio-derived 1,3-BG mixture to produce a first bio-derived 1,3-BG-containing product stream of (a). In some embodiments, refining involves, for example, ion exchange chromatography or contact with activated carbon.

[0176] The reflux ratio in a distillation system or method is the ratio of the boil-up rate to the take-off rate. In other words, the reflux ratio is the ratio of the amount of reflux returning to the distillation column to the amount of reflux (distillate) collected in the receiver. For example, a reflux ratio of 2:1 indicates that the reflux returning to the distillation column is twice (e.g., on a volume or weight basis) that collected as distillate.

[0177] In some embodiments, the reflux ratio of the dehydration column or the first, second, or third distillation column in the methods or systems provided herein is 1:1 or more, 2:1 or more, 3:1 or more, 4:1 or more, 5:1 or more, 6:1 or more, 7:1 or more, 8:1 or more, 9:1 or more, or 10:1 or more.

[0178] In some embodiments, the reflux ratio of the dehydration column, or the first, second, or third distillation column, in the methods or systems provided herein is 1:1 or less, 1:2 or less, 1:3 or less, 1:4 or less, 1:5 or less, 1:6 or less, 1:7 or less, 1:8 or less, 1:9 or less, or 1:10 or less.

[0179] In some embodiments, the method includes adding a base to a bioderived 1,3-BG-containing product stream either before or after any one of (a), (b), or (c). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream before (a). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream before the bioderived crude or partially purified 1,3-BG is subjected to polishing. In some embodiments, polishing involves, for example, ion exchange chromatography, or contact with activated carbon, or both, or includes these. In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream after the bioderived crude or partially purified 1,3-BG has been subjected to polishing. In some embodiments, the base is added to the crude bioderived 1,3-BG mixture or partially purified bioderived 1,3-BG obtained from polishing before a dehydration column is performed. In some embodiments, the base is added to the crude bioderived 1,3-BG mixture or partially purified bioderived 1,3-BG obtained from polishing after a dehydration column is performed. In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream after (a). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream between (a) and (b). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream before (b). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream after (b). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream between (b) and (c). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream before (c). In some embodiments, the base is added to the bioderived 1,3-BG-containing product stream after (c).

[0180] In some embodiments, the base is added to a dehydration column, or to the reboiler of a first, second, or third distillation column, or a combination thereof.

[0181] In some embodiments, the base is added into an alkali reactor such as a circulating tube reactor.

[0182] In some embodiments, the base may be, for example, an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, ammonium hydroxide, or a combination thereof.

[0183] In some embodiments, the base is added in an amount of 0.05% to 10%, for example, 0.05 wt% to 1 wt%, 1 wt% to 2 wt%, 2 wt% to 3 wt%, 3 wt% to 4 wt%, 4 wt% to 5 wt%, 5 wt% to 6 wt%, 6 wt% to 7 wt%, 7 wt% to 8 wt%, 8 wt% to 9 wt%, or 9 wt% to 10% based on the weight of the crude bio-derived 1,3-BG mixture or the partially purified bio-derived 1,3-BG.

[0184] In some embodiments, the addition of the base is carried out at a temperature of 90 - 140 °C in the alkali reactor, for example, 90 - 110 °C, 110 - 130 °C, or 120 - 140 °C.

[0185] In some embodiments, the residence time in the alkali reactor is 5 to 120 minutes, for example, 5 to 15 minutes, 10 to 30 minutes, 20 to 40 minutes, 30 to 50 minutes, 40 to 60 minutes, 50 to 70 minutes, 60 to 80 minutes, 70 to 90 minutes, 80 to 100 minutes, 90 to 110 minutes, or 100 to 120 minutes.

[0186] In some embodiments, after adding the base, for example, de-alkalization is carried out using a thin-film evaporator. In some embodiments, during de-alkalization, the base added to the crude bio-derived 1,3-BG mixture or the partially purified bio-derived 1,3-BG is removed together with high-boiling materials from the bio-derived 1,3-BG-containing product stream.

[0187] In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction either before or after any one of (a), (b), or (c). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction before (a). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction between (a) and (b). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction after (a). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction before (b). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction after (b). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction between (b) and (c). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction before (c). In some embodiments, the method includes treating a biologically-derived 1,3-BG-containing product stream with a hydrogenation reaction after (c).

[0188] In some embodiments, the hydrogenation reaction reduces the concentration of 3-hydroxy-butan-al or 4-hydroxy-2-butanone in the second biologically-derived 1,3-BG-containing product stream by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0189] In some embodiments, the hydrogenation reaction reduces the UV absorbance of the second biologically-derived 1,3-BG-containing product stream at 270 nm or 220 nm by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0190] In some embodiments, the method includes contacting a biomass-derived 1,3-BG-containing product stream with activated carbon. In some embodiments, the activated carbon is chemically activated carbon. As used herein, "chemically activated carbon" refers to activated carbon that has been activated by chemical treatment as opposed to oxidation with air or other gases. In some embodiments, the chemically activated carbon is subjected to a second activation with steam and given physical properties that do not occur during chemical activation. Chemically activating agents that can be used include phosphoric acid; sulfuric acid; zinc chloride; potassium sulfide; potassium thiocyanate; hydroxides, carbonates, sulfides, and sulfates of alkali metals; and carbonates, chlorides, sulfates, and phosphates of alkaline earths. In some embodiments, the chemically activated carbon used in the methods and systems provided herein is wood-based (sawdust) activated carbon activated with phosphoric acid. Exemplary chemically activated carbon is commercially available, for example, the Nuchar® WV-B grade activated carbon material from MeadWestvaco Corp. (Richmond, VA).

[0191] The activated carbon can be, for example, in a micronized or granular form. In some embodiments, the activated carbon is coal-based, wood-based, or coconut shell-based. In some embodiments, the activated carbon is steam-activated. In some embodiments, the activated carbon is washed with an acid. In some embodiments, the activated carbon can be Cabot Darco S-51A M-1967 (Darco; Cabot Corp., Boston, MA), Calgon FILTRASORB 300 (FS 300; Calgon Carbon Corp., Moon Township, PA), or Calgon CPG-LF (CPG-LF; Calgon Carbon Corp., Moon Township, PA).

[0192] In some embodiments, the biomass-derived 1,3-BG treated with activated carbon is provided to a customer and / or is "consumed" without further purification if, for example, it is incorporated into another composition immediately after the activated carbon treatment without further subsequent purification steps such as distillation.

[0193] In some embodiments, the method includes contacting a first bioderived 1,3-BG-containing product stream with activated carbon. In some embodiments, the method includes contacting a second bioderived 1,3-BG-containing product stream with activated carbon. In some embodiments, the method includes contacting a third bioderived 1,3-BG-containing product stream with activated carbon. In some embodiments, the method includes contacting a second high-boiling stream with activated carbon.

[0194] In some embodiments, upon contacting the bioderived 1,3-BG-containing product stream with activated carbon, the concentration of 3-hydroxy-butanol or 4-hydroxy-2-butanone in the second bioderived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0195] In some embodiments, the method includes contacting the bioderived 1,3-BG-containing product stream with sodium borohydride (NaBH4). In some embodiments, the method includes contacting a first bioderived 1,3-BG-containing product stream with NaBH4. In some embodiments, the method includes contacting a second bioderived 1,3-BG-containing product stream with NaBH4. In some embodiments, the method includes contacting a third bioderived 1,3-BG-containing product stream with NaBH4. In some embodiments, the method includes contacting a second high-boiling stream with NaBH4.

[0196] In some embodiments, when a bioderived 1,3-BG-containing product stream is contacted with NaBH4, the concentration of 3-hydroxy-butan-al or 4-hydroxy-2-butanone in the distillate of the second bioderived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more. In some embodiments, when a bioderived 1,3-BG-containing product stream is contacted with NaBH4, the UV absorbance at 270 nm or 220 nm of the second bioderived 1,3-BG-containing product stream decreases by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more.

[0197] In some embodiments, the method includes subjecting a first high-boiling stream to wiped film evaporation (WFE) to produce a WFE distillate and subjecting the WFE distillate to a first column distillation procedure.

[0198] In some embodiments, the method includes subjecting a second high-boiling stream to WFE to produce a WFE distillate and subjecting the WFE distillate to a third column distillation procedure.

[0199] In some embodiments, the distillation includes subjecting a first high-boiling stream from the distillation to WFE to produce a WFE distillate. The WFE distillate can be further subjected to a first column distillation procedure of the system provided herein. In some embodiments, the WFE distillate can be further subjected to a fourth column distillation procedure of the system provided herein.

[0200] WFE is also known as wiped film evaporation and can be useful for relatively rapidly separating volatile components from low volatility components when the components are heat sensitive, viscous, and tend to contaminate heated surfaces (such as amino acids, sugars, and other components often found in fermentation broths). Typically, in embodiments of the systems and methods described herein, the evaporable components (distillate) from a wiped film evaporator (“WFE”) include biogenic 1,3 - BG. Thus, as utilized in the systems and methods described herein, the WFE is a distillation component that increases the product yield by recovering biogenic 1,3 - BG, which would otherwise be disposed of, from the heavy material stream. For example, in a column distillation system or method, a crude biogenic 1,3 - BG mixture (or a partially purified biogenic 1,3 - BG such as the biogenic 1,3 - BG (1,3 - BDO) product stream from a dehydration column) is fed into a given distillation column, from which 1,3 - BG is taken out as the distillate (“low boilers”), and wiped film evaporation is performed on the bottoms purge (“high boilers”) from the distillation column (which would otherwise be disposed of). The 1,3 - BG - containing distillate of the WFE is returned to the column distillation system or method, increasing the recovery rate of 1,3 - BG. The heating time in the wiped film evaporator can be shortened to minimize decomposition.

[0201] In some embodiments, the WFE is a single pass distillation apparatus (SPD). In some embodiments, the WFE is a vertical WFE. In some embodiments, the WFE is a horizontal WFE.

[0202] The wiped-film evaporator can operate under vacuum conditions such as 50 mmHg, 25 mmHg, 10 mmHg, 1 mmHg, 0.1 mmHg, less than 0.01 mmHg, or even lower. The operating conditions for wiped-film evaporation can be, for example, pressures in the range of about 0.1 mmHg to 25 mmHg, about 1 mmHg to 10 mmHg, about 2 mmHg to 7.5 mmHg, about 4 mmHg to 7.5 mmHg, or about 4 mmHg to 15 mmHg, and temperature ranges of about 100 °C to 150 °C, 110 °C to 150 °C, 115 °C to 150 °C, 115 °C to 140 °C, 115 °C to 130 °C or 125 °C to 150 °C can be used.

[0203] In some embodiments, the WFE can operate at a temperature below 160 °C. In some embodiments, the WFE can operate at a temperature between 145 °C and 155 °C. In some embodiments, the WFE can operate under vacuum. In some embodiments, the operating conditions for the wiped-film evaporator include a temperature of about 145 °C to 155 °C and a vacuum of about 4 mmHg to 15 mmHg.

[0204] In some embodiments, the method for purifying the bio-derived 1,3-BG provided herein includes one or more of fermentation, cell separation, salt separation, evaporation, or combinations thereof. In some embodiments, the method includes fermentation, followed by cell separation, followed by salt separation, followed by evaporation. In some embodiments, fermentation, cell separation, salt separation, and evaporation result in a crude bio-derived 1,3-BG mixture or a partially purified bio-derived 1,3-BG, which can be fed into a polishing column (e.g., polishing ion exchange), a dehydration column, or a first distillation column in the methods or systems provided herein.

[0205] In some embodiments, the method includes fermentation. In some embodiments, the fermentation includes culturing a non-naturally occurring microorganism to produce bio-derived 1,3-BG in a fermentation broth. Exemplary non-naturally occurring microorganisms and methods for producing bio-derived 1,3-BG in a fermentation broth are described, for example, in WO2010 / 127319A2 and WO2011 / 071682A1, the entire contents of each of which are hereby incorporated by reference.

[0206] In some embodiments, the method includes cell separation. In some embodiments, the cell separation includes separating a liquid fraction from a commercially available fraction containing cells and a fermentation broth enriched in bio-derived 1,3-BG. In some embodiments, the separation includes centrifugation or filtration, or a combination thereof. In some embodiments, the filtration includes microfiltration, ultrafiltration, or nanofiltration, or a combination thereof. In some embodiments, the filtration consists of microfiltration. In some embodiments, the filtration consists of ultrafiltration. In some embodiments, the filtration consists of microfiltration and nanofiltration. In some embodiments, the filtration consists of ultrafiltration and nanofiltration.

[0207] Using centrifugation, a crude bio-derived 1,3-BG mixture or a partially purified bio-derived 1,3-BG substantially free of solids including cell masses can be obtained. Depending on the equipment configuration and size of the centrifuge, the operating speed can be changed from less than 500 rpm to generally 500 rpm to 12,000 rpm or faster than 12,000 rpm. At 500 to 12,000 rpm, centrifugal forces up to and exceeding 15,000 times the force of gravity can be generated. Many equipment configurations of centrifuges for removing cells and solids from fermentation broth are known in the art and can be used in the systems and methods provided herein. Such equipment configurations include, for example, disk stack centrifuges and decanters or solid bowl centrifuges. Centrifugation can be performed batchwise or continuously. All combinations of centrifuge equipment configurations well known in the art can be used in the systems and methods provided herein.

[0208] Microfiltration involves, for example, a low-pressure membrane method for separating colloids and suspended particles in the range of about 0.05 to 10 microns. Useful equipment configurations include cross-flow filtration using spiral-wound, hollow fiber, or flat sheet (cartridge) microfiltration elements. Microfiltration includes filtration through a membrane having a pore size from about 0.05 microns to about 10.0 microns. Microfiltration membranes can have a nominal molecular weight cut-off (MWCO) of about 20,000 Daltons and higher. The term molecular weight cut-off is used to indicate the size of particles, including polypeptides or peptide aggregates, that will be approximately 90% retained by the membrane. Polymers, ceramics, or steel microfiltration membranes can be used to separate cells. Ceramic or steel microfiltration membranes have a long operating life, such as up to 10 years or longer. Microfiltration can be used in the purification of fermentation broths. For example, the microfiltration membrane can have a pore size from about 0.05 microns to 10 microns, or from about 0.05 microns to 2 microns, from about 0.05 microns to 1.0 microns, from about 0.05 microns to 0.5 microns, from about 0.05 microns to 0.2 microns, from about 1.0 microns to 10 microns, or from about 1.0 microns to 5.0 microns; or the membrane can have a pore size of about 0.05 microns, about 0.1 microns, or about 0.2 microns. For example, the microfiltration membrane can have an MWCO from about 20,000 Daltons to 500,000 Daltons, from about 20,000 Daltons to 200,000 Daltons, from about 20,000 Daltons to 100,000 Daltons, from about 20,000 Daltons to 50,000 Daltons, or from about 50,000 Daltons to 300,000 Daltons; or an MWCO of about 20,000 Daltons, about 50,000 Daltons, about 100,000 Daltons or about 300,000 Daltons can be used for the separation of cells and solids from fermentation broths.

[0209] Ultrafiltration is a selective separation method that passes a membrane using a pressure of up to about 145 psi (10 bar). Useful equipment configurations include cross-flow filtration using spiral wound, hollow fiber, or flat sheet (cartridge) ultrafiltration elements. These elements consist of polymeric or ceramic membranes with a molecular weight cut-off of less than about 200,000 Daltons. Ceramic ultrafiltration membranes are also useful because of their long operating life of up to 10 years or more. Ceramics have the disadvantage of being considerably more expensive than polymeric membranes. Ultrafiltration concentrates suspended solids and solutes with a molecular weight greater than about 1,000 Daltons. Ultrafiltration includes filtration through a membrane having a nominal molecular weight cut-off (MWCO) of from about 1,000 Daltons to about 200,000 Daltons (pore sizes of from about 0.005 to 0.1 microns). For example, the ultrafiltration membrane can have a pore size of from about 0.005 microns to 0.1 microns, or from about 0.005 microns to 0.05 microns, from about 0.005 microns to 0.02 microns, or from about 0.005 microns to 0.01 microns. For example, the ultrafiltration membrane can have an MWCO of from about 1,000 Daltons to 200,000 Daltons, from about 1,000 Daltons to 50,000 Daltons, from about 1,000 Daltons to 20,000 Daltons, from about 1,000 Daltons to 5,000 Daltons, or from about 5,000 Daltons to 50,000 Daltons. The liquid permeated using ultrafiltration will contain low molecular weight organic solutes such as bioderived 1,3-BG, media salts, and water. The captured solids can include, for example, residual cell debris, DNA, and proteins. The known diafiltration technique in the art can be used to increase the recovery rate of bioderived 1,3-BG in the ultrafiltration step.

[0210] Using a further filtration procedure called nanofiltration, certain materials can be separated by size and charge, including carbohydrates, inorganic and organic salts, residual proteins, and other high molecular weight impurities remaining after the previous filtration step. By this procedure, for example, certain salts can be recovered without prior evaporation of water. Nanofiltration can separate salts, remove color, and perform desalination. In nanofiltration, the permeate generally contains monovalent ions and low molecular weight organic compounds such as those exemplified by bio-derived 1,3-BG. Nanofiltration involves filtration through a membrane having a nominal molecular weight cut-off (MWCO) of from about 100 Daltons to about 2,000 Daltons (pore size of from about 0.0005 to 0.005 microns). For example, the nanofiltration membrane can have an MWCO of from about 100 Daltons to 500 Daltons, from about 100 Daltons to 300 Daltons, or from about 150 Daltons to 250 Daltons. The mass transfer mechanism in nanofiltration is diffusion. The nanofiltration membrane allows partial diffusion of certain ionic solutes (such as sodium and chloride), mainly monovalent ions, and water. Larger ionic species including divalent and polyvalent ions, as well as more complex molecules, are substantially retained (rejected). Larger non-ionic species such as carbohydrates are also substantially retained (rejected). Nanofiltration is generally operated at pressures of from 70 psi to 700 psi, 200 psi to 650 psi, 200 psi to 600 psi, 200 psi to 450 psi, 70 psi to 400 psi, about 400 psi, about 450 psi, or about 500 psi.

[0211] One embodiment of nanofiltration has a membrane with a molecular weight cut-off of about 200 Daltons, which rejects about 99% of divalent salts such as magnesium sulfate, for example. Certain embodiments will have a nanofiltration membrane with a molecular weight cut-off of about 150 - 300 Daltons for uncharged organic molecules.

[0212] In some embodiments, the method includes salt separation. In some embodiments, the salt separation is performed before water removal. In some embodiments, the salt removal includes nanofiltration. In some embodiments, the salt removal includes ion exchange. In some embodiments, the salt removal includes nanofiltration and ion exchange.

[0213] Ion exchange can be used to remove salts from mixtures such as fermentation broths. Ion exchange elements can take the form of resin beads as well as membranes. The resin is frequently cast in the form of porous beads. The resin can be or include a cross-linked polymer having active groups in the form of charged sites. At these sites, ions of opposite charge are attracted, but may be replaced by other ions depending on their relative concentrations and affinities for the site. Ion exchange resins can be, for example, cationic or anionic. Factors that determine the efficiency of a given ion exchange resin include the preference for a given ion and the number of available active sites. It may be useful to increase the surface area in order to maximize the active sites. Thus, small porous particles are useful because they increase the surface area per unit volume.

[0214] The anion exchange resin can be a strongly basic or weakly basic anion exchange resin, and the cation exchange resin can be a strongly acidic or weakly acidic cation exchange resin. Non-limiting examples of ion exchange resins that are strongly acidic cation exchange resins include AMBERJET™ 1000Na, AMBERLITE™ IR10, or DOWEX™ 88; examples of weakly acidic cation exchange resins include AMBERLITE™ IRC86 or DOWEX™ MAC3; examples of strongly basic anion exchange resins include AMBERJET™ 4200Cl or DOWEX™ 22; examples of weakly basic anion exchange resins include AMBERLITE™ IRA96, DOWEX™ 77, or DOWEX™ Marathon WMA. Ion exchange resins can be obtained from various manufacturers such as Dow, Purolite, Rohm and Haas, Mitsubishi Chemical Corporation, or other companies.

[0215] In some embodiments, the primary ion exchange chromatography is performed using DOWEX™ 88 (cation exchange) and DOWEX™ 77 (anion exchange) resins.

[0216] In some embodiments, the polished ion exchange chromatography is performed using DOWEX™ 88 (cation exchange) and DOWEX™ 22 (anion exchange) resins.

[0217] Primary ion exchange can be utilized to remove salts. Primary ion exchange can include, for example, both cation exchange or anion exchange, or cation-anion mixed exchange including both a cation exchange resin and an anion exchange resin. In certain embodiments, primary ion exchange can be cation exchange and anion exchange in any order. In some embodiments, primary ion exchange is anion exchange followed by cation exchange, or cation exchange followed by anion exchange, or cation-anion mixed exchange. In certain embodiments, primary ion exchange is anion exchange or cation exchange. More than one given type of ion exchange can be used in primary ion exchange. For example, primary ion exchange can include cation exchange, followed by anion exchange, followed by cation exchange, and finally followed by anion exchange.

[0218] In certain embodiments, strong acid cation exchange and weak base anion exchange are used in primary ion exchange. Ion exchange, such as primary ion exchange, can be carried out at a temperature of 20°C to 60°C, 30°C to 60°C, 30°C to 50°C, 30°C to 40°C or 40°C to 50°C; or at a temperature of about 30°C, about 40°C, about 50°C, or about 60°C. The flow rate in ion exchange such as primary ion exchange can be 1 bed volume per hour (BV / h) to 10 BV / h, 2 BV / h to 8 BV / h, 2 BV / h to 6 BV / h, 2 BV / h to 4 BV / h, 4 BV / h to 6 BV / h, 4 BV / h to 8 BV / h, 4 BV / h to 10 BV / h or 6 BV / h to 10 BV / h.

[0219] In some embodiments, the bio-derived 1,3-BG product obtained after salt removal and / or water removal is a crude bio-derived 1,3-BG mixture or a partially purified bio-derived 1,3-BG. The obtained crude bio-derived 1,3-BG or partially purified bio-derived 1,3-BG or target compound mixture is, for example, on a weight / weight basis, at least 50%, 60%, 70%, 80%, 85% or 90% 1,3-BG, and less than 50%, 40%, 30%, 20%, 15%, 10% or 5% water.

[0220] In some embodiments, the method includes the step of evaporating to remove water from the bioderived 1,3-BG product. There are many types and configurations of evaporators well known to those skilled in the art available for removing moisture. An evaporator is a heat exchanger in which a liquid boils and vapor is obtained, i.e., it is also a low-pressure steam generator. This vapor can be used to further heat in another evaporator called a "utility". The removal of water is achieved by evaporation using an evaporator system, which includes one or more utilities. In some embodiments, a double or triple utility evaporator system can be used to separate water from the bioderived 1,3-BG. Any number of multiple utility evaporator systems can be used in the removal of water. A triple utility evaporator or other evaporator equipment configuration can include a dedicated utility, such as the last utility of a triple utility configuration, which is an evaporative crystallization device for recovering salts. Alternatively, a mechanical vapor recompression or thermal vapor recompression evaporator can be utilized to reduce the energy required for the evaporation of water beyond what can be achieved in a standard multiple utility evaporator.

[0221] Examples of evaporators include falling film evaporators (which can be single-pass evaporators), forced circulation evaporators, plate evaporators, circulation evaporators, fluidized bed evaporators, rising film evaporators, countercurrent trickle evaporators, agitated evaporators, and spiral tube evaporators.

[0222] In some embodiments, the purified bioderived 1,3-BG product produced by the method provided herein comprises the bioderived 1,3-BG provided herein.

[0223] In some embodiments, the purified bioderived 1,3-BG product is collected as the distillate of a third column distillation procedure.

[0224] In another aspect, provided herein is a biologically-derived 1,3-BG produced by the methods provided herein.

[0225] In some embodiments, the method comprises subjecting a crude biologically-derived 1,3-BG mixture or a partially purified biologically-derived 1,3-BG to a dehydrating column distillation procedure to remove materials having a boiling point lower than that of the biologically-derived 1,3-BG from the crude biologically-derived 1,3-BG mixture or the partially purified biologically-derived 1,3-BG to produce a first biologically-derived 1,3-BG-containing product stream; subjecting the first biologically-derived 1,3-BG-containing product stream to a first column distillation procedure to remove materials having a boiling point higher than that of the biologically-derived 1,3-BG as a first high-boiling material stream to produce a second 1,3-BG-containing product stream; optionally adding a base to the second 1,3-BG-containing product stream; optionally treating the second 1,3-BG-containing product stream with a hydrogenation reaction; subjecting the second biologically-derived 1,3-BG-containing product stream to a second column distillation procedure to remove materials having a boiling point lower than that of the biologically-derived 1,3-BG to produce a third biologically-derived 1,3-BG-containing product stream; subjecting the third biologically-derived 1,3-BG-containing product stream to a third column distillation procedure to remove materials having a boiling point higher than that of the biologically-derived 1,3-BG as a second high-boiling material stream to produce a fourth 1,3-BG-containing product stream, and optionally exposing the fourth 1,3-BG-containing product stream to activated carbon to produce a purified biologically-derived 1,3-BG product, wherein the purified biologically-derived 1,3-BG product is the biologically-derived 1,3-BG provided herein.

[0226] In another aspect, a first distillation column that receives a first biological-derived 1,3-BG-containing product stream and produces a first material stream having a boiling point higher than that of 1,3-BG and a second biological-derived 1,3-BG-containing product stream; a second distillation column that receives the second biological-derived 1,3-BG-containing product stream and produces a material stream having a boiling point lower than that of 1,3-BG and a third biological-derived 1,3-BG-containing product stream; and a third distillation column that receives the third 1,3-BG-containing product stream at a feed point and produces a second material stream having a boiling point higher than that of 1,3-BG and a fourth biological-derived 1,3-BG-containing product stream containing a purified biological-derived 1,3-BG product are provided herein. In some embodiments, the fourth biological-derived 1,3-BG-containing product stream consists essentially of the biological-derived 1,3-BG provided herein. For example, see FIG. 15A.

[0227] In some embodiments, the system includes a polishing column that receives a crude biological-derived 1,3-BG mixture or a partially purified biological-derived 1,3-BG and produces a crude biological-derived 1,3-BG mixture or a partially purified biological-derived 1,3-BG with a reduced salt content. In some embodiments, the crude biological-derived 1,3-BG mixture or the partially purified biological-derived 1,3-BG with a reduced salt content is the first biological-derived 1,3-BG-containing product stream received by the first distillation column. In some embodiments, the crude biological-derived 1,3-BG mixture or the partially purified biological-derived 1,3-BG with a reduced salt content is received by a dehydration column. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon.

[0228] In some embodiments, the system receives a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG and includes a dehydration column that produces a material stream having a boiling point lower than 1,3-BG and a first bioderived 1,3-BG-containing product stream. In some embodiments, the crude bioderived 1,3-BG mixture or the partially purified bioderived 1,3-BG has a reduced salt content and is produced by a polishing column. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon.

[0229] In some embodiments, the system receives a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG and includes a polishing column that produces a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG having a reduced salt content, and a dehydration column that receives the crude bioderived 1,3-BG mixture or the partially purified bioderived 1,3-BG having a reduced salt content and produces a material stream having a boiling point lower than 1,3-BG and a first bioderived 1,3-BG-containing product stream. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon.

[0230] In some embodiments, the dehydration column in a four-column system has 5 to 15 stages. In some embodiments, the dehydration column in a four-column system has 10 stages.

[0231] In some embodiments, the first column in a four-column system has 10 to 40 stages. In some embodiments, the first column in a four-column system has 15 to 35 stages. In some embodiments, the first column in a four-column system has 18 stages. In some embodiments, the first column in a four-column system has 30 stages.

[0232] In some embodiments, the second column in the four-column system has from 10 to 40 stages. In some embodiments, the second column in the four-column system has from 15 to 35 stages. In some embodiments, the second column in the four-column system has 18 stages. In some embodiments, the second intermediate column in the four-column system has 30 stages.

[0233] In some embodiments, the third column in the four-column system has from 5 to 35 stages. In some embodiments, the third column in the four-column system has from 10 to 30 stages. In some embodiments, the third column in the four-column system has from 15 to 25 stages. In some embodiments, the third column in the four-column system has 18 stages. In some embodiments, the third column in the four-column system has 23 stages.

[0234] In some embodiments of the four-column system, the dehydration column has 10 stages, the first column has 30 stages, the second intermediate column has 30 stages, and the third column has 23 stages.

[0235] In some embodiments of the four-column system, the dehydration column has 8 stages, the first column has 18 stages, the second column has 18 stages, and the third column has 18 stages.

[0236] In some embodiments, the system includes an alkali reactor. In some embodiments, the alkali reactor can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG and produce a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG having a high pH level, which can be fed into a polishing column or a dehydration column. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon. In some embodiments, the alkali reactor can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG with reduced salt content and produce a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG having a high pH level, which can be fed into a dehydration column. In some embodiments, the alkali reactor can receive a first bioderived 1,3-BG-containing product stream and produce a first bioderived 1,3-BG-containing product stream having a high pH level, which can be fed into a first distillation column. In some embodiments, the alkali reactor can receive a second bioderived 1,3-BG-containing product stream and produce a second bioderived 1,3-BG-containing product stream having a high pH level, which can be fed into a second distillation column. In some embodiments, the alkali reactor can receive a third bioderived 1,3-BG-containing product stream and produce a third bioderived 1,3-BG-containing product stream having a high pH level, which can be fed into a third distillation column.

[0237] In some embodiments, the system provided herein that includes an alkali reactor also includes a dealkalization column for removing the base used in the alkali reactor, and a high-boiling material is obtained from the bottom of the column. In some embodiments, the dealkalization column is a thin-film evaporator. In some embodiments, the evaporator used as the dealkalization column is a natural-flow thin-film evaporator or a forced-agitation thin-film evaporator, which has a short residence time and suppresses the thermal hysteresis of the process fluid. In some embodiments, in the evaporator, evaporation is carried out at a reduced pressure of 100 Torr or less, for example, 90 Torr or less, 80 Torr or less, 70 Torr or less, 60 Torr or less, 50 Torr or less, 40 Torr or less, 30 Torr or less, 20 Torr or less, 10 Torr or less, or 5 Torr or less. In some embodiments, the evaporation temperature ranges from 90°C to 120°C.

[0238] In some embodiments, the system includes a hydrogenation reactor configured to process a biologically-derived 1,3-BG-containing product stream. In some embodiments, the hydrogenation reactor can receive a crude biologically-derived 1,3-BG mixture or a partially purified biologically-derived 1,3-BG and produce a hydrogenated crude biologically-derived 1,3-BG mixture or a partially purified biologically-derived 1,3-BG, which can be fed into a polishing column or a dehydration column. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon. In some embodiments, the hydrogenation reactor can receive a crude biologically-derived 1,3-BG mixture or a partially purified biologically-derived 1,3-BG with a reduced salt content and produce a hydrogenated crude biologically-derived 1,3-BG mixture or a partially purified biologically-derived 1,3-BG, which can be fed into a dehydration column. In some embodiments, the hydrogenation reactor can receive a first biologically-derived 1,3-BG-containing product stream and produce a hydrogenated first biologically-derived 1,3-BG-containing product stream, which can be fed into a first distillation column. In some embodiments, the hydrogenation reactor can receive a second biologically-derived 1,3-BG-containing product stream and produce a hydrogenated second biologically-derived 1,3-BG-containing product stream, which can be fed into a second distillation column. In some embodiments, the hydrogenation reactor can receive a third biologically-derived 1,3-BG-containing product stream and produce a hydrogenated third biologically-derived 1,3-BG-containing product stream, which can be fed into a third distillation column.

[0239] A hydrogenation unit can be used to react hydrogen with a material under pressure and heat using a catalyst. The hydrogenation unit can be operated, for example, in a batch mode or continuously. Some types of catalysts that can be used can have a metal support. Non-limiting examples of metals useful for hydrogenation include palladium, platinum, nickel, and ruthenium. Non-limiting examples of supports for metal catalysts include carbon, alumina, and silica. The catalyst can also be in the form of a sponge metal such as, for example, Raney nickel. Other nickel catalysts are available from commercial suppliers and are, for example, NISAT 310 (trademark), E-3276 (BASF, Ludwigshafen, Germany), RANEY® 2486, or E-474 TR (Mallinckrodt Co., Calsicat Division, PA, USA). The pressure can be at least 50 psig, 100 psig, 200 psig, 300 psig, 400 psig, 500 psig, 600 psig or 1000 psig of hydrogen pressure, or a hydrogen pressure of about 100 psig to 1000 psig, about 200 psig to 600 psig, or about 400 psig to 600 psig. The temperature can be from ambient temperature to 200 °C, about 50 °C to 200 °C, about 80 °C to 150 °C, about 90 °C to 120 °C, about 100 °C to 130 °C, or about 125 °C to 130 °C. Hydrogenation is preferably carried out after a distillation procedure and includes substantially removing materials having a boiling point higher than 1,3-BG, such as unfermented sugars, nitrogen-containing compounds, otherwise heavy materials may contaminate the hydrogenation catalyst.

[0240] In some embodiments, the system includes an activated carbon unit configured to remove impurities from a bioderived 1,3-BG-containing product stream. In some embodiments, the activated carbon unit can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG and produce an activated-carbon-treated crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG, which can be fed into a polishing column or a dehydration column. In some embodiments, the polishing column is an ion-exchange chromatography column. In some embodiments, the activated carbon unit can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG with a reduced salt content and produce an activated-carbon-treated crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG, which can be fed into a dehydration column. In some embodiments, the activated carbon unit can receive a first bioderived 1,3-BG-containing product stream and produce an activated-carbon-treated first bioderived 1,3-BG-containing product stream, which can be fed into a first distillation column. In some embodiments, the activated carbon unit reactor can receive a second bioderived 1,3-BG-containing product stream and produce an activated-carbon-treated bioderived 1,3-BG-containing product stream, which can be fed into a second distillation column. In some embodiments, the activated carbon unit can receive a third bioderived 1,3-BG-containing product stream and produce an activated-carbon-treated third bioderived 1,3-BG-containing product stream, which can be fed into a third distillation column. In some embodiments, the activated carbon unit can receive a fourth bioderived 1,3-BG-containing product stream and produce an activated-carbon-treated fourth bioderived 1,3-BG-containing product stream. In some embodiments, the fourth bioderived 1,3-BG-containing product stream includes a purified bioderived 1,3-BG product. In some embodiments, the first, second, third, or fourth bioderived 1,3-BG-containing product stream consists essentially of the bioderived 1,3-BG provided herein.

[0241] In some embodiments, the system includes a sodium borohydride (NaBH4) addition device. In some embodiments, the NaBH4 addition device can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG and produce a NaBH4-treated crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG, which can be fed into a polishing column or a dehydration column. In some embodiments, the polishing column is an ion exchange chromatography column or includes activated carbon. In some embodiments, the NaBH4 addition device can receive a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG with reduced salt content and produce a NaBH4-treated crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG, which can be fed into a dehydration column. In some embodiments, the NaBH4 addition device can receive a first bioderived 1,3-BG-containing product stream and produce a NaBH4-treated first bioderived 1,3-BG-containing product stream, which can be fed into a first distillation column. In some embodiments, the NaBH4 addition device can receive a second bioderived 1,3-BG-containing product stream and produce a NaBH4-treated second bioderived 1,3-BG-containing product stream, which can be fed into a second distillation column. In some embodiments, the NaBH4 addition device can receive a third bioderived 1,3-BG-containing product stream and produce a NaBH4-treated third bioderived 1,3-BG-containing product stream, which can be fed into a third distillation column. In some embodiments, the NaBH4 addition device can receive a fourth bioderived 1,3-BG-containing product stream and produce a NaBH4-treated fourth bioderived 1,3-BG-containing product stream. In some embodiments, the fourth bioderived 1,3-BG-containing product stream includes a purified bioderived 1,3-BG product. In some embodiments, the first, second, third, or fourth bioderived 1,3-BG-containing product stream consists essentially of the bioderived 1,3-BG provided herein.

[0242] In some embodiments, the system includes a wiped film evaporator (WFE) that receives a first material stream having a boiling point higher than 1,3-BG and produces a distillate, while the distillate is fed to a first distillation column. In some embodiments, the system includes a WFE that receives a second material stream having a boiling point higher than 1,3-BG and produces a distillate, while the distillate is fed to a third distillation column. In some embodiments, the system includes a WFE that receives a first material stream having a boiling point higher than 1,3-BG and produces a distillate, while the distillate is fed to a first distillation column, and the system includes a WFE that receives a second material stream having a boiling point higher than 1,3-BG and produces a distillate, while the distillate is fed to a third distillation column.

[0243] In some embodiments, the system includes one or more reboilers. A reboiler is a heat exchanger typically used to provide heat to the bottom of an industrial distillation column. The reboiler boils the liquid from the bottom of the distillation column to generate vapor, and the vapor returns to the column, for example, to perform the distillation separation of bio-derived 1,3-BG. The heat supplied to the distillation column by the reboiler at the bottom of the column is generally removed by a condenser at the top of the column. Examples of reboilers include kettle reboilers, thermosyphon reboilers, fired reboilers, or forced circulation reboilers.

[0244] In some embodiments, the system includes a reboiler that receives liquid from a dehydration column and generates vapor, whereby the vapor returns to the dehydration column. In some embodiments, the system includes a reboiler that receives liquid from a first, second, or third distillation column, or a combination thereof, and generates vapor, whereby the vapor returns to the first, second, or third distillation column, or a combination thereof. In some embodiments, the system includes a reboiler that receives liquid from a dehydration column and generates vapor, whereby the vapor returns to the dehydration column. In some embodiments, the system includes a reboiler that receives liquid from a dehydration column and generates vapor, whereby the vapor returns to the dehydration column, and the system includes a reboiler that receives liquid from a first, second, or third distillation column, or a combination thereof, and generates vapor, whereby the vapor returns to the first, second, or third distillation column, or a combination thereof.

[0245] In some embodiments, the reboiler is used to add reagents, such as bases, to the system or the process using the system.

[0246] In some embodiments, the purified bio-derived 1,3-BG product produced by the system provided herein consists essentially of the bio-derived 1,3-BG provided herein.

[0247] In another aspect, a bio-derived 1,3-BG produced by the system provided herein is provided. In some embodiments, the bio-derived 1,3-BG produced by the system provided herein is the bio-derived 1,3-BG provided herein.

[0248] In some embodiments, the bio-derived 1,3-BG has a chiral purity of 55% or higher, or 95% or higher, or any other chiral purity disclosed herein. For example, as described with reference to FIGS. 15A-15C, the crude bio-derived 1,3-BG mixture or partially purified bio-derived 1,3-BG, such as that fed into a distillation system, may contain bio-derived 1,3-BG having a chiral purity of 55% or higher.

[0249] In some embodiments, the purified bio-derived 1,3-BG product has a chemical purity of 99.0% or higher, or 99.5% or higher, or any other chemical purity disclosed herein. For example, as described with reference to FIGS. 15A-15C, the purified bio-derived 1,3-BG product produced from a distillation system may contain bio-derived 1,3-BG having a chemical purity of 99.0% or higher. Further, in some embodiments, the purified bio-derived 1,3-BG product produced may contain 1,3-BG having a chiral purity of 55% or higher.

[0250] An example of the distillation system provided in this specification is shown in FIG. 15A. The crude bio-derived 1,3-BG mixture or the partially purified bio-derived 1,3-BG 500 is supplied to the dehydration column 510, where the light material 512 (a material having a boiling point lower than 1,3-BG such as water) is removed from the top of the first column 510. The bio-derived 1,3-BG-containing product stream 514 is discharged from the bottom of the first column and supplied to the first distillation column 520. The heavy material 524 (a material having a boiling point higher than 1,3-BG) is removed from the bottom of the first distillation column 520, and the bio-derived 1,3BG-containing product stream 522 is discharged from the top of the first distillation column 520. The heavy material 524 can be supplied to the wiped film evaporator (WFE) 525 as needed, where the WFE distillate 542 and the heavy material are produced. The WFE distillate 542 is supplied to the first distillation column 520 as needed. The bio-derived 1,3-BG-containing product stream 522 is supplied to the second distillation column 530. The distillation column 530 removes the light material 532 from the top of the column 530 and the third bio-derived 1,3-BG-containing product stream 534 from the bottom of the column 530. The third bio-derived 1,3-BG-containing product stream (1,3-BDO-containing product stream) 534 is supplied to the third distillation column 550. The purified bio-derived 1,3-BG (1,3-BDO) product 552 is collected from the top of the column 550, and the heavy material 554 is discharged from the bottom of the column 550.

[0251] The example shown in Fig. 15B is obtained by adding an alkali reactor 560' to the system of Fig. 15A. For example, the crude bioderived 1,3-BG mixture or the partially purified bioderived 1,3-BG 500' is supplied to the dehydration column 510', where the light material 512' (materials having a boiling point lower than 1,3-BG such as water) is removed from the top of the first column 510'. The bioderived 1,3-BG-containing product stream 514' is discharged from the bottom of the first column and supplied to the first distillation column 520'. The heavy material 524' (materials having a boiling point higher than 1,3-BG) is removed from the bottom of the first distillation column 520', and the bioderived 1,3-BG-containing product stream 522' is discharged from the top of the first distillation column 520'. The heavy material 524' can be supplied to the WFE 525' as needed, where the WFE distillate 542' and the heavy material are produced, and the WFE distillate 542' is supplied to the first distillation column as needed. The bioderived 1,3-BG-containing product stream 522' is supplied to the alkali reactor 560', which sends the stream 562'' to the second distillation column 530'. The distillation column 530' removes the light material 532' from the top of the column 530' and the third bioderived 1,3-BG-containing product stream 534' from the bottom of the column 530'. The third bioderived 1,3-BG-containing product stream (1,3-BDO-containing product stream) 534' is supplied to the third distillation column 550'. The purified bioderived 1,3-BG (1,3-BDO) product 552' is collected from the top of the column 550', and the heavy material 554' is discharged from the bottom of the column 550'.

[0252] The example shown in FIG. 15C is the one in which an activated carbon unit 570'' is added to the system of FIG. 15A. For example, a crude bioderived 1,3-BG mixture or a partially purified bioderived 1,3-BG 500'' is supplied to a dehydration column 510'', where light material 512'' (a material having a lower boiling point than 1,3-BG such as water) is removed from the top of the first column 510''. The bioderived 1,3-BG-containing product stream 514'' is discharged from the bottom of the first column and supplied to a first distillation column 520''. Heavy material 524'' (a material having a higher boiling point than 1,3-BG) is removed from the bottom of the first distillation column 520'', and the bioderived 1,3BG-containing product stream 522'' is discharged from the top of the first distillation column 520''. The heavy material 524'' can be supplied to the WFE 525'' as needed, where a WFE distillate 542'' and a heavy material are produced, and the WFE distillate 542'' is supplied to the first distillation column as needed. The bioderived 1,3-BG-containing product stream 522'' is supplied to an alkali reactor (not particularly shown in FIG. 15C), which sends the stream to a second distillation column 530'' in a manner as described with reference to FIG. 15B. The distillation column 530'' removes light material 532'' from the top of the column 530'' and a third bioderived 1,3-BG-containing product stream 534'' from the bottom of the column 530''. The third bioderived 1,3-BG-containing product stream (1,3-BDO-containing product stream) 534'' is supplied to a third distillation column 550''. The purified bioderived 1,3-BG (1,3-BDO) product 552'' is collected from the top of the column 550'', and the heavy material 554'' is discharged from the bottom of the column 550''. The purified bioderived 1,3-BG (1,3-BDO) product 552'' is supplied to the activated carbon unit 570'', where an activated carbon-treated product 572'' is produced.

[0253] In some embodiments, the carbon raw material, as well as other cell uptake raw materials such as phosphate, ammonia, sulfate, chloride, and other halogens, can be selected such that the isotope distribution of the atoms present in the bioderived 1,3-BG (1,3-BDO), or its related downstream products such as esters or amides thereof, or any bioderived 1,3-BG (1,3-BDO) pathway intermediate, is changed. The various carbon raw materials and the other uptake raw materials listed above will collectively be referred to herein as "uptake raw materials". The uptake raw materials can enrich the isotope of any atom present in the product bioderived 1,3-BG (1,3-BDO), or its related downstream products such as esters or amides thereof, or the bioderived 1,3-BG (1,3-BDO) pathway intermediate, or by-products generated by reactions different from the bioderived 1,3-BG (1,3-BDO) pathway. Isotope enrichment can be achieved, for example, for any target atom containing carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, chloride, or other halogens.

[0254] In some embodiments, the uptake raw materials can be selected such that the ratios of carbon-12, carbon-13, and carbon-14 are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of oxygen-16, oxygen-17, and oxygen-18 are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of hydrogen, deuterium, and tritium are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of nitrogen-14 and nitrogen-15 are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of sulfur-32, sulfur-33, sulfur-34, and sulfur-35 are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of phosphorus-31, phosphorus-32, and phosphorus-33 are changed. In some embodiments, the uptake raw materials can be selected such that the ratios of chlorine-35, chlorine-36, and chlorine-37 are changed.

[0255] In some embodiments, the isotope ratio of the target atom can be changed to a desired ratio by selecting one or more incorporation raw materials. The incorporation raw materials can be derived from natural raw materials or artificial raw materials found in nature, and those skilled in the art can select natural raw materials, artificial raw materials, or combinations thereof to achieve the desired isotope ratio of the target atom. Examples of artificial incorporation raw materials include, for example, incorporation raw materials at least partially derived from chemical synthesis reactions. Such isotope-enriched incorporation raw materials can be purchased commercially, prepared in a laboratory, and / or mixed with natural raw materials of the incorporation raw materials as needed to achieve the desired isotope ratio. In some embodiments, the target atom isotope ratio of the incorporation raw materials can be achieved by selecting the desired origin of the incorporation raw materials found in nature. For example, as discussed herein, natural raw materials can be bio-based raw materials derived from or synthesized by raw materials such as biological organisms or petroleum-based products or derived from or synthesized by the atmosphere. In some such embodiments, for example, the source of carbon can be selected from a fossil fuel-derived carbon source that may have relatively little carbon-14, or an environmental or atmospheric carbon source such as CO2 that may have a greater amount of carbon-14 than its petroleum-derived equivalent.

[0256] The unstable carbon isotope carbon-14 or radiocarbon makes up approximately 1 out of 10 12 carbon atoms in the Earth's atmosphere and has a half-life of about 5700 years. Stored carbon is replenished in the upper atmosphere by nuclear reactions involving cosmic rays and ordinary nitrogen ( 14 N). Fossil fuels do not contain carbon-14 because they decayed long ago. When fossil fuels are burned, the fraction of carbon-14 in the atmosphere decreases, which is called the "Suess effect".

[0257] Methods for determining the isotope ratios of atoms in a compound are well known to those skilled in the art. Isotope enrichment can be readily evaluated by mass spectrometry using techniques known in the art such as accelerator mass spectrometry (AMS), stable isotope ratio mass spectrometry (SIRMS), and site-specific natural isotopic fractionation by nuclear magnetic resonance (SNIF-NMR). Such mass spectral techniques can be integrated with separation techniques such as liquid chromatography (LC), high performance liquid chromatography (HPLC), and / or gas chromatography.

[0258] In the case of carbon, ASTM D6866 was developed in the United States as a standardized analytical method by the American Society for Testing and Materials (ASTM) International for determining the bio-based content of solid, liquid, and gaseous samples using radiocarbon dating. The standard method is based on the use of radiocarbon dating to determine the bio-based content of a product. ASTM D6866 was first published in 2004, and the current active version of the standard is ASTM D6866-11 (implemented on April 1, 2011). Radiocarbon dating techniques are well known to those skilled in the art and include those described herein.

[0259] The bio-based content of a compound is estimated by the ratio of carbon-14 ( 14 C) to carbon-12 ( 12 C). In particular, the fraction modern (Fm) is computer calculated from the equation: Fm = (S - B) / (M - B), where B, S, and M are the 14 C / 12 C ratios of the blank, sample, and modern reference, respectively. The fraction modern is a measure of the deviation of the 14 C / 12 C ratio of a sample from that of a "modern". A modern has a δ 13 C VPDB=-19 per mil normalized to the radiocarbon concentration (in AD 1950) of the National Bureau of Standards (NBS) Oxalic Acid I (i.e., Standard Reference Material (SRM) 4990b) as defined by 95% (Olsson, The use of Oxalic acid as a Standard, Radiocarbon Variations and Absolute Chronology, Nobel Symposium, Proc. 12th ed., John Wiley & Sons, New York (1970), the entire content of which is hereby incorporated by reference). For example, the results of mass spectrometry measured by ASM are δ 13 C VPDB =-19 per mil normalized to 0.95 times the specific activity of NBS Oxalic Acid I (SRM 4990b) using the internationally approved definition. This is equivalent to an absolute (AD 1950) 14 C / 12 C ratio of 1.176 ± 0.010 × 10 -12 (Karlen et al., Arkiv Geofysik, Vol. 4: pp. 465 - 471 (1968), the entire content of which is hereby incorporated by reference). Standard calculations take into account the differential uptake of one isotope compared to another, e.g., the preferential uptake of C 12 <C 13 <C 14 in biological systems, and these corrections are reflected as Fm corrected with respect to δ 13 .

[0260] The oxalic acid standard (SRm4990b or HOx1) was prepared from sugar beets harvested in 1955. Although 1000 lb were produced, this oxalic acid standard is no longer commercially available. The oxalic acid II standard (HOx2; N.I.S.T. designated SRM 4990 C) was prepared from French beet molasses harvested in 1977. In the early 1980s, a group of 12 laboratories measured the ratio of the two standards. The ratio of the activity of oxalic acid II to 1 is 1.2933 ± 0.001 (weighted average). The isotope ratio of HOxII is -17.8 per mil. ASTM D6866-11 recommends the use of the oxalic acid II standard SRM 4990C (Hox2) available for modern standards (see discussion of original vs. currently available oxalic acid standards in Mann, Radiocarbon, Vol. 25(2):519 - 527 (1983), which is hereby incorporated by reference in its entirety). Fm = 0% represents the absence of carbon-14 atoms in the material and thus indicates a fossil (e.g., petroleum-based) carbon source. Fm = 100% represents a complete modern carbon source after correction for the injection of carbon-14 into the atmosphere from nuclear tests since 1950. Such "modern" feedstocks described herein include bio-based feedstocks.

[0261] As described in ASTM D6866-11, the effect of the 1950s nuclear test program, which caused a significant enrichment of carbon-14 in the atmosphere, continues but is decreasing, so that the modern carbon percentage (pMC) may exceed 100% as described in ASTM D6866. Since the carbon-14 activity of all samples is referenced to a "pre-bomb" standard and almost all new bio-based products are produced in a post-bomb environment, it is necessary to multiply all pMC values (after correction for isotope fractionation) by 0.95 (as of 2010) to improve the reflection of the true bio-based content of the samples. A bio-based content exceeding 103% suggests either that an analytical error has occurred or that the feedstock of the bio-based carbon is older than several years.

[0262] ASTM D6866 quantifies the bio-based content relative to the total organic content of a material, without consideration of the presence of inorganic carbon and other carbon-free substances. For example, a product that is 50% starch-based material and 50% water would be considered to have a bio-based content = 100% (50% of the organic content is 100% bio-based) based on ASTM D6866. In another example, a product that is 50% starch-based material, 25% petroleum-based, and 25% water would have a bio-based content = 66.7% (75% is the organic content, but only 50% of the product is bio-based). In another example, a product that is 50% organic carbon and a petroleum-based product would be considered to have a bio-based content = 0% (50% is organic carbon, but from fossil feedstocks). Thus, based on well-known methods and known standards for determining the bio-based content of a compound or material, one of ordinary skill in the art can readily determine the bio-based content of a compound or material and / or prepare downstream products utilizing the compounds or materials provided herein having a desired bio-based content.

[0263] The use of carbon-14 dating techniques to quantify the biobased content of materials is known in the art (Currie et al., Nuclear Instruments and Methods in Physics Research B, Vol. 172: 281-287 (2000), the entire content of which is incorporated herein by reference). For example, carbon-14 dating has been used to quantify the biobased content in terephthalate-containing materials (Colonna et al., Green Chemistry, Vol. 13: 2543-2548 (2011), the entire content of which is incorporated herein by reference). In particular, polypropylene terephthalate (PPT) polymers derived from renewable 1,3-propanediol and petroleum-derived terephthalic acid yielded an Fm value of approximately 30% (i.e., 3 / 11 of the macromolecular carbon was derived from renewable 1,3-propanediol and 8 / 11 was derived from terephthalic acid, which is a fossil end member) (Currie et al., see above, 2000). In contrast, polybutylene terephthalate polymers derived from both renewable 1,4-butanediol and renewable terephthalic acid yielded a biobased content of over 90% (Colonna et al., see above, 2011).

[0264] Accordingly, in some embodiments, the present disclosure provides bio-derived 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-derived 1,3-BG (1,3-BDO) pathway intermediates, produced by suitable cells having carbon-12, carbon-13, and carbon-14 ratios that reflect atmospheric carbon uptake feedstocks, also referred to as environmental carbon. For example, in some aspects, the bio-derived 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-derived 1,3-BG (1,3-BDO) pathway intermediates can have an Fm value of at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100%. In some such embodiments, the uptake feedstock is CO2. In some embodiments, the compositions, systems, and methods provide bio-derived 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-derived 1,3-BG (1,3-BDO) pathway intermediates, having carbon-12, carbon-13, and carbon-14 ratios that reflect petroleum-based carbon uptake feedstocks. In this aspect, the bio-derived 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-derived 1,3-BG (1,3-BDO) pathway intermediates can have an Fm value of less than 95%, less than 90%, less than 85%, less than 80%, less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, less than 2% or less than 1%.In some embodiments, the compositions, systems, and methods provide bio-derived 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-derived 1,3-BG (1,3-BDO) pathway intermediates having carbon-12, carbon-13, and carbon-14 ratios obtained by a combination of atmospheric carbon capture feedstocks and petroleum-based capture feedstocks. The use of such a combination of capture feedstocks is one way by which the carbon-12, carbon-13, and carbon-14 ratios can be altered, and each ratio will reflect the ratio of the capture feedstocks.

[0265] Furthermore, the compositions, systems, and methods herein relate to biologically produced bio-based 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-based 1,3-BG (1,3-BDO) pathway intermediates, and products derived therefrom, where the bio-based 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-based 1,3-BG (1,3-BDO) pathway intermediates have a carbon-12, carbon-13, and carbon-14 isotope ratio that is approximately the same value as the CO2 that occurs in the environment. For example, in some embodiments, the compositions, systems, and methods provide bio-based 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-based 1,3-BG (1,3-BDO) intermediates having a carbon-12 to carbon-13 to carbon-14 isotope ratio that is approximately the same value as the CO2 that occurs in the environment, or any of the other ratios disclosed herein. As disclosed herein, the products can have a carbon-12 to carbon-13 to carbon-14 isotope ratio that is approximately the same value as the CO2 that occurs in the environment, or any of the ratios disclosed herein, where the products are produced from bio-based 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or bio-based 1,3-BG (1,3-BDO) pathway intermediates disclosed herein, and it is understood that the bio-based products are chemically modified to produce the final product. Methods of chemically modifying bio-based products of bio-based 1,3-BG (1,3-BDO), or related downstream products thereof such as esters or amides, or intermediates of bio-based 1,3-BG (1,3-BDO) to produce the desired products are well known to those of ordinary skill in the art described herein.

[0266] The compositions, systems, and methods can be based on biogenic 1,3-BG (1,3-BDO), or downstream products related thereto such as esters or amides thereof, including plastics, elastic fibers, polyurethanes, polyesters including polyhydroxyalkanoates, nylon, organic solvents, polyurethane resins, polyester resins, hypoglycemic agents, butadiene and / or butadiene-based products, and plastics, elastic fibers, polyurethanes, polyhydroxyalkanoates such as poly-4-hydroxybutyrate (P4HB) or copolymers thereof, poly(tetramethylene ether) glycol (PTMEG) (also referred to as PTMO, polytetramethylene oxide), polybutylene terephthalate (PBT), and polyesters including polyurethane-polyurea copolymers referred to as spandex, elastane or Lycra™, nylon, etc., where the plastics, elastic fibers, polyurethanes, polyhydroxyalkanoates such as poly-4-hydroxybutyrate (P4HB) or copolymers thereof, poly(tetramethylene ether) glycol (PTMEG) (also referred to as PTMO, polytetramethylene oxide), polybutylene terephthalate (PBT), and polyesters including polyurethane-polyurea copolymers referred to as spandex, elastane or Lycra™, nylon, organic solvents, polyurethane resins, polyester resins, hypoglycemic agents, butadiene, and / or butadiene-based products are produced directly from or in combination with biogenic 1,3-BG (1,3-BDO), or downstream products related thereto such as esters or amides thereof, or biogenic 1,3-BG (1,3-BDO) pathway intermediates disclosed herein.

[0267] Biologically-derived 1,3-BG (1,3-BDO) can react with an acid either in vivo or in vitro and can be converted to an ester, for example using a lipase. Such esters can have uses in nutraceuticals, pharmaceuticals and foods and, when the R form of 1,3-BG (1,3-BDO) is used, it is the form that is most utilized as an energy source in both animals and humans (e.g., (R)-3-hydroxybutyl-R-1,3-butanediol monoester (which has Generally Recognized As Safe (GRAS) approval in the United States) and ketoesters such as (R)-3-hydroxybutyrate glycerol monoester or diester) as compared to the S form or racemic mixture. The ketoester can be delivered orally and the ester releases R-1,3-butanediol which is used by the body (see, e.g., WO2013150153, the entire contents of which are incorporated herein by reference). Thus the compositions, systems, and methods are particularly useful for providing improved enzyme pathways and microorganisms for providing a biologically-derived 1,3-BG (1,3-BDO) that further has a highly enriched or essentially enantiopure and improved purity quality with respect to by-products, i.e., an improved composition of, for example, R-1,3-butanediol.

[0268] Biologically-derived 1,3-BG (1,3-BDO) has, or can have, further food-related uses including direct use as a food ingredient, food component, flavoring agent, solvent or solubilizing agent for flavoring agents, stabilizer, emulsifier, and antibacterial agent, and preservative. Biologically-derived 1,3-BG (1,3-BDO) is used, or can be used, as a parenteral drug solvent in the pharmaceutical industry. Biologically-derived 1,3-BG (1,3-BDO) is found, or can be found, in cosmetics as a skin softening agent, a wetting agent to prevent crystallization of insoluble components, a solubilizing agent component for poorly water-soluble components such as fragrances, and as an antibacterial agent and preservative. For example, it can be used especially as a wetting agent in hair sprays and setting lotions; it can reduce, or can reduce, the loss of fragrance from essential oils, protect against spoilage by microorganisms, and is used, or can be used, as a solvent for benzoates. Biologically-derived 1,3-BG (1,3-BDO) can be used at concentrations of 0.1% to 50%, further less than 0.1%, further higher than 50%. It is used, or can be used, in hair and bath products, eye and facial makeup, fragrances, personal cleansing products, and shaving and skin care preparations (see, for example, the Cosmetic Ingredient Review board’s report: “Final Report on the Safety Assessment of Butylene Glycol, Hexylene Glycol, Ethoxydiglycol, and Dipropylene Glycol”, Journal of American College of Toxicology, Volume 4, Number 5, 1985, which is hereby incorporated by reference in its entirety). This report provides specific uses and concentrations of 1,3-BG (1,3-BDO) in cosmetics; see, for example, Table 2 entitled “Product Formulation Data” in that report.

[0269] The recitation of elements in any definition of a variable group in this specification includes the definition of the variable group as any single element or combination (or sub - combination) of the recited elements. The description of embodiments in this specification includes any single embodiment or an embodiment in combination with any other embodiment or portions thereof.

[0270] All patents and documents mentioned in this specification are hereby incorporated by reference in their entirety to the same extent as if each individual patent and document was specifically and individually indicated to be incorporated by reference.

[0271] The following examples are provided by way of illustration and not limitation.

Example

[0272] (Example 1) Laboratory - scale production and purification of Bio - BG A fermentation broth enriched with biogenic 1,3 - BG was produced using, for example, strains and the following protocol as described in WO2010 / 127319A2 and WO2011 / 071682A1. The entire content of each of these is hereby incorporated by reference into this specification. Briefly stated, an exemplary or preferred microbial pathway to bio - BG is described in WIPO patent document WO2010127319A2, and reference is particularly made to pathways including 3 - hydroxybutyryl - CoA dehydrogenase, such as the pathway from acetoacetyl - CoA to 1,3 - butanediol in Figure 2 thereof including step H. In one embodiment, the 3 - hydroxybutyryl - CoA dehydrogenase may be specific for the R enantiomer and can be modified to have such specificity. The following provisional applications are also referenced, and these provisional applications are also hereby incorporated by reference into this specification in their entirety: (1) US Patent Provisional Application No. 62 / 480,208 (Attorney Docket No. 12956 - 409 - 888) entitled "3 - HYDROXYBUTYRYL - COA DEHYDROGENASE VARIANTS AND METHODS OF USE", filed on March 31, 2017; (2) US Patent Provisional Application No. 62 / 480,194 (Attorney Docket No. 12956 - 408 - 888) entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE", filed on March 31, 2017; (3) International Patent Application No. _ (Attorney Docket No. 12956 - 409 - 228) entitled "3 - HYDROXYBUTYRYL - COA DEHYDROGENASE VARIANTS AND METHODS OF USE", filed on the same date as this application; and (4) International Patent Application No. _ (Attorney Docket No. 12956 - 408 - 228) entitled "ALDEHYDE DEHYDROGENASE VARIANTS AND METHODS OF USE", filed on the same date as this application.

[0273] Thereafter, the bio-derived 1,3-BG was purified from the fermentation broth using the sequence of (1) microfiltration, (2) nanofiltration, (3) ion exchange chromatography, (4) evaporation of water, and (5) polishing ion exchange to produce a crude mix containing bio-derived 1,3-BG. The crude mix was then fed to a dehydration distillation column to produce a 1,3-BG-containing product stream, which was fed to a 2 L batch distillation column to produce the bio-derived 1,3-BG product. The batch distillation column was a randomly packed column with a diameter of 1 inch and a height of about 2 feet, and had a condenser and a reflux controller mounted directly on top of the column. Batch distillation at a high reflux rate can produce high-purity bio-derived 1,3-BG.

[0274] This example demonstrates that the highest purity bio-BG can be obtained by a batch distillation process using, for example, a laboratory-scale distillation system as described above, even in the absence of additional purification steps involving, for example, activated carbon treatment, hydrogenation, base addition, or borohydride treatment. Exemplary results for a distillation process involving dehydration / heavy (DW / HV) distillation at a reflux ratio of 3:1, followed by light / 1,3-BG (LT / BG) distillation at a reflux ratio of 3:1 are shown in Table 2. A high-purity bio-derived 1,3-BG fraction was obtained, having a purity of 99.9% on a dry basis and 4-hydroxy-2-butanone and 3-butanedial levels of less than 50 ppm.

[0275] It is believed that further improvements can be achieved in the purity and odor of bio-derived 1,3-BG using a continuous distillation process. A continuous distillation process, especially with a high degree of vacuum and a high reflux ratio, is believed to be useful in reducing the odor of bio-1,3-BG. Without wishing to be bound by theory, it is believed that under such a process conditions, when 4-hydroxy-2-butanone (4-OH-2-butanone) and 3-hydroxy-butanedial (3-OH-butanedial) decompose, strong odor by-products such as MVK and Cr-Ald may be reduced or avoided.

Table 2

[0276] The comparative purity assessment of bio-BG and petro-BG samples was performed using gas chromatography / mass spectrometry (GC-MS) analysis. Representative bio-BG samples were obtained on a laboratory scale as described in Example 1. Representative industrial grade and cosmetic grade petro-BG reference samples are commercially available, e.g., manufactured by Oxea Corp., Bay City, TX. Compounds having a GC retention time shorter than that of 1,3-BG are referred to herein as "light substances". Compounds having a GC retention time longer than that of 1,3-BG are referred to herein as "heavy substances".

[0277] Briefly stated, 3-hydroxy-butan-al (3OH-butan-al) and 4-hydroxy-2-butanone (4OH-2-butanone) were identified or considered to be identified as two bio-BG specific compounds present at substantially high levels (about 1,000 ppm) in bio-BG samples. Neither 3-hydroxy-butan-al nor 4-hydroxy-2-butanone could be detected by GC-MS in industrial grade petro-BG or cosmetic grade petro-BG samples, or were present at substantially lower levels (e.g., about 100 - 1,000 times lower levels) in industrial grade or cosmetic grade petro-BG compared to bio-BG.

[0278] Two additional bio-BG specific compounds were identified as heavies in the bio-BG sample and are referred to herein as "Compound 7" and "Compound 9". Neither Compound 7 nor 9 could be detected by GC-MS in industrial grade or cosmetic grade petro-BG, or were present at substantially lower levels (e.g., about 100 - 1,000 times lower) in industrial grade or cosmetic grade petro-BG compared to bio-BG. The proposed structures for Compounds 7 and 9 are provided elsewhere herein, but such proposed structures are not intended to be limiting.

[0279] Generally, industrial grade and cosmetic grade petro-BG samples were found to have numerous and high levels of "heavies" impurities compared to the bio-BG sample, such as the bio-BG sample of Example 1 as determined by GC-MS.

[0280] The 1,3-BG sample was diluted 2-fold (DF2) or 20-fold (DF20) with acetonitrile and subjected to GC-MS analysis. The DF2 sample was used to quantify known impurities in the sample based on an external standard calibration consisting of multiple levels as described below. The DF20 sample was used to determine the (area) purity % of 1,3-BG "lights" and "heavies" based on the total ion current (TIC) peak area.

[0281] 1,3-BG analysis was performed using an Agilent gas chromatograph 6890N connected to a mass selective detector (MSD) 5973N and operated in electron impact ionization (EI) mode. 0.5 μL of the 1,3-BG sample was diluted 2-fold or 20-fold with acetonitrile and introduced in split injection mode with a split ratio of 50:1 and an injection port temperature of 250 °C. Helium was used as the carrier gas and a constant flow rate of the carrier gas was maintained at 1.5 mL / min. The following high-speed GC temperature program was developed and the 1,3-BG purity was analyzed on an HP-INNOWax (trademark) column (Agilent Technologies, Santa Clara, CA): the oven was first maintained at 50 °C for 3 minutes, then raised to 250 °C at 15 °C / min and maintained for 5 minutes (total run time was 21.33 minutes). The MS interface transfer line was maintained at 280 °C. Data was acquired using 25 - 500 m / z mass range scans.

[0282] The typical retention times (RT) on an HP-INNOWax (trademark) capillary column (30 m × 0.25 mm × 0.25 μm (Agilent)) for all known heavy or light compounds in the 1,3-BG sample were established by injecting undiluted reference compounds.

[0283] An external standard calibration was developed to identify heavy or light compounds such as 3-hydroxy-butan-al or 4-hydroxy-2-butanone. The standard calibration included a series of six reference compound concentrations in the range of 5 to 1000 ppm of the reference compound. Quantification was performed using total ion current (TIC) and / or extracted ion current (XIC) chromatograms based on characteristic target ions for each compound of interest. Furthermore, qualifier ions were selected from the mass spectra of each target compound. The relative signal intensity of the qualifier ions to the target ions was determined to confirm the identity with the target compound. Quantification of the test compound was performed based on the standard curve of the reference compound using a second-order fit.

[0284] The calculation regarding the purity % represents the GC purity based on the GC peak area. Compounds having a retention time shorter than that of 1,3-BG (RT approximately 11.85 minutes) are referred to as "light substances", and compounds having a retention time longer than that of 1,3-BG are referred to as "heavy substances".

[0285] Figure 1 shows an overlay of exemplary GC-MS chromatograms (total ion current, TIC) of the bio-BG sample as well as industrial grade petro-BG and cosmetic grade petro-BG samples in 2-fold sample dilution (DF2 sample). The major peak (retention time (RT): 11.85 minutes) at the center of each of the three chromatograms represents 1,3-BG.

[0286] Table 3 shows the results of the overall GC-MS purity analysis of the bio-BG and petro-BG samples in Figure 1. It was recognized that industrial grade and cosmetic grade petro-BG samples have overall higher levels of heavy and light substance impurities compared to bio-BG.

Table 3

[0287] Table 4 shows the results of the quantitative analysis of 3-hydroxy-butanals and 4-hydroxy-2-butanone levels in the 1,3-BG sample in Figure 1. 3-Hydroxy-butanals (RT: 9.51) and 4-hydroxy-2-butanone (RT: 10.08) are detectable as bio-BG specific "light substance" compounds, which were present at 100-fold or higher levels in the bio-BG sample compared to industrial grade petro-BG or cosmetic grade petro-BG samples.

Table 4

[0288] A heavy compound (Compound 9) with a retention time of about 12.5 minutes, which is an additional bio - BG - specific compound, was detected in the bio - BGD2 sample and not detected in the petro - BGD2 sample. See Figure 1. Generally, more heavy compounds were detected in cosmetic - grade petro - BG and industrial - grade petro - BG than in bio - BG. See Figure 1 for example. Heavy compounds detected in both the petro - BG sample and the bio - BG sample were found to be present at high levels in the petro - BG sample compared to the bio - BG sample, or, for example, for individual heavy compounds, at low levels in the petro - BG sample compared to the bio - BG sample. See Figure 1 for example. A specific petro - BG - specific light compound was detected at a retention time in the range of 10.1 minutes to 11.5 minutes. Cosmetic - grade and industrial - grade Petro - BGDF2 samples were generally found to have similar numbers and levels of light and heavy compounds. See Figure 1 for example.

[0289] Figure 2 shows an overlay of exemplary GC - MS chromatograms of the bio - BG sample and industrial - grade petro - BG and cosmetic - grade petro - BG samples at 20 - fold sample dilution (DF20 samples). The bio - BG - specific compounds 3 - hydroxy - butanal, 4 - hydroxy - 2 - butanone, and Compound 9 were also detected in the DF20 1,3 - BG sample. Additionally, Compound 7, an additional bio - BG - specific heavy compound, was detected at a retention time of about 12.05 minutes. The level of Compound 7 was about 1,000 ppm in the bio - BG sample. Compound 7 was not detected by GC - MS in either cosmetic - grade or industrial - grade petro - BG, or was found to be present at a concentration at least 100 - fold lower compared to bio - BG.

[0290] Figure 3 shows an exemplary mass spectrum of bio - BG - specific heavy compound 7 observed at a retention time of about 12.05 minutes in the GC - MS chromatogram, along with the proposed interpretation of a particular mass fragment being displayed. Without wishing to be bound by any theory, m / z = 161 is thought to be the molecular ion peak of compound 7. Without wishing to be bound by any theory, m / z = 183 is thought to be the sodium adduct of the molecular ion of compound 7.

[0291] Figure 4 shows an exemplary mass spectrum of bio - BG - specific heavy compound 9 observed at a retention time of about 12.51 minutes in the GC - MS chromatogram, along with the proposed interpretation of a particular mass fragment being displayed. Without wishing to be bound by any theory, m / z = 161 is thought to be the molecular ion peak of compound 9. Without wishing to be bound by any theory, m / z = 183 is thought to be the sodium adduct of the molecular ion of compound 9.

[0292] While not wishing to be bound by theory, for example, the fragmentation mass spectra of compounds 7 and 9 as shown in Figures 3 and 4 indicate that compounds 7 and 9 have the same elemental composition (C8H 16It is considered to be, or to suggest the possibility of, a structural isomer sharing O3). In particular, Compounds 7 and 9 are thought to exhibit similar fragmentation patterns. The individual fragments shared by Compounds 7 and 9 were frequently detectable at various TIC intensities. For example, the mass spectra of Compounds 7 and 9 share characteristic 115 m / z and 145 m / z fragments. The 145 m / z fragment of Compound 7 (Figure 3) was found to have a higher intensity than the corresponding 145 m / z fragment of Compound 9 (Figure 4). The 115 m / z fragment of Compound 7 was found to have a slightly lower intensity compared to the corresponding 115 m / z fragment of Compound 9. Further fragments shared in the mass spectra of Compounds 7 and 9 are the 45 m / z and 73 m / z fragments. The presence of a sufficient 145 m / z fragment is thought to indicate, or to suggest, a high-frequency loss of a methyl group (-CH3) (-15) from Compound 7, while the 73 m / z and 45 m / z fragments are thought to indicate, or to suggest, the presence of hydroxybutyl (73 m / z) and hydroxyl ethyl (45 m / z) fragments. The prominent 115 m / z fragment of Compound 9 is thought to indicate, or to suggest, a high-frequency loss of the hydroxyethyl moiety from Compound 9. Table 5 shows the proposed chemical structures for Compounds 7 and 9 based on the observed mass spectrometry fragmentation patterns shown, for example, in Figures 3 and 4. Figure 5 shows a chemical structure diagram explaining the proposed structures and proposed fragmentation of Compounds 7 and 9 based on the proposed mass fragments thought to be observed by mass spectrometry. The structures proposed in Figure 5 and Table 5 and the proposed fragmentation shown in Figure 5 are not intended to be limiting.

Table 5

[0293] Although not wishing to be bound by theory, it is possible that Compounds 7 and 9 are, or could be, the products of a condensation reaction that occurred between, for example, 3-hydroxy-butanals and 4-hydroxy-2-butanone, particularly in bio-BG.

[0294] Figure 6A shows an exemplary extracted ion chromatogram for m / z 115 of a bio-BG sample.

[0295] Figure 6B shows an exemplary extracted ion chromatogram for m / z 115 of a petro-BG sample.

[0296] Figure 7 shows exemplary liquid chromatography mass spectrometry (LC-MS) chromatograms (TIC: total ion current) of a bio-BG sample (upper panel), a cosmetic grade petro-BG sample (central panel), and an industrial grade petro-BG sample (lower panel). The base peak LCMS chromatogram reveals differences in the impurity profiles between bio-BG and petro-BG. The major BG peak elutes early at a retention time of 3 minutes, followed by the elution of impurities in the range of 5 - 9 minutes. The cosmetic and industrial grade petro-BG appear similar, while bio-BG has a relatively low impurity content. Figures 8A - 8B are comparable to the XIC for the most intense m / z values (peaks eluting at 6.25, 6.45, and 6.65 minutes) obtained from the TIC data in Figure 7.

[0297] Figures 8A and 8B show the results of LC-MS analysis of an exemplary 1,3-BG sample, along with the proposed interpretation of a specific mass fragment shown in Figure 8B. The upper panel in Figure 8A shows the total ion current (TIC) profile of a bio-BG sample. The bottom three panels in Figure 8A show the extracted ion current chromatograms (XIC(IEX), C8H 16The theoretical exact masses of the O3 heavy compounds (±10 ppm width around) are exemplified. A number of heavy peaks were detected at retention times of 6.2 min, 6.4 min, and 6.6 min in all three samples. See Figure 8A. The mass spectrometry fragmentation patterns of the compounds from the three heavy peaks indicated that all three peaks represented molecules with the same elemental composition C8H 16 O3. See Figure 8B. Although not wishing to be bound by theory, the three heavy peaks observed in the bio-BG and petro-BG samples are thought to represent structural isomers. The structures proposed in Figure 8B are not intended to be limiting.

[0298] By LC-MS analysis, a petro-specific heavy compound with a retention time of 7.3 min and an elemental composition of C8H 14 O3 and a molecular weight of 158 was further identified. See Figure 9A. Although not wishing to be constrained by any theory, for example, the observed fragmentation pattern of the petro-BG-specific heavy compound as shown in Figure 9B along with the proposed interpretation of a particular mass fragment presented is thought to suggest the chemical structure of 1-4-(4-methyl-1,3-dioxan-2-yl)propan-2-one. See also Table 6. The structures proposed in Figure 9B and Table 6 are not intended to be limiting. [Table 6] (Example 3) Identification of Odor-Causing Compounds in Bio-BG by GC-MS / O

[0299] Bio-BG and petro-BG samples were submitted to Volatile Analysis Corporation (VAC, Grant, AL), and the compounds causing off-odors were identified using VAC's gas chromatography mass spectrometry / olfaction (GC-MS / O) analysis service.

[0300] The GC-MS / O service of VAC involves trained odor assessors evaluating GC eluates and rating their odor intensity and characteristics, for example by providing qualitative odor descriptors. This perceptual information and the GC retention time (RT) of the odor are recorded and computer-aligned using the total ion chromatogram MS peaks. By understanding which chemical peaks exhibit the off-odors associated with the odor problem, all chemical off-odors can be identified and measured. Industrial grade and cosmetic grade petro-BG are commercially available from several sales companies. Samples were prepared using solid phase microextraction (SPME). SMPE is a solid phase extraction sampling technique involving the use of fibers coated with a liquid or solid extraction phase that can extract both volatile and non-volatile analytes from liquid samples or the gas phase.

[0301] Figures 10 and 11 show exemplary GC-MS / O analysis results for cosmetic grade petro-1,3-BG (Figure 10) and bio-BG (Figure 11). The upper traces and upward-pointed peaks in Figures 10 and 11 represent human perception scores of odor intensity obtained by olfactory analysis by trained VAC odor assessors. The bottom traces and downward-pointed peaks in Figures 10 and 11 represent the GC-MS chromatogram peaks (TIC), and the largest peak at a retention time of about 13 minutes represents 1,3-BG.

[0302] For example, as shown by the GC-MS / O analysis results such as those shown in FIGS. 10 and 11, it was shown that the total number of odor fractions in bio-BG was greater than that in cosmetic-grade petro-BG, particularly at retention times shorter than that of 1,3-BG. At retention times longer than that of 1,3-BG, slightly fewer odor compounds were detected in bio-BG than in cosmetic-grade petro-BG. Many of the odors resulting in fractions in bio-BG and cosmetic-grade petro-BG did not contain compounds showing strong or some UV absorption. Cosmetic-grade petro-BG contained GC fractions having sweet (5 fractions), musty (4 fractions), fruity (1 fraction), oily (3 fractions), citrusy (1 fraction), soil (1 fraction), aldehyde (1 fraction), sharp (1 fraction), or fecal (1 fraction) odors. Bio-derived 1,3-BG contained GC fractions having sweet (6 fractions), musty (6 fractions), oily (4 fractions), aldehyde (1 fraction), sharp (2 fractions), buttery (1 fraction), solvent (1 fraction), or unknown (1 fraction) odors. Bio-derived 1,3-BG did not contain fractions having fecal, soil, or citrusy odors. Bio-derived 1,3-BG contained fractions having buttery or solvent odors that were not present in cosmetic-grade petro-BG. Bio-derived 1,3-BG did not contain fractions having GC retention times longer than that of 1,3-BG and having fecal, musty, or sharp odors.

[0303] By GC-MS / O analysis, all bio-BGs were characterized as mainly having an "oily, paint-like, glue-like" odor, while petro-BGs were characterized as "sharp, sweet, alcohol-like, and fruity" at the same time. In particular, by GC-MS / O analysis, eight specific odor annotations of four known compounds (methyl vinyl ketone (MVK), 4-methyl-1-penten-3-one, 1-hepten-3-one, and diacetyl) and four unknown compounds were identified. (Example 4) GC-MS identification of odor-causing compounds in bio-BG

[0304] GC-MS analysis (by SPME-GCMS) of liquid samples of bio-BG and headspace samples derived from bio-BG gave proposed identifications of some of the impurities that cause several odors listed in Table 7. Some of the identified compounds (e.g., 1-hydroxy-2-propanone, 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, 3-hydroxy-2-butanone) were identified only by liquid GC-MS analysis. This may indicate that the identified compounds are of low volatility. It is generally considered that low-volatility compounds are substantially less likely to contribute to any off-odor of liquid samples such as liquid bio-derived 1,3-BG samples than high-volatility compounds. Other compounds such as acetaldehyde, 3-buten-2-one or methyl vinyl ketone, diacetyl, crotonaldehyde were detected only in the headspace of liquid bio-derived 1,3-BG samples, and it was shown that these compounds are present in the liquid fraction of bio-derived 1,3-BG samples only at concentrations below the liquid GC-MS detection limit. Compounds observed only in the headspace are likely to contribute to the off-odor of bio-derived 1,3-BG. [Table 7-1] [Table 7-2] [Table 7-3] (Example 5) Decomposition of 1,3 - BG using heat and formation of dehydration products

[0305] During the development of the GC - MS method described in Example 4, it was found or considered that methyl vinyl ketone (MVK, 3 - buten - 2 - one) and crotonaldehyde (Cr - Ald) were formed during injection inside the GC inlet port at temperatures of 250 °C and 150 °C. MVK is formed or considered to be formed through dehydration of 4 - hydroxy - 2 - butanone, as shown in the proposed diagram shown in Figure 5, and Cr - Ald is formed or considered to be formed through dehydration of 3 - hydroxy - butanal. MVK and Cr - Ald are compounds that result in odors with reported odor thresholds of 200 ppb (MVK) and 35 - 120 ppb (Cr - Ald). The low odor thresholds of MVK and Cr - Ald mean that MVK and Cr - Ald, which cause odors, result in significant odors at levels lower than the detection limits of analytical methods such as GC - MS. Cr - Ald has a reported odor threshold of 35 - 120 ppb, and MVK has a reported odor threshold of 200 ppb.

[0306] By observing the formation of MVK and Cr - Ald during the GC - MS analysis, the same proposed dehydration of 4 - hydroxy - 2 - butanone and 3 - hydroxy - butanal, where temperatures of 120 - 130 °C are typically observed and the residence time can exceed 6 hours, was also tested for occurrence in a batch distillation reboiler. Three 2 - mL test samples were prepared in 20 - mL GC - MS headspace vials as follows: 1) Cosmetic - grade petro - BG 2) Cosmetic petro - BG with 100 ppm of 3 - hydroxy - butanal added 3) Cosmetic petro - BG with 100 ppm of 4 - hydroxy - 2 - butanone added

[0307] Next, test samples 1) to 3) were heated to 120 °C in a silicone oil bath, incubated in the oil bath for 6 hours, and analyzed by SPME-GCMS and GCMS. The test results are shown in Tables 8 and 9. [Table 8] [Table 9]

[0308] Table 8 shows that higher levels of Cr-Ald were observed in the 3-hydroxy-butan-aldehyde-added sample than in the undiluted cosmetic-grade petro-BG or the 4-hydroxy-2-butanone-added sample. Furthermore, higher levels of MVK were observed in the 4-hydroxy-2-butanone-added sample than in the undiluted cosmetic-grade petro-BG or the 3-hydroxy-butan-aldehyde-added sample. The levels of Cr-Ald and MVK increased after heating the samples at 120 °C for 6 hours.

[0309] Table 9 shows that the levels of 3-hydroxy-butan-aldehyde and 4-hydroxy-2-butanone decreased in the 3-hydroxy-butan-aldehyde- and 4-hydroxy-2-butanone-added petro-BG samples after heating the samples at 120 °C for 6 hours. It was confirmed that the total purity levels of the undiluted and 3-hydroxy-butan-aldehyde- and 4-hydroxy-2-butanone-added petro-BG samples did not change substantially by the heat treatment.

[0310] This experiment confirmed that under the conditions of the batch distillation process, 4-hydroxy-2-butanone may decompose into MVK, and 3-hydroxy-butan-aldehyde may decompose into Cr-Ald, and the two are strong odor by-products. (Example 6) Activated carbon treatment

[0311] Activated carbon is commonly used in laboratory-scale and industrial-scale production and purification processes to remove impurities that impart color and odor from products such as petro-BG. For example, US8,445,733B1 intends to describe a method for reducing the odor of petro-BG products using a specific activated carbon preparation, and the entire content of which is hereby incorporated by reference into this specification.

[0312] This example shows the results of an experiment in which the bio-BG product was treated with an activated carbon preparation. Description of the activated carbon tested

[0313] Type and properties of the activated carbon tested: · Cabot Darco S-51A M-1967 (Darco; Cabot Corp., Boston, MA). This activated carbon preparation is coal-based, steam-activated, neutralized to pH 6 - 8, and exists in a micronized form. It is frequently used to remove taste, odor, or bright color in sugar applications. · Calgon FILTRASORB 300 (FS 300; Calgon Carbon Corp., Moon Township, PA). This activated carbon preparation is coal-based and exists in a 12×40 granular form. It is frequently used to remove taste, odor, and color from water, wastewater, and industrial and food processing streams. · Calgon BG HHM (BG HHM; Calgon Carbon Corp., Moon Township, PA). This activated carbon preparation is wood-based, acid-activated, and exists in a micronized form. It is designed by the manufacturer for decolorization in food and beverage processes and pharmaceutical purification. In particular, this preparation is developed to effectively adsorb high and low molecular weight organic impurities and meets the requirements of the Food Chemical Codex. ·Coconut shell (CS; Calgon Carbon Corp., Moon Township, PA). This activated carbon preparation is of coconut shell origin and exists in granular form. The preparation is characterized by a very large internal surface area due to its microporous structure, relatively high hardness, and low dust absorption. It is frequently used for water and stringent air purification applications, such as in water purifiers and respirators. ·Calgon CPG-LF (CPG-LF; Calgon Carbon Corp., Moon Township, PA). This activated carbon preparation is of coal origin, acid-washed to a neutral pH, exists in 12×40 granular form, and contains low iron and ash levels. The preparation has a strong adsorption pore structure designed to adsorb organic substances, pigment bodies, and odor molecules. Activated Carbon Testing by the Shake Flask Method

[0314] Multiple activated carbon preparations were immediately tested using the shake flask method with a minimal or low essential amount of 1,3-BG material. The test procedure was as follows: 1) The carbon sample was pulverized using a mortar and pestle. 2) The carbon was then washed several times with water. 3) The carbon was completely dried, for example, using an oven. 4) Equal amounts of the carbon preparation and bio-BG were added into a 125 mL flask at a target ratio of 0.2 g carbon / bio-BG g. 5) The flask was shaken at 40 °C and 200 rpm for 24 hours. 6) The carbon was separated from the bio-BG using a 0.22 μM vacuum filter. 7) The bio-BG was analyzed for odor, purity, and UV.

[0315] In one shake flask experiment, three activated carbon preparations: FS300, CS, and BGHHM were tested. Table 10 shows GC-MS purity data for the bio-BG-containing feedstock not treated with activated carbon preparation, and three bio-BG samples treated with different activated carbon preparations.

Table 10

[0316] The FS300-treated bio-BG sample showed the most significant decrease in 4-hydroxy-2-butanone. The CS-treated bio-BG sample showed the most significant decrease in 3-hydroxy-butyraldehyde. Treatment with all of the tested activated carbon preparations decreased 4-hydroxy-2-butanone and 3-hydroxy-butyraldehyde in the bio-BG samples. FS300 and CS increased the purity of bio-BG by 0.7%, and BGHHM increased the purity of bio-derived 1,3-BG by 0.5%.

[0317] In a second shake flask study, CPG-LF activated carbon was compared against FS300 and Darco activated carbon preparations. 3-Hydroxy-butyraldehyde was quantified by SPME-GCMS. The bio-BG feed samples tested in the second study were obtained from the final bio-BG distillate (see Example 1), while the bio-BG feed samples tested in the first study were obtained from earlier distillation fractions and differed in terms of their total purity levels. The SPME and GC-MS purity results are shown in Tables 11 and 12.

Table 11

Table 12

[0318] It was found that in all three activated carbon preparations, 3-hydroxy-butyraldehyde and 4-hydroxy-2-butanone decreased and some unknown heavy and light substances were removed.

[0319] The bio-BG feedstock and the FS300 and CPG-LF treated bio-BG samples were analyzed by trained odor panelists. The results from the odor panelists indicated that carbon treatment does not further complicate the identification of bio-BG samples from commercially available cosmetic grade petro-BG materials. Qualitatively, the odor intensity of the activated carbon treated bio-BG material was slightly lower than that of the feedstock material. Activated carbon obtained from a 0.59-inch column run

[0320] FS300 was tested in column format for its ability to remove impurities and odor from bio-BG.

[0321] The first FS300 column run was performed using a high purity bio-BG “light ends” distillate. See Example 1 and Table 13. To avoid or reduce the addition of water, the FS300 material was added dry to a 0.59-inch column. The operating parameters for the FS300 column run are shown in Table 13.

Table 13

[0322] Table 14 shows the results of the analysis of the FS300 treated (feedstock) and untreated (product) bio-BG samples. The UV absorbance at 270 nm of the FS300 treated bio-BG sample decreased by only a factor of 10 and the total purity of the bio-BG product increased by 0.1%.

Table 14

[0323] The 50 mL of the bio-BG fraction was collected through an FS300 column run, and the odor of each fraction was screened directly from 50 mL tubes by untrained panelists. The FS300 fractions of bio-BG selected based on the initial screening were pooled and submitted to VAC. Odor analysis by trained odor assessors indicated that treatment with FS300 did not reduce the odor of the test bio-BG samples.

[0324] A second activated carbon column run was performed using CPG-LF (12×40 granular size in a 0.59-inch diameter column) and bio-BG heavy distillate, which has a lower purity and a stronger odor than the bio-BG light distillate. The CPG-LF column was wetted to prevent channeling and improve the absorption of bio-BG impurities onto the CPG-LF activated carbon. Six bio-BG fractions were collected from the CPG-LF column. The total purity of the CPG-LF column fractions was 0.7%, and the UV absorbance of the CPG-LF fractions was only one-tenth lower compared to the bio-BG feed. No improvement in relative odor intensity was observed for any of the six CPG-LF column fractions compared to the bio-BG feed added to the column.

[0325] Finally, this example is thought to illustrate that substantial reduction of odor in bio-BG was not observed upon activated carbon treatment of the bio-BG sample. This observation is different from the odor reduction effect of activated carbon on petro-BG as described, for example, in US8,445,733 in the art. (Example 7) Base Addition to the Final Distillation Reboiler

[0326] It has been reported that adding a base to crude or low-quality petro-BG helps reduce the odor of the petro-BG preparation. See, for example, JP-A-7-258129, US6,376,725, and EP1046628, the entire contents of each of which are hereby incorporated by reference. This example describes the experimental results using the addition of a base to reduce the odor of bio-BG.

[0327] While not wishing to be bound by theory, it is thought that adding a base to bio-BG may reduce the dehydration of 3-hydroxy-butanals to croton aldehydes and of 4-hydroxy-2-butanones to methyl-vinyl-ketones (see, for example, Example 5 and Figure 12), and may promote the reaction of aldehydes and ketones to heavier, less volatile compounds. In the presence of a base, aldehydes and ketones such as 4-hydroxy-2-butanone and 3-hydroxy-butanals may form enolates and undergo condensation reactions, resulting in certain enols and aldols. The enols and aldols can further oligomerize to form heavier boiling compounds that can be separated from bio-BG by distillation.

[0328] In the examples described below, a base was added to the crude bio-BG preparation obtained after heavy fraction distillation in a laboratory scale (2L) batch distillation system as described, for example, in Example 1. Bio-BG with a purity of 99.8% and a strong odor was used as the "feed" for the distillation system. 2.73 mL of 10M sodium hydroxide (NaOH) (equivalent to 0.2 wt% NaOH) was added to the reboiler. The distillation was carried out at a low pressure of 10 - 11 torr and a low reboiler temperature between 118 and 124 °C. The UV absorbance analysis of the sample showed a relatively high UV absorbance. The GC-MS analysis results of an exemplary bio-BG distillation run using the addition of a base are described in Table 15.

Table 15

[0329] Several highly pure bio - BG distillation fractions, such as Cut #4 in Tables 15 and 16, with high purity and reduced odor compared to the feedstock were obtained. The NaOH remaining as a distillate in the reboiler was removed, and the concentration of the base in the reboiler increased over time. Without wishing to be bound by theory, when this increase in base concentration is combined with a long bio - BG residence time, the formation of isopropyl alcohol (IPA), n - butanol (n - But), cis - and trans - crotonyl alcohol, and 3 - buten - 2 - ol occurs, and all of these are thought to have strong odors. Cut #4 was the purified bio - BG fraction produced, as determined by GC - MS. See Tables 15 and 16. Cut #4 also had the lowest levels of MVK and Cr - Ald observed in the distillation fraction, as analyzed by SPME - GCMS. See Tables 15 and 16. However, overall the lowest levels of MVK and Cr - Ald were observed in the bio - BG feedstock. The odor of the feedstock is thought to be due to the presence of certain bio - BG light components. The odor of Cuts #3 and #4 decreased compared to the bio - BG feedstock, as determined by odor panelists. See Tables 15 and 16. Nevertheless, Cuts #3 and #4 were found to have a higher odor intensity (and different odor characteristics) than commercially available cosmetic - grade petro - BG by the same odor panelists.

Table 16

[0330] Figure 13 shows the overlay UV-VIS spectra of several 1,3-BG preparations. Cut #4 (preparation #7 in Figure 13) has the lowest among all materials except for the sodium borohydride-treated version of Cut #4 and has a relatively high absorbance (see preparation #8 in Figure 13, Example 9). Some commercially available petro-BG preparations (e.g., preparations #3 and #4 in Figure 13 (cosmetic grade) and preparations #5 and #6 in Figure 13 (industrial grade)) showed higher UV-VIS absorbance than Cut #4 (preparations #7 and #8 in Figure 13). It was not found that the UV absorbance correlates with the odor intensity or characteristics of the test 1,3-BG preparations.

[0331] Finally, this example is thought to illustrate that when a base is added to the final distillation reboiler, the UV-VIS absorbance of the bio-BG preparation decreases and there is no significant improvement in the odor characteristics of the bio-BG preparation. The latter observation is different from the odor reduction effect by base addition described in the literature related to the petro-BG purification process. For example, reference is made to JP-A-7-258129, the entire content of which is hereby incorporated by reference into this specification. (Example 8) Hydrogenation

[0332] Hydrogenation has been reported to be useful for the production of high-purity petro-BG and for reducing the level of aldehydes that cause odor in petro-BG preparations. This example describes the experimental results using hydrogenation to reduce the odor of bio-BG.

[0333] Preliminary experiments are thought to have demonstrated that when petro-BG and Raney nickel catalyst are hydrogenated for a long time (more than 3 to 4 hours), IPA and butanol are formed and the UV absorbance at 270 nm increases. This observation is thought to have demonstrated that any IPA and butanol formation observed after nickel-catalyzed hydrogenation of bio-BG may not be due to origin-specific trace impurities in the bio-BG fermentation process.

[0334] Three nickel catalysts: NiSAT320®, NiSAT330®, and NiSAT340® (Clariant, Muttenz, Switzerland) were tested in the bio-BG hydrogenation reaction. It was observed that reducing the residence time with the nickel catalyst improved the purity of the bio-BG preparation and decreased the formation of by-products. The three NiSAT catalysts were tested at a 1 wt% addition level and their performance was compared to that of a Raney nickel catalyst. The operating conditions were 130 °C, 500 psi, and a reaction time of approximately 2 hours. In Figures 14A and 14B, and Figures 14C and 14D, 0 minutes refers to the time when the hydrogenation reactor reached the target temperature of 130 °C. The heating time was between 16 and 20 minutes. The 120-minute end point refers to the sum of the residence time at the target temperature of 130 °C and the cooling time between 15 and 20 minutes.

[0335] Figures 14A, 14B, 14C, and 14D show the results of the bio-BG hydrogenation reaction. A decrease in UV absorbance and 4-hydroxy-butanone levels was observed after a long hydrogenation time exceeding 90 minutes. See Figures 14A and 14B. An increase in IPA and n-butanol levels was already observed (proposed) in bio-BG after a short hydrogenation time of about 30 minutes, and further increases were observed over time. See Figures 14C and 14D. Raney nickel was found to increase the IPA and n-butanol levels more strongly than the NiSAT320®, NiSAT330®, or NiSAT340® catalysts.

[0336] Finally, this example illustrates that prolonged hydrogenation of bio - BG may reduce the levels of certain contaminants such as UV absorbance and 4 - hydroxy - butanone, and at the same time increase the levels of other compounds such as IPA or n - butanol. These results suggest that hydrogenation may affect the purity and odor characteristics of bio - BG, which are different from those of petro - BG as described in the literature related to the isolation of petro - BG. (Example 9) Sodium borohydride (NaBH4)

[0337] In this example, the experimental results of using sodium borohydride (NaBH4) to reduce the odor of bio - BG through the disappearance of impurities such as MVK or Cr - Ald are described.

[0338] 20 g of the bio - BG sample was reduced using 1000 ppm equivalent (20 mg) of NaBH4. The feed and product samples were analyzed by SPME - GCMS and GCMS, and qualitatively evaluated for their odor characteristics. The results of the SPME - GCMS and GCMS analyses are shown in Tables 17 and 18. [Table 17] [Table 18]

[0339] By SPME analysis, it was demonstrated that the levels of the ketones and aldehydes (proposed compounds) in the bio-BG samples were substantially reduced by NaBH4 treatment. Also, by GCMS purity analysis, it was confirmed that the bio-BG concentrations of 3-hydroxy-butan-al and 4-hydroxy-2-butanone (proposed compounds) decreased by 10-fold, and at the same time the corresponding alcohols were obtained. The unidentified light substances in the bio-BG samples were found to increase by 150 ppm, and the unidentified heavy substances were found to increase by 4500 ppm. The UV absorbance at 270 nm of the NaBH4-treated bio-BG samples was found to decrease from 0.429 to 0.048. For example, see Figure 13 (bio-BG preparation #7 vs. #8). The substantial decrease in UV absorbance indicated that most of the absorbance in bio-BG probably originated from aldehydes and ketones that were selectively reduced by NaBH4, and not from the conjugated double bond system that was not reduced by NaBH4.

[0340] Qualitatively, the odor of the NaBH4-treated bio-BG samples was found to be strong and unpleasant. (Example 10) ASPEN Modeling of Compounds that Result in Known Odors

[0341] To understand the issues that may remove impurities from bio-derived 1,3-BG, a 4-column distillation simulation was created in ASPEN. See also Figure 16. The following proposed trace contaminants of bio-derived 1,3-BG were included in the distillation simulation: · 2,3-Butanediol · 1,2-Propanediol · Acetaldol (3-hydroxy-butan-al) · 4-OH-2-butanone

[0342] In the model, the vacuum for the dehydration column was set to 80 torr, and the bottom temperature was estimated to be 144 °C. The vacuum for the following three distillation columns was set to 25 torr in each column, and the bottom temperature was estimated to be 118 - 119 °C.

[0343] The results of the ASPEN modeling showed that all of water, 3-hydroxy-butanol and 4-hydroxy-2-butanone, as well as small amounts of 2,3-BDO, were removed as dehydration distillate from the biologically derived 1,3-BG-containing product stream. The remaining light impurities (residual 2,3-BDO and 1,2-PDO) were found to be removed in the light column. These findings are consistent with the boiling point differences of the modeled trace contaminants as listed, for example, in Table 7. No azeotropic mixtures were observed. Other alternative embodiments

[0344] Although the present invention has been described with reference to the above-described embodiments and examples, it should be understood that various improvements can be made without departing from the spirit of the present invention.

Claims

[Claim 1] An object, method or system as described in this specification and drawings.

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