Diamine synthesis process

Abstract

The present disclosure relates to a process for making a diamine from an organic compound formed by such carbohydrate sources as six-carbon (C6) sugars, starchy materials, cellulosic mater, and particularly, such compounds as 5-(hydroxymethyl)furfural and 5-(halomethyl)furfural.

Description

DIAMINE SYNTHESIS PROCESSCLAIM OF PRIORITY

[0001] This patent application claims the benefit of priority to U.S. Application Serial No. 63 / 570,244, filed March 27, 2024, which is incorporated by reference herein in its entirety.FIELD

[0002] This disclosure relates to a process for making a diamine from an organic compound formed by such carbohydrate sources as six-carbon (Ce) sugars, starchy materials, cellulosic mater, and particularly, such compounds as 5-(hydroxymethyl)furfural and 5- (halomethyl)furfural .BACKGROUND

[0003] An organic molecule, diamine, is an important intermediate in many useful chemistries.SUMMARY

[0004] In some aspects, the techniques described herein relate to a method of making a diamine; the method including the steps of (a) contacting a furfural compound with an ammonia source and an oxygen source in the presence of a catalyst, and optionally, a solvent in a first reaction zone; (b) maintaining the first reaction zone conditions for a sufficient time to effectively convert the furfural compound to at least one cyanofuran compound; (c) recovering the first reaction zone effluent to obtain the cyanofuran compound; (d) contacting the cyanofuran compound from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst, and optionally, a solvent in a second reaction zone; (e) maintaining the second reaction zone conditions for a sufficient time to effectively convert the cyanofuran compound to at least one diamine compound; (f) and recovering the second reaction zone effluent to obtain the diamine.

[0005] In some aspects, the techniques described herein relate to a method of making 1,6-hexanediamine; the method including the steps of (g) contacting 5- (hydroxymethyl)furfural with an ammonia source and an oxygen source in the presence of a catalyst, and optionally, a solvent in a first reaction zone; (h) maintaining the first reactionzone conditions for a sufficient time to effectively convert 5-(hydroxymethyl)furfural to at least one cyanofuran compound including 2, 5 -di cyanofuran; (i) recovering the first reaction zone effluent to obtain 2,5-dicyanofuran; (j) contacting the 2,5-dicyanofuran from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst, and optionally, a solvent in a second reaction zone; (k) maintaining the second reaction zone conditions for a sufficient time to effectively convert the 2,5-dicyanofuran to at least one diamine compound including 1,6-hexanediamine; (1) recovering the second reaction zone effluent to obtain the 1,6- hexanedi amine.BRIEF DESCRIPTION OF THE FIGURES

[0006] The drawings, which are not necessarily drawn to scale, illustrate generally, by way of example, but not by way of limitation, the present invention.

[0007] FIGURE 1 is a representation of the powdered catalysts XRD patterns according to the present disclosure.DETAILED DESCRIPTION

[0008] Reference will now be made in detail to certain aspects of the disclosed subject matter. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter.

[0009] Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0010] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “atleast one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section.

[0011] In the methods described herein, the acts can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0012] The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0013] The term “substantially” as used herein refers to a majority of, or mostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. The term “substantially free of’ as used herein can mean having none or having a trivial amount of, such that the amount of material present does not affect the material properties of the composition including the material, such that the composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less. The term “substantially free of’ can mean having a trivial amount of, such that a composition is about 0 wt% to about 5 wt% of the material, or about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.01, or about 0.001 wt% or less, or about 0 wt%.

[0014] All publications, including non-patent literature (e.g., scientific journal articles), patent application publications, and patents mentioned in this specification are incorporated by reference as if each were specifically and individually indicated to be incorporated by reference.

[0015] It is understood that the descriptions herein are intended to be illustrative, and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. The scope of the invention should, therefore, be determinedwith reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. In the appended claims, the terms “including” and “in which” are used as the plain-English equivalents of the respective terms “comprising” and “wherein,” respectively. Moreover, the terms “first,” “second,” “third,” and the like are used merely as labels, and are not intended to impose numerical requirements on their objects.

[0016] The term “furfural compound”, as used herein, means a derivative of 2- furaldehyde [CAS No. 98-01-1] having the following molecular structure:0; wherein, Ri is a linear Ci-4 alkylene group, and X is independently selected from hydroxyl and halogen groups. Non-limiting examples of the furfural compound may include one or more of the compounds having the following molecular structures:wherein, Ri is independently selected from methylene, ethylene, propylene and butylene groups. In one aspect, the furfural compound is 5-(chloromethyl)furfural as represented by themolecular formula:0In another aspect, the furfural compound is 5-(hydroxymethyl)furfural as represented by the molecular formula:0

[0017] One example of industrial relevance is a six-carbon diamine that can be formed by the disclosed method is 1,6-hexanediamine or hexamethylenediamine (HMD).

[0018] HMD is an important chemical intermediate in the production of nylon 66 (polyhexamethylene adipamide), hexamethylene isocyanate, organic cross-linking agent, curing agent, synthetic resin and many other industrial chemicals.

[0019] The current industrial routes for making HMD are by 1,6-hexanedinitrile (or adiponitrile) hydrogenation, wherein adiponitrile can be made from either adipic acid amination using ammonia and acid catalyst, acrylonitrile coupling or 1,3 -butadiene double hydrocyanation using a cyanide source. Each process has its own advantages (mature technology, high yields, etc.) and disadvantages (economy of scale, significant capital investment, high energy footprint, process complexity, use of hazardous chemicals, etc.).

[0020] In literature, various routes of making 1,6-hexanediamine (HMD) from such feeds as 1,6-hexanedialdehyde (or adipaldehyde), 1,6-hexanediol (HDO), 1,6-hexanediacid (oradipic acid), caprolactam are discussed. However, commercially viable routes of making HMD in good yields from such biomass feedstocks as reduced sugars, starchy materials, cellulosic mater, etc. are almost non-existent.

[0021] United States Patent application publication numbers 20170144962 and 20180170844 relate to a two-step method of preparing HMD by reacting a furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol and by reductively aminating the 1,6-hexanediol to diamine.

[0022] Chinese patent application publication number CN101628875 discloses production of HMD by liquefying starch and saccharifying to make glucose; hydrogenating glucose to make sorbite using Raney nickel catalyst; and hydrogenating sorbite, cracking, rectifying, and separating by high pressure to make HDO. HDO is then treated with highly efficient nickel alloy to make HMD.

[0023] Chinese patent application publication number 112898164 relates to a method for preparing 1,6-hexanediamine (HMD) from 5-(hydroxymethyl)furfural (5-HMF). The two- step method employs reductive amination of 5-HMF in a hydrogen and ammonia presence to afford 2,5-bis(aminomethyl)furan followed by ring opening reaction on the hydrodeoxygenation catalyst to obtain HMD. The overall yield of HMD from the starting 5- HMF was low and estimated in the 25-53 % range. A high HMD yield process from the starting 5-HMF feedstock would be desirable from a commercial standpoint.

[0024] United States Patent Number 11214559 relates to a production method for 2,5- bis(aminomethyl)furan by reacting 5-(halomethyl)furfural, for example, 5- (chloromethyl)furfural (CMF), with hydrogen and an amine compound in a one-pot catalytic reductive amination reaction.

[0025] Chinese patent application publication number 112979474 relates to a method for synthesizing 1,6-hexanediamine by catalyzing 2, 5-di cyanofuran hydrogenation ringopening. It would be desirable to make 1,6-hexanediamine from raw materials other than 2,5- dicy anofuran.

[0026] Chinese patent application publication number 109956918 relates to a method of preparing 2,5-furandicarboxamide by catalytic ammoxidation of 5-(hydroxymethyl)furfural.

[0027] Chinese patent application publication number 107814781 relates to a method of preparing 5-cyano-2-furanamide by catalytic ammoxidation of 5-(hydroxymethyl)furfural.

[0028] Chinese patent numbers 104066710 and 106008163 disclose a process for preparing hexamethylenediamine from a carbohydrate source, comprises: (a) converting acarbohydrate source to a furfural substrate; (b) reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6- hexanediol; and (c) converting at least a portion of the 1,6-hexanediol to hexamethylenediamine.

[0029] Research journal article by Wei et. al., ChemSusChem 2021, 14, p2308-2312 relates to one-Step reductive amination of 5-HMF into 2,5-Bis(aminomethyl)furan (BAMF) with 82.3% yield over Raney Ni catalyst at 160°C for 12h. In a subsequent research journal article by Wei et. al., ChemSusChem 2022, 15, the BAMF yield in the 82-86% range was achieved by using lONi / y-AhCh and 10NiMn(4 : Ij / y-AhCh catalysts. It would be desirable to make 1,6-hexanediamine directly from 5-HMF in high yields.

[0030] It is clear from the above summary that an industrial need exists to synthesize HMD in high yield from abundantly available such renewable carbohydrate sources as six- carbon (Ce) sugars, starchy materials, cellulosic mater, etc., and by consuming less petroleum resources while lowering the cost of production. It would be highly desirable to produce HMD in high yields by using biomass and carbohydrate sources that are carbon-neutral, renewable feedstocks.

[0031] This present disclosure relates to a process for making a diamine from an organic compound formed by such carbohydrate sources as six-carbon (Ce) sugars, starchy materials, cellulosic mater, and particularly, such compounds as 5-(hydroxymethyl)furfural and 5-(halomethyl)furfural.

[0032] Disclosed herein is a process for producing a diamine based on an ammoxidation of 5 -(hydroxy alkyl (furfural to a dicyanofuran compound, and subsequent ring opening by hydrogenation / hydro-deoxygenation of the resulting dicyanofuran to diamine.

[0033] In one aspect, disclosed herein is a process for producing 1,6-hexanediamine (HMD) based on an ammoxidation of 5-(hydroxymethyl)furfural (5-HMF) to 2,5- dicyanofuran, and subsequent ring opening by hydrogenation / hydro-deoxygenation of the resulting 2,5-dicyanofuran to HMD.

[0034] 5 -HMF [CAS No. 67-47-0] can be produced by dehydrating carbohydrates, which are abundantly available as six-carbon (Ce) sugars, low-cost high-fructose corn syrup (HFCS) as well as starchy, cellulosic raw materials. It is produced industrially on a modest scale as a carbon-neutral feedstock for fuel production and such chemicals as 2,5- furandicarboxylic acid, 2,5-dimethylfurane, 2,5-bis(hydroxymethyl)furan, y-hydroxyvaleric acid, y-valerolactone, etc. Other industrial uses of 5-HMF include food improvement additivesuch as a biomarker and flavoring agent for food products.

[0035] To produce HMD from 5-HMF, 5-HMF is mixed in a parr reactor with a cryptomelane manganese oxide catalyst. Following mixing, anhydrous NH3 is added and the mixture is agitated and heated for a time ranging from about 0.5 hours to about 8 hours, about 0.5 hours to about 60 hours, about 0.5 hours, 1.5, 2, 2.5, 3. 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or about 8 hours. The reaction yields 2,5-dicyanofuran in a range of from about 90 wt% to about 100 wt%, about 95 wt% to about 99.5 wt%, less than, equal to, or greater than about 90 wt%, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, 99, 99.5, or about 100 wt%.

[0036] The 2,5-dicyanofuran is recovered by distillation and separated from the spent catalyst. The recovered 2,5-dicyanofuran is placed in a Parr reactor along with a solvent and catalyst. Catalysts can include sulfided nickel-molybdenum or cobalt-molybdenum on y- alumina support, or unsupported, copper chromite, and Raney Nickel type. Solvents can include ammonia, ethanol, and mid-high range boiling solvents. Hydrogen is added to the reaction until such a point that hydrogen uptake ceases. The purified HMD product yield is about 85 wt% to about 100 wt%, about 90 wt% to about 97 wt%, less than, equal to, or greater than about 85 wt%, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt%.

[0037] Also, disclosed herein is a process for production hexamethylenediamine (HMD) from substituted furans, for example, 5-(halomethyl)furfural. One such commercially viable substituted furan is 5-(chloromethyl)furfural or 5-CMF as commonly known in the industry. An on-going commercial scale-up of 5-CMF production by Origin Materials, Inc. would make this starting feedstock available for the diamine production according to the present disclosure. 5-CMF may be produced by acid-catalyzed conversion of renewable feedstocks, mono- / di- or polymeric six-carbon (Ce) sugars in particular, and as described in United States Patent numbers 9388151, 9586922, 9718798, 10011577 and 10093638.

[0038] HMD can be produced from 5-CMF by hydrolyzing 5-CMF in the presence of water with an optional acid catalyst to form 5-HMF. The 5-HMF is mixed in a parr reactor with a cryptomelane manganese oxide catalyst. Following mixing, anhydrous NH3 is added and the mixture is agitated and heated for a time ranging from about 0.5 hours to about 8 hours, about 0.5 hours to about 6 hours, about 0.5 hours, 1.5, 2, 2.5, 3. 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or about 8 hours. The reaction yields 2,5-dicyanofuran in a range of from about 90 wt% to about 100 wt%, about 95 wt% to about 99.5 wt%, less than, equal to, or greater than about 90 wt%, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5 99, 99.5, orabout 100 wt%.

[0039] The 2,5-dicyanofuran is recovered by distillation and separated from the spent catalyst. The recovered 2,5-dicyanofuran is placed in a Parr reactor along with a solvent and catalyst. Catalysts can include sulfided nickel-molybdenum or cobalt-molybdenum on y- alumina support, or unsupported, copper chromite, and Raney Nickel type. Solvents can include ammonia, ethanol, and mid-high range boiling solvents. Hydrogen is added to the reaction until such a point that hydrogen uptake ceases. The purified HMD product yield is about 85 wt% to about 100 wt%, about 90 wt% to about 97 wt%, less than, equal to, or greater than about 85 wt%, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt%.

[0040] Another useful substituted furan is 5-(bromomethyl)furfural (5-BMF). 5- (haloalkyl)furfurals are reactive, which makes them useful for the synthesis of 5- (hydroxyalkyl)furfural derivatives. In one aspect, 5-CMF and 5-BMF both may undergo hydrolysis quantitatively to 5-HMF in hot water.

[0041] As mentioned hereinabove several different catalysts can be used in the formation of HMD. The yield of the HMD using copper chromite is from about 90 wt% to about 100 wt%, about 95 wt% to about 99.5 wt%, less than, equal to, or greater than about 90 wt%, 90.5, 91, 91.5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5 99, 99.5, or about 100 wt% when the hydrogenation / hydro-deoxygenation was completed at 150°C for 1 hours. The yield of HMD using Raney nickel about 85 wt% to about 100 wt%, about 90 wt% to about 97 wt%, less than, equal to, or greater than about 85 wt%, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or about 100 wt% when the hydrogenation / hydro-deoxygenation was completed at 150°C for 1 hours.Material Names and Abbreviations used in the disclosure:

[0042] BMF or 5-BMF 5-(bromomethyl)furfural;

[0043] CMF or 5-CMF 5-(chloromethyl)furfural;

[0044] DCF or 2,5-DCF 2,5-dicyanofuran

[0045] HMD or HMDA hexamethylene diamine or 1,6-hexanediamine;

[0046] HMF or 5-HMF 5-(hydroxymethyl)furfural;EXAMPLES

[0047] Various aspects of the present disclosure can be better understood by reference to the following Examples which are offered by way of illustration. The present disclosure is not limited to the Examples given herein.Materials

[0048] 5-HMF and 5-CMF are obtained from commercial sources.

[0049] Bottled 30 wt% NEE in water was used in the ammoxidation reaction.

[0050] Dried ambient air was used as a source of oxygen for the reaction.

[0051] The catalyst used in the present disclosure was cryptomelane manganese oxide. Synthesis of cryptomelane manganese oxide ammoxidation catalyst was performed as described in Yamaguchi, et al., Angew. Chem. Int. Ed. 2012, 51, 544. The resulting material was characterized by powder x-ray diffraction (XRD) at Missouri University of Science and Technology for comparison to published results. Powder XRD results were compared to those published in the literature and represented in FIG. 1.

[0052] FIG. l is a representation of the XRD patterns for the catalysts according to the present disclosure. The catalyst materials appear to match other than some differences in crystallite size. In FIG. 1, the powder XRD patterns are shown for the catalysts: K-OMS-2, MnCh, [Al]-K-OMS-2 and MnOx.Ammoxidation of 5-(hydroxymethyl)furfural

[0053] The cryptomelane manganese oxide catalyst material, and liquid ingredients were weighed and charged to a 300 mL Parr reactor equipped with a gas entrainment impeller. Anhydrous NEE was weighed in, and the pressure was recorded. Air was pressured in and recorded. After all reactants were added and the agitator started a sample at room temperature and time zero was collected for analysis. The reactor was then heated to the target temperature. Once at desired temperature, samples were collected at 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours from the start, and analyzed.

[0054] The 2,5-dicyanofuran (DCF) yield of 99.5% was confirmed by GC / MS.

[0055] Example 1 is repeated except the ammoxidation was carried out using 30 wt% concentrated ammonium hydroxide. The product was exclusively the 2,5-furandicarboxamide in >99.9% yield when the ammoxidation was completed at 130°C for 4 hours.Hydrogenation / hydro-deoxygenation of 2,5-dicyanofuran

[0056] The ammoxidation reaction effluent from Example 1 is collected, the spent catalyst is filtered out, and the intermediate product 2,5-dicyanofuran is recovered from the filtrate using distillative separation. The refined 2,5-dicyanofuran is charged to the 300 mL Parr reactor along with a solvent and catalyst. Suitable catalysts may include sulfided nickelmolybdenum or cobalt-molybdenum on y-alumina support, or unsupported, copper chromite, and Raney Nickel type. Further, an improved yield may be obtained by alkalizing the Co / NiMoSx prior to use with potassium or cesium. Suitable solvents may include ammonia, ethanol, and mid-high range boiling solvents The reactor headspace is purged three times with nitrogen. Next, a pressurized hydrogen feed is introduced to the headspace and the reactor head pressure is monitored over time. The reaction is continued until no further hydrogen uptake is detected from the reactor head pressure.

[0057] Upon completion, the reaction effluent is collected, the catalyst filtered and the filtrate is purified via vacuum distillation. The target product, 1,6-hexanediamine, is obtained in high yields. The overall yield of HMD from the starting 5-HMF is greater than 90%.

[0058] 5-(chloromethyl)furfural (5-CMF) is hydrolyzed in the presence of water, and optionally, an acid catalyst to obtain 5-HMF in good yields. Example 1 is repeated except the 5-HMF formed from CMF is used as a starting material, and the 2,5-dicyanofuran is further converted into HMD as per Example 3 procedure. The overall yield of HMD from 5-CMF is greater than 80%.

[0059] A similar Parr reactor setup, as used in Example 1, is used for reductive amination of 5-HMF with a catalyst, hydrogen and ammonia, but in the absence of oxygen source. The intermediate, 2,5-bis(aminomethyl)furan is recovered followed by itshydrodeoxygenation to 1,6-hexanediamine. The overall HMD yield from 5-HMF is not more than 50%.

[0060] Comparative Example 1 is repeated except the starting 5-HMF is prepared from the hydrolysis of 5-CMF as described in Example 4. The Example 1 Parr reactor setup is used wherein the 5-HMF is reductively aminated to 2,5-bis(aminomethyl)furan using a catalyst, hydrogen and ammonia, but in the absence of oxygen source. The intermediate, 2,5- bis(aminomethyl)furan is recovered followed by its hydrodeoxygenation to 1,6- hexanediamine. The overall HMD yield from 5-CMF is not more than 40%.

[0061] The hydrogenation / hydro-deoxygenation procedure of Example 3 is repeated except the hydrogenation / hydro-deoxygenation is carried out using copper chromite (Adkins catalyst) as the catalyst. The product was exclusively the 1,6-hexamethylenediamine in >90% yield when the hydrogenation / hydro-deoxygenation was completed at 150°C for 1 hours.

[0062] The hydrogenation / hydro-deoxygenation procedure of Example 3 is repeated except the hydrogenation / hydro-deoxygenation is carried out using Raney nickel as the catalyst. The product was exclusively the 1,6-hexamethylenediamine in >85% yield when the hydrogenation / hydro-deoxygenation was completed at 150°C for 1 hours.

[0063] The product made via Example 2, i.e., 2,5-furandicarboxamide is converted to 1,6-hexamethylenediamine is high yields.

[0064] The terms and expressions that have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the aspects of the present invention. Thus, it should be understood that although the presentinvention has been specifically disclosed by specific aspects and optional features, modification and variation of the concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of aspects of the present invention.

[0065] The following exemplary aspects are provided, the numbering of which is not to be construed as designating levels of importance:

[0066] Aspect 1 provides a method of making a diamine; the method comprising the steps of a) contacting a furfural compound with an ammonia source and an oxygen source in the presence of a catalyst , and optionally, a solvent in a first reaction zone; b) maintaining the first reaction zone conditions for a sufficient time to effectively convert the furfural compound to at least one cyanofuran compound; c) recovering the first reaction zone effluent to obtain the cyanofuran compound; d) contacting the cyanofuran compound from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst , and optionally, a solvent in a second reaction zone; e) maintaining the second reaction zone conditions for a sufficient time to effectively convert the cyanofuran compound to at least one diamine compound; f) and recovering the second reaction zone effluent to obtain the diamine.

[0067] Aspect 2 provides the method of Aspect 1, wherein the furfural compound is a dehydration reaction product of a carbohydrate compound.

[0068] Aspect 3 provides the method of Aspect 2, wherein the carbohydrate compound is selected from one or more of six-carbon sugars, saccharides, fructose, glucose, high fructose corn syrup, cellulosic, hemi-cellulosic and starchy compounds.

[0069] Aspect 4 provides the method of any of Aspect 1-3, wherein the furfural compound is selected from one or more of the compounds having the following molecular structure:wherein, R1 is a linear Cl -4 alkylene group, and X is independently selected from hydroxyl and halogen groups.

[0070] Aspect 5 provides the method of Aspect 4, wherein the furfural compound is selected from one or more of the compounds having the following molecular structures:wherein, R1 is independently selected from methylene, ethylene, propylene and butylene groups.

[0071] Aspect 6 provides the method of Aspect 4 further comprises a hot-water hydrolysis of the furfural compound selected from one or more of the compounds having the following molecular structures:wherein, R1 is independently selected from methylene, ethylene, propylene and butylene groups.

[0072] Aspect 7 provides the method of Aspect 6, wherein the furfural compound is 5-(chloromethyl)furfural and the hydrolysis product is 5-(hydroxymethyl)furfural.

[0073] Aspect 8 provides the method of Aspect 6, wherein the furfural compound is 5-(bromomethyl)furfural and the hydrolysis product is 5-(hydroxymethyl)furfural.

[0074] Aspect 9 provides the method of Aspect 1, wherein the catalyst of a) is a hydrodeoxidation catalyst.

[0075] Aspect 10 provides the method of Aspect 1, wherien the catalyst of a), d), or both comprises sulfided nickel-molybdenum catalyst, cobalt-molybdenum catalyst, on y- alumina support, unsupported catalyst thereof, copper chromite catalyst, and Raney Nickel type catalyst, or a mixture thereof.

[0076] Aspect 11 provides the method of Aspect 1, wherien the solvent comprises ammonia, ethanol, a mid-high range boiling solvents.

[0077] Aspect 12 provides the method of Aspect 1, wherein the sufficient amount of time at a), e), or both independently ranges from about 0.5 hours to about 8 hours.

[0078] Aspect 13 provides a method of making 1,6-hexanediamine; the method comprising the steps of:g) contacting 5-(hydroxymethyl)furfural with an ammonia source and an oxygen source in the presence of a catalyst, and optionally, a solvent in a first reaction zone; h) maintaining the first reaction zone conditions for a sufficient time to effectively convert 5-(hydroxymethyl)furfural to at least one cyanofuran compound comprising 2,5- dicy anofuran; i) recovering the first reaction zone effluent to obtain 2,5-dicyanofuran; j) contacting the 2,5-dicyanofuran from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst, and optionally, a solvent in a second reaction zone; k) maintaining the second reaction zone conditions for a sufficient time to effectively convert the 2,5-dicyanofuran to at least one diamine compound comprising 1,6- hexanedi amine; l) recovering the second reaction zone effluent to obtain the 1,6-hexanediamine.

[0079] Aspect 14 provides the method of Aspect 13, wherein the catalyst of g) is a hydrodeoxidation catalyst

[0080] Aspect 15 provides the method of Aspect 13, wherien the catalyst of g), j), or both comprises sulfided nickel-molybdenum catalyst, cobalt-molybdenum catalyst, on y- alumina support, unsupported catalyst thereof, copper chromite catalyst, Raney Nickel type catalyst, or a mixture thereof.

[0081] Aspect 16 provides the method of Aspect 13, wherien the solvent comprises ammonia, ethanol, a mid-high range boiling solvents.

[0082] Aspect 17 provides the method of Aspect 13, wherein the sufficient amount of time at h), k), or both independently ranges from about 0.5 hours to about 8 hours.

Claims

CLAIMSWhat is claimed is:

1. A method of making a diamine; the method comprising the steps of: a) contacting a furfural compound with an ammonia source and an oxygen source in the presence of a catalyst, and optionally, a solvent in a first reaction zone; b) maintaining the first reaction zone conditions for a sufficient time to effectively convert the furfural compound to at least one cyanofuran compound; c) recovering the first reaction zone effluent to obtain the cyanofuran compound; d) contacting the cyanofuran compound from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst, and optionally, a solvent in a second reaction zone; e) maintaining the second reaction zone conditions for a sufficient time to effectively convert the cyanofuran compound to at least one diamine compound; f) and recovering the second reaction zone effluent to obtain the diamine.

2. The method of claim 1, wherein the furfural compound is a dehydration reaction product of a carbohydrate compound.

3. The method of claim 2, wherein the carbohydrate compound is selected from one or more of six-carbon sugars, saccharides, fructose, glucose, high fructose corn syrup, cellulosic, hemi-cellulosic and starchy compounds.

4. The method of any of claim 1-3, wherein the furfural compound is selected from one or more of the compounds having the following molecular structure:0; wherein, Ri is a linear Ci-4 alkylene group, and X is independently selected from hydroxyl and halogen groups.

5. The method of claim 4, wherein the furfural compound is selected from one or more of the compounds having the following molecular structures:wherein, Ri is independently selected from methylene, ethylene, propylene and butylene groups.

6. The method of claim 4 further comprises a hot-water hydrolysis of the furfural compound selected from one or more of the compounds having the following molecular structures:wherein, Ri is independently selected from methylene, ethylene, propylene and butylene groups.

7. The method of claim 6, wherein the furfural compound is 5-(chloromethyl)furfural and the hydrolysis product is 5-(hydroxymethyl)furfural.

8. The method of claim 6, wherein the furfural compound is 5-(bromomethyl)furfural and the hydrolysis product is 5-(hydroxymethyl)furfural.

9. The method of claim 1, wherein the catalyst of a) is a hydrodeoxidation catalyst.

10. The method of claim 1, wherien the catalyst of a), d), or both comprises sulfided nickelmolybdenum catalyst, cob al t-molyb denum catalyst, on y-alumina support, unsupported catalyst thereof, copper chromite catalyst, Raney Nickel type catalyst, or a mixture thereof.

11. The method of claim 1, wherien the solvent comprises ammonia, ethanol, a mid-high range boiling solvents.

12. The method of claim 1, wherein the sufficient amount of time at a), e), or both independently ranges from about 0.5 hours to about 8 hours.

13. A method of making 1,6-hexanediamine; the method comprising the steps of: g) contacting 5-(hydroxymethyl)furfural with an ammonia source and an oxygen source in the presence of a catalyst, and optionally, a solvent in a first reaction zone; h) maintaining the first reaction zone conditions for a sufficient time to effectively convert 5-(hydroxymethyl)furfural to at least one cyanofuran compound comprising 2,5-dicyanofuran;i) recovering the first reaction zone effluent to obtain 2,5-dicyanofuran; j) contacting the 2,5-dicyanofuran from c) with a hydrogen source in the presence of a hydrodeoxidation catalyst, and optionally, a solvent in a second reaction zone; k) maintaining the second reaction zone conditions for a sufficient time to effectively convert the 2,5-dicyanofuran to at least one diamine compound comprising 1,6-hexanediamine; l) recovering the second reaction zone effluent to obtain the 1,6-hexanediamine.

14. The method of claim 13, wherein the catalyst of g) is a hydrodeoxidation catalyst.

15. The method of claim 13, wherien the catalyst of g), j), or both comprises sulfided nickelmolybdenum catalyst, cob al t-molyb denum catalyst, on y-alumina support, unsupported catalyst thereof, copper chromite catalyst, Raney Nickel type catalyst, or a mixture thereof.

16. The method of claim 13, wherien the solvent comprises ammonia, ethanol, a mid-high range boiling solvents.

17. The method of claim 13, wherein the sufficient amount of time at h), k), or both independently ranges from about 0.5 hours to about 8 hours.