Processes for separating solvents from waste streams

Abstract

The process for recovering solvent from a waste stream includes adding the waste stream containing process solvent, titanium tetrachloride, titanium alkoxide, organic compounds, and / or their decomposition products to a distillation apparatus, adding additives to the distillation apparatus to form a distillation mixture, and distilling the distillation mixture to recover the solvent exhibiting increased purity compared to the waste stream.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 484,422, filed February 10, 2023, which is incorporated herein by reference in its entirety. [Background technology]

[0002]

[0002] Process solvents from catalysts produced using internal donors undergo side reactions during recovery of TiCl4, producing materials that are difficult to separate using standard separation methods. Waste streams containing donor decomposition products are difficult to separate and cause disposal problems due to deposition on vessel walls. Therefore, improved methods are needed to recover solvents from waste streams resulting from catalyst production. Summary of the Invention

[0003] In one aspect, a method for concentrating a waste stream is provided. The method includes adding an additive to a waste stream to form an additive mixture, the waste stream including a process solvent, titanium tetrachloride, a titanium alkoxide, an organic compound, and / or decomposition products thereof, and concentrating the additive mixture to form a concentrated waste stream having a reduced volume relative to the waste stream. Methods for concentrating the additive mixture may include, but are not limited to, evaporating the process solvent from the additive mixture or distilling the additive mixture.

[0004] In another aspect, a method for separating a solvent from a waste stream is provided. The method includes adding an additive to a waste stream to form an additive mixture, the waste stream including a process solvent, titanium tetrachloride, a titanium alkoxide, an organic compound, and / or decomposition products thereof, and separating the process solvent from the additive mixture. The separated process solvent may have an increased purity compared to the waste stream. An exemplary method for separating the process solvent from the additive mixture is distillation of the additive mixture.

[0005] In another aspect, a method for recovering a solvent from a waste stream is provided, the method comprising the steps of adding a waste stream containing a process solvent, titanium tetrachloride, a titanium alkoxide, an organic compound, and / or decomposition products thereof to a distillation apparatus, adding an additive to the distillation apparatus to form a distillation mixture, and distilling the distillation mixture to recover a solvent exhibiting increased purity relative to the waste stream.

[0006] In some embodiments, the waste stream has an acidic pH. In some embodiments, the method further comprises neutralizing the waste stream with a neutralizing agent before adding the additive. In some embodiments, the method further comprises neutralizing the waste stream during addition of the additive. In one embodiment, the additive neutralizes the waste stream. In some embodiments, the waste stream is partially neutralized. In other embodiments, the waste stream is completely neutralized.

[0007] In some embodiments, the additive is added to the waste stream as an aqueous solution. In other embodiments, the additive is added to the waste stream as a suspension in water. In some embodiments, adding the additive as an aqueous solution or suspension in water results in the waste stream being hydrolyzed.

[0008] In some embodiments, the organic compound is an alcohol, an ester, a ketone, an ether, an amide, an amine, a carbonate, a carbamide, an alkyl urea, an imine, a sulfide, a thioester, or a combination of two or more thereof. In some embodiments, where the organic compound is an alcohol, the alcohol may be a polydentate alcohol, such as a catechol, a diol, a glycol, or a diol diester. In one embodiment, the organic compound is an internal donor. In some embodiments, the waste stream further comprises a decomposition product of the internal donor. The decomposition product of the internal donor may be present in the waste stream initially, or the decomposition product of the internal donor may be formed from neutralization or hydrolysis of the waste stream.

[0009] In some embodiments, the additive comprises a metal salt, hi some embodiments, the additive comprises a metal hydroxide salt, a metal chloride salt, a metal sulfate salt, or a combination of two or more thereof.

[0010] In some embodiments, the additive comprises a metal salt having a metal source with a valence of 1 or greater. Examples of metal sources include Na + , Mg 2+ , Ca 2+ , Fe 2+ , Fe 3+ , Ni 2+ , or Cu 2+ The additives include, but are not limited to, a metal salt and another additive selected from silica, silicone oil, silica-containing materials, and combinations of two or more thereof.

[0011] In other embodiments, the additive comprises silica, silicone oil, a silica-containing material, or a combination of two or more thereof. In other embodiments, the additive comprises a compound comprising Si and O. In some embodiments, the additive comprises SiR 1 a (OR 2 ) 4-a (wherein a is 0, 1, 2, or 3).

[0012] In some embodiments, the additive reduces the volume of the waste stream during distillation, and the additive also prevents waste stream components from fouling the distillation equipment. DETAILED DESCRIPTION OF THE INVENTION

[0013]

[0013] Various embodiments are described below. It should be noted that the specific embodiments are not intended as exhaustive descriptions or as limitations on the broader aspects discussed herein. An aspect described in connection with a specific embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0014]

[0014] As used herein, "about" will be understood by one of ordinary skill in the art and will vary to some extent depending on the context in which it is used. If there are uses of the term that are unclear to a person of ordinary skill in the art, "about" will mean up to ±10% of the particular period, taking into account the context in which it is used.

[0015] The use of the terms "a," "an," and "the" and similar referents in the context of describing elements (particularly in the context of the claims below) should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is intended merely to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise specified herein, and each separate value is incorporated into this specification as if it were individually set forth in this specification. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better describe embodiments and does not limit the scope of the claims unless otherwise specified. No language herein should be construed as indicating any non-claimed element as required.

[0016] Distillation of waste streams containing process solvents, titanium tetrachloride, titanium alkoxides, organic compounds, and / or their decomposition products is difficult at high concentrations. This disclosure relates to a method for adding an additive to the waste stream to separate the solvent from the mixture, thereby recovering a solvent that exhibits improved purity relative to the waste stream. This disclosure also relates to a method for concentrating the waste stream to recover the process solvent.

[0017] In some embodiments, the waste stream is produced from the production of a solid catalyst component comprising magnesium, titanium, and an organic compound. In some embodiments, the solid catalyst component is produced from the production or dissolution of magnesium chloride species. In some embodiments, the magnesium chloride species are treated with titanium species, such as TiCl4. In some embodiments, the species are treated with an organic compound comprising an ester, an ether, an amide, a carbonate, an amine, a carbamide, or a combination of two or more thereof. The process solvent is produced by separating the solvent and soluble components from the produced species.

[0018] Non-limiting examples include, but are not limited to, the following organic compounds:

[0019] [ka]

[0020]

[0019] (wherein, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0021] [ka]

[0022]

[0020] (wherein, R 10 ~R 13 are each independently H, a heteroatom, or C1-C 20 Alkyl, C5-C20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 Aralkyl, alkylaryl, or -OR 15 (In the formula, R 15 is C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 Aralkyl, or C6-C 20 alkylaryl); R 9 and R 14 are each independently F, Cl, Br, I, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 Aralkyl, alkylaryl, -OR 16 or -NR2 17 Selected from;R 16 is C1~C 20 Alkyl, C6-C 20 aryl, or alkylaryl; X 1 and X 2 are O, S or NR 18 and;R 17 H, C1~C 20 Alkyl, C6-C 20 Aryl, or C6-C 20 Aralkyl; R 18 H, C1~C 20 Alkyl, C6-C 20 Aryl, or C6-C 20 aralkyl.) and

[0023] [ka]

[0024]

[0021] (wherein, R 19 From R 32 Each of the groups up to is independently H, F, Cl, Br, I, C1 to C20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0025] [ka]

[0026]

[0022] (In the formula, R 33 From R 38 Each of the groups up to is independently H, F, Cl, Br, I, NR2 39 , S.I.R. 40 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12; R 39 are each independently H, C1 to C 20 Alkyl, C6-C 20 R is selected from aryl or alkylaryl; 40 are independently C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C1-C 20 Alkoxy, cycloalkyl alkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0027] [ka]

[0028]

[0023] (In the formula, R 41 From R 46 Each of the groups up to is independently H, F, Cl, Br, I, NR2 47 , SiR 48 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; r is an integer from 0 to 12; R 47 are each independently H, C1 to C 20 Alkyl, C6-C 20 R is selected from aryl or alkylaryl; 48 are independently C1 to C 20 Alkyl, cycloalkyl, C1-C 20 alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0029] [ka]

[0030]

[0024] (wherein, R 49 From R 54 Each of the groups up to is independently H, F, Cl, Br, I, NR2 55 , SiR 56 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; t is an integer from 0 to 12; R 55 are each independently H, C1 to C 20 Alkyl, C6-C 20R is selected from aryl or alkylaryl; 56 are independently C1 to C 20 Alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and E 1 and E 2 are each independently O, S, or NR 57 (In the formula, R 57 is H, C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 aralkyl. ) and

[0031] [ka]

[0032]

[0025] (wherein, R 58 From R 65 Each of the groups up to 1000 is independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0033] [ka]

[0034]

[0026] (wherein, R 66 From R 79 Each of the groups up to 1000 is independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; X 3 and X 4 are each independently O, S, or NR 80 (In the formula, R 80 is H, C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 aralkyl. ) and

[0035] [ka]

[0036]

[0027] (wherein, R 81 , R 82 , R 83 , R 84 , R 85 and R 86 are each independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; Examples include:

[0037] In some embodiments, the solvent stream is separated from the solid catalyst component and then mixed with an aqueous solvent. Optionally, the aqueous solvent may contain a base or other ionic salt. In some embodiments, the aqueous solvent containing the base has a neutral or basic pH.

[0038] In some embodiments, the waste stream is acidic. The pH of the waste stream may be less than about 7. The waste stream may be neutralized with a neutralizing agent prior to the addition of the additive. In some embodiments, the additive neutralizes the waste stream. As a non-limiting example, the additive may be added to the waste stream as a metal hydroxide salt. In some embodiments, the waste stream is partially or completely neutralized. The additive may be added to the waste stream as a salt, an aqueous solution, or a suspension in water. Addition of the additive as an aqueous solution or a suspension in water may result in hydrolysis of the waste stream.

[0039] The waste stream may include decomposition products of organic compounds. In some embodiments, the organic compound is an alcohol, ester, ketone, ether, amide, amine, carbonate, carbamide, alkyl urea, imine, sulfide, thioester, or a combination of two or more thereof. In some embodiments, the organic compound and / or its decomposition products may be polydentate compounds (i.e., compounds that bond to a metal atom through at least two atoms on the compound). In some embodiments, the organic compound may include a diol, such as a catechol or a glycol. In other embodiments, the organic compound is an internal donor. The decomposition products may be present in the waste stream prior to the addition of the additive or prior to neutralization or hydrolysis of the waste stream. The decomposition products may be the result of neutralization or hydrolysis of the waste stream.

[0040]

[0031] Examples of additives that can be used in the process of the present invention include, but are not limited to, metal salts capable of separating solvent from a neutralized process solvent-water mixture at high solvent concentrations. Suitable metal salts for use in the process of the present invention include metal salts containing a Group 1 metal, a Group 2 metal, a transition metal, or a combination of two or more thereof. Other exemplary additives include metal sources with a valence of one or more. Suitable metal sources with a valence of one or more include Na. + , Mg 2+ , Ca 2+ , Fe2+ , Fe 3+ , Ni 2+ , or Cu 2+ In some embodiments, the additive can be a metal hydroxide salt, a metal chloride salt, or a metal sulfate salt.

[0041] Other embodiments of the additive can include silica, silicone oil, silica-containing materials, or combinations of two or more thereof. Other embodiments of the additive can include silica, silicone oil, silica-containing materials, or combinations of two or more thereof. In further embodiments, a metal salt having a metal source with a valence of 1 or greater is added to the silica, silicone oil, and / or silica-containing materials to facilitate separation of the waste stream. In other embodiments, the additive comprises a compound comprising Si and O. In some embodiments, the additive comprises SiR 1 a (OR 2 ) 4-a (wherein a is 0, 1, 2, or 3; R 1 and R 2 are each independently H, alkyl, or aryl. In some embodiments where the additive comprises Si, Si is a polymer.

[0042] Adding these additives to the waste stream prevents components of the waste stream from adhering to materials commonly used in process vessels, such as glass and steel. In the event of a process upset, the additives described herein prevent components of the waste stream from adhering to the distillation apparatus and / or other components involved in conveying the waste stream to the distillation apparatus, such as mixers, mixer shafts, piping, or columns. Additionally, the additives reduce the volume of the waste stream during distillation.

[0043] The invention thus generally described will be more readily understood by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the invention. [Example]

[0044]

[0035] Recovery of titanium tetrachloride in the presence of selective donor species results in decomposition of the donor, producing surfactant species that make separation difficult. To keep the distillation for TiCl recovery functioning, the decomposition species must be removed from the process solvent after TiCl recovery. Process solvents rich in donor decomposition products can be neutralized to allow for further solvent recovery.

[0045] Examples of donor species that make separation difficult include the following:

[0046] [ka]

[0047]

[0037] (wherein, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0048] [ka]

[0049]

[0038] (wherein, R 10 ~R 13 are each independently H, a heteroatom, or C1-C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C20 Aralkyl, alkylaryl, or -OR 15 (In the formula, R 15 is C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 Aralkyl, or C6-C 20 alkylaryl); R 9 and R 14 are each independently F, Cl, Br, I, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 Aralkyl, alkylaryl, -OR 16 or -NR2 17 Selected from;R 16 is C1~C 20 Alkyl, C6-C 20 aryl or alkylaryl; X 1 and X 2 are O, S or NR 18 and;R 17 H, C1~C 20 Alkyl, C6-C 20 Aryl, or C6-C 20 Aralkyl; R 18 H, C1~C 20 Alkyl, C6-C 20 Aryl, or C6-C 20 aralkyl.) and

[0050] [ka]

[0051]

[0039] (wherein, R 19 From R 32 Each of the groups up to is independently H, F, Cl, Br, I, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0052] [ka]

[0053]

[0040] (In the formula, R 33 From R 38 Each of the groups up to is independently H, F, Cl, Br, I, NR2 39 , SiR 40 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12; R 39 are each independently H, C1 to C 20 Alkyl, C6-C 20 R is selected from aryl or alkylaryl; 40 are independently C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C1-C 20 Alkoxy, cycloalkyl alkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0054] [ka]

[0055]

[0041] (In the formula, R 41 From R 46 Each of the groups up to is independently H, F, Cl, Br, I, NR247 , SiR 48 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; r is an integer from 0 to 12; R 47 are each independently H, C1 to C 20 Alkyl, C6-C 20 R is selected from aryl or alkylaryl; 48 are independently C1 to C 20 Alkyl, cycloalkyl, C1-C 20 alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0056] [ka]

[0057]

[0042] (In the formula, R 49 From R 54 Each of the groups up to is independently H, F, Cl, Br, I, NR2 55 , SiR 56 3. C1~C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; t is an integer from 0 to 12; R 55 are each independently H, C1 to C 20 Alkyl, C6-C 20 R is selected from aryl or alkylaryl; 56 are independently C1 to C 20Alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and E 1 and E 2 are each independently O, S, or NR 57 (In the formula, R 57 is H, C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 aralkyl. ) and

[0058] [ka]

[0059]

[0043] (In the formula, R 58 From R 65 Each of the groups up to 1000 is independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0060] [ka]

[0061]

[0044] (In the formula, R 66 From R 79 Each of the groups up to 1000 is independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; X 3 and X 4 are each independently O, S, or NR 80 (R in the formula 80 is H, C1~C 20 Alkyl, C6-C 20 Aryl, C6-C 20 aralkyl).

[0062] [ka]

[0063]

[0045] (In the formula, R 81 , R 82 , R 83 , R 84 , R 85 and R 86 are each independently H, F, Cl, Br, I, a heteroatom, C1 to C 20 Alkyl, C5-C 20 Cycloalkyl, C5-C 20 Cycloalkylalkyl, C6-C 20 Aryl, C6-C 20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; is shown.

[0064]

[0046] Catalyst compositions containing difficult-to-separate donor species can be prepared, for example, according to the methods described in WO2023 / 034334, WO2022 / 197491, WO2010 / 078494, and / or U.S. Patent Nos. 7,381,779; 7,491,670; 7,678,868; 7,781,363; 7,989,383; 8,288,585; 8,536,372; and 8,778,826; and U.S. Patent Application Publication No. 2013 / 0338321.

[0065] Distillation of neutralized titanium tetrachloride containing waste streams has proven difficult as the concentration of process solvent increases. The presence of titanium alkoxide and decomposition products of the donor species makes distillation of the neutralized solvent impossible. Distillation can cause uncontrolled volume expansion.

[0066] The addition of a species containing a metal ion with a valence greater than one results in chelation of the metal ion in the decomposed donor species. The resulting donor metal species allows for separation of the process solvent. The metal species can be added at any stage in the process to achieve this effect. Any metal species containing a metal with a valence greater than one may achieve this effect.

[0067] The addition of salt additives during the distillation of neutralized process solvents reduces the volume of the solvent. Salt additives can include Group 2 metal sources, including magnesium and calcium ions. In addition to reducing the volume required for distillation, the addition of these salts has also been found to prevent material from fouling equipment.

[0068]

[0050]

[0069] [Table 1]

[0070] This effect allows it to be used in combination with other additives to affect the separation ability of the material.

[0052]

[0071] [Table 2]

[0072] The process solvent may contain one or more organic components or decomposition products of these organic components, which may be present in the process solvent during the synthesis of the solid catalyst component.

[0073] [Table 3]

[0074] The use of divalent or higher valent salts can prevent the neutralization of process solvents from producing problematic surfactant species, where the metal source can be added before or during neutralization, or can be added as a hydroxide source.

[0075] [Table 4]

[0076] [Table 5-1]

[0077] [Table 5-2]

[0078]

[0055] While particular embodiments have been illustrated, changes and modifications can be made in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0079]

[0056] The embodiments illustratively described herein can suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising," "including," and "containing" are intended to be read expansively and without limitation. Furthermore, the terms and expressions used herein are used as terms of description, not of limitation, and the use of such terms and expressions is not intended to exclude any equivalents of the shown and described features or portions thereof, recognizing that various modifications are possible within the scope of the claimed technology. Furthermore, the phrase "consisting essentially of" will be understood to include the elements specifically recited and additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any elements not specified.

[0080]

[0057] The present disclosure is not limited with respect to the specific embodiments described in this application. As will be apparent to those skilled in the art, many modifications and variations are possible without departing from the spirit and scope thereof. Functionally equivalent methods and compositions within the scope of the present disclosure, in addition to the methods and compositions recited herein, will be apparent to those skilled in the art from the above description. Such modifications and variations are intended to be included within the scope of the appended claims. The present disclosure is limited only by the appended claims, and the full scope of equivalents to such claims. It will be understood that the present disclosure is not limited to particular methods, reagents, compounds, or compositions, which can, of course, vary. It will also be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0081]

[0058] Furthermore, where features or aspects of the present disclosure are described in terms of a Markush group, those skilled in the art will recognize that the present disclosure also is described in terms of any individual member or subgroup of members of the Markush group.

[0082]

[0059] It will be apparent to those skilled in the art that, for any and all purposes, particularly in view of providing a written description, all ranges disclosed herein encompass all possible subranges and combinations thereof. All recited ranges are fully described, and it will be readily apparent that the same ranges can be divided into at least two, three, four, five, ten, etc., equal parts. As a non-limiting example, each range described herein can be readily divided into a lower third, a middle third, an upper third, etc. It will also be apparent to those skilled in the art that all terms such as "up to," "at least," "greater than," "less than," etc., also include the recited numbers and refer to ranges that can be subsequently divided into subranges as described above. Finally, it will be apparent to those skilled in the art that a range includes each individual member.

[0083]

[0060] All publications, patent applications, issued patents, and other documents mentioned herein are incorporated by reference in their entirety herein, to the same extent as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions contained in the text incorporated by reference are excluded to the extent they conflict with definitions in this disclosure.

[0084]

[0061] Other embodiments are set forth in the following claims.

Claims

1. 1. A method for concentrating a waste stream, comprising: adding an additive to the waste stream to form an additive mixture, the waste stream comprising process solvent, titanium tetrachloride, titanium alkoxide, organic compounds, and / or decomposition products thereof; concentrating the additive mixture to form a concentrated waste stream having a volume that is smaller than the volume of the waste stream; A method comprising:

2. 1. A method for recovering solvent from a waste stream, comprising: adding said waste stream containing process solvent, titanium tetrachloride, titanium alkoxide, organic compounds, and / or decomposition products thereof to a distillation apparatus; adding an additive to the distillation apparatus to form a distillation mixture; distilling the distillation mixture to recover a solvent exhibiting increased purity relative to the waste stream; A method comprising:

3. The method of claim 1 or 2, wherein the additive comprises a metal salt.

4. 4. The method of claim 1, wherein the additive comprises a metal hydroxide salt, a metal chloride salt, a metal sulfate salt, or a combination of two or more thereof.

5. 5. The method of claim 3 or 4, wherein the metal salt comprises sodium ions, magnesium ions, calcium ions, iron ions, nickel ions, copper ions, or a combination of two or more thereof.

6. 6. The method of claim 3, wherein the additive further comprises silica, silicone oil, a silica-containing material, or a combination of two or more thereof.

7. 3. The method of claim 1 or 2, wherein the additive comprises silica, silicone oil, a silica-containing material, or a combination of two or more thereof.

8. 8. The method of any one of claims 1 to 7, further comprising neutralizing the waste stream with a neutralizing agent prior to adding the additive.

9. 8. The method of claim 1, further comprising neutralizing the waste stream during addition of the additive.

10. 10. The method of any one of claims 1 to 9, wherein the additive neutralizes the waste stream.

11. 11. The method of any one of claims 8 to 10, wherein the waste stream is partially neutralized.

12. 11. The method of any one of claims 8 to 10, wherein the waste stream is completely neutralized.

13. 13. The method of any one of claims 1 to 12, wherein the additive is added as an aqueous solution.

14. 13. The method of any one of claims 1 to 12, wherein the additive is added as a suspension in water.

15. 15. The method of claim 13 or 14, wherein the waste stream is hydrolyzed.

16. 16. The method of any one of claims 1 to 15, wherein the organic compound comprises an alcohol, an ester, a ketone, an ether, an amide, an amine, a carbonate, a carbamide, an alkyl urea, an imine, a sulfide, a thioester, or a combination of two or more thereof.

17. 17. The method of any one of claims 1 to 16, wherein the organic compound is an internal donor.

18. 18. The method of any one of claims 1 to 17, wherein the waste stream further comprises decomposition products of an internal donor.

19. 20. The method of claim 18, wherein the decomposition products of the internal donor are formed by neutralization of the waste stream.

20. 20. The method of claim 18, wherein the decomposition products of the internal donor are formed from hydrolysis of the waste stream.

21. 21. The method of any one of claims 1 to 20, wherein the additive reduces the volume of waste streams during distillation.

22. 22. The method of any one of claims 1 to 21, wherein the additive prevents waste stream components from fouling the distillation apparatus.

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