WO2024168274A1

WO2024168274A1 - Process for the separation of solvent from waste streams

Info

Publication number: WO2024168274A1
Application number: PCT/US2024/015212
Authority: WO
Inventors: Nathan Andrew EBERHARDT; Nick Sherman; Jonathan Isaac POLLACK; Demetrius Michos
Original assignee: W.R. Grace & Co.-Conn.
Priority date: 2023-02-10
Filing date: 2024-02-09
Publication date: 2024-08-15

Abstract

A process for recovering solvent from a waste stream includes adding the waste stream including a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation 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 the solvent exhibiting an increased purity compared to the waste stream.

Description

PROCESS FOR THE SEPARATION OF SOLVENT FROM WASTE STREAMS

CROSS-REFERENCE TO RELATED APPLICATIONS

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

BACKGROUND

[0002] Process solvent from catalysts made using internal donors undergo side reactions during TiCk recovery to generate material that is difficult to separate using standard mechanisms. Waste streams containing donor decomposition products present difficulties in separation and present processing problems from adhering to vessel walls. There is therefore a need for improved methods for the recovery of solvent from waste streams resulting from the manufacture of catalysts.

SUMMARY

[0003] In one aspect, a method of concentrating a waste stream is provided. The methods include adding an additive to the waste stream to form an additive mixture, where the waste stream comprises a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation products thereof; and concentrating the additive mixture to form a concentrated waste stream having a lower volume compared to the waste stream. Methods for concentrating the additive mixture can 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 of separating solvents from a waste stream is provided. The methods include adding an additive to the waste stream to form an additive mixture, where the waste stream comprises a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation 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 may be distillation of the additive mixture.

[0005] In another aspect, a method of recovering solvents from a waste stream is provided. The methods include adding the waste stream comprising a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation 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 the solvent exhibiting an increased purity compared to the waste stream.

[0006] In some embodiments, the pH of the waste stream is acidic. In some embodiments, the method(s) further comprises neutralizing the waste stream with a neutralizing agent before adding the additive. In some embodiments, the method further includes neutralizing the waste stream during addition of the additive. In an embodiment, the additive neutralizes the waste stream. In some embodiments, the waste stream is partially neutralized. In other embodiments, the waste stream is fully 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, the waste stream is hydrolyzed as a result of the addition of the additive as an aqueous solution or as a suspension in water.

[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 catechol, a diol, a multidentate alcohol such as glycol, or a diol diester. In an embodiment, the organic compound is an internal donor. In some embodiments, the waste stream further comprises an internal donor decomposition product. The internal donor decomposition product may initially be present in the waste stream, or the internal donor decomposition product may be formed from neutralization or hydrolysis of the waste stream.

[0009] In some embodiments, the additive comprises a metal salt. In 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 valency of 1 or greater. Examples of a metal source include, but are not limited to, Na⁺, Mg²⁺, Ca²⁺, Fe²⁺, Fe³⁺, Ni²⁺, or Cu²⁺. In some embodiments, the additive comprises a metal salt and another additive selected from silica, silicone oil, a silica containing material, and a combination of two or more thereof.

[0011] In other embodiments, the additive includes 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'a(OR²)4-a, where a is 0, 1, 2, or 3.

[0012] In some embodiments, the additive reduces waste stream volume during distillation, and the additive prevents waste stream components from adhering to the distillation apparatus.

DETAILED DESCRIPTION

[0013] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0014] As used herein, “about” will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, “about” will mean up to plus or minus 10% of the particular term.

[0015] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise 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 illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0016] Distillation of waste streams that include a process solvent, titanium tetrachloride, titanium alkoxides, organic compounds, and/or degradation products thereof are difficult at high concentrations. The present disclosure relates to the addition of an additive(s) to the waste streams to separate the solvent from the mixture, to recover the solvent that exhibits an increased purity compared to the waste stream. The present disclosure also relates to methods of concentrating waste streams, leading to the recovery of process solvents.

[0017] In some embodiments, the waste stream is produced from the generation of a solid catalyst component comprising magnesium, titanium, and an organic compound. In some embodiments, the solid catalyst component is generated from the creation or dissolution of a magnesium chloride species. In some embodiments, the magnesium chloride species is treated with a titanium species such as TiCk. In some embodiments, the species is treated with an organic compound containing an ester, an ether, an amide, a carbonate, an amine, a carbamide, or a combination of two or more thereof. The process solvent may be generated from the separation of solvent and soluble components from the generated species.

[0018] Non-limiting examples organic compounds include, but are not limited to, those shown below:

[0019] wherein: R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0020] wherein: R¹⁰-R¹³ are each independently selected from H, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, alkylaryl, or an -OR¹⁵ where R¹⁵ is C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl, or C6-C20 alkylaryl; R⁹ and R¹⁴ are each independently selected from F, Cl, Br, I, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, alkylaryl, -OR¹⁶, or -NR2¹⁷; R¹⁶ is C1-C20 alkyl, C6-C20 aryl, or alkylaryl; X¹ and X² are each O, S, or NR¹⁸; R¹⁷ is H, C1-C20 alkyl, C6-C20 aryl, or C6-C20 aralkyl; and R¹⁸ is H, C1-C20 alkyl, C6-C20 aryl, or C6-C20 aralkyl;

[0021] where each of R¹⁹ through R³² is independently H, F, Cl, Br, I, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0022] wherein: each of R³³ through R³⁸ is independently H, F, Cl, Br, I, NR2³⁹, SiR⁴⁰3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12; each R³⁹ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; and each R⁴⁰ is independently C1-C20 alkyl, C5-C20 cycloalkyl, C1-C20 alkoxy, cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0023] wherein: each of R⁴¹ through R⁴⁶ is independently H, F, Cl, Br, I, NR2⁴⁷, SiR⁴⁸3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; r is an integer from 0 to 12; each R⁴⁷ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; and each R⁴⁸ is independently C1-C20 alkyl, cycloalkyl, C1-C20 alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0024] wherein: each of R⁴⁹ through R⁵⁴ is independently H, F, Cl, Br, I, NR2⁵⁵, SiR⁵⁶3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; t is an integer from 0 to 12; each R⁵⁵ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; each R⁵⁶ is independently C1-C20 alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and each E¹ and E² is independently O, S, or NR57, where R57 is H, C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl;

[0025] wherein: each of R⁵⁸ through R⁶⁵ are independently H, F, Cl, Br, I, a heteroatom, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0026] wherein each R⁶⁶ through R⁷⁹ is independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and each X³ and X⁴ is independently O, S, or NRso, where Rso is H, C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl; and

[0027] wherein: R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, and R⁸⁶ are each independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl.

[0028] In some embodiments, the solvent stream is mixed with an aqueous solvent after separation from the solid catalyst components. Optionally, the aqueous solvent may include a base or other ionic salts. In some embodiments, the aqueous solvent including a base is neutral or basic in pH.

[0029] 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 neutralization agent before 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 fully neutralized. The additive may be added to the waste stream as a salt, as an aqueous solution, or as a suspension in water. The addition of the additive as an aqueous solution or as a suspension in water may result in hydrolysis of the waste stream.

[0030] The waste stream may include a decomposition product of the organic compound. 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, the organic compound and/or its decomposition product may be a multidentate compound (i.e., a compound that binds 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 product may be present in the waste stream before the addition of the additive or before neutralization or hydrolysis of the waste stream. In some embodiments, the decomposition product may be a result of neutralization or hydrolysis of the waste stream.

[0031] Examples of additives that may be used in the methods of the present invention include, but are not limited to, a metal salt which allows for the separation of solvents from neutralized process solvent water mixtures at higher solvent concentrations. Suitable metal salts for use in the present methods include metal salts having a group 1 metal, a group 2 metal, a transition metal, or a combination of two or more thereof. Other illustrative additives include metal sources with valency of one or greater. Suitable metal sources with valency of one or greater include, but are not limited to, Na⁺, Mg²⁺, Ca²⁺, Fe ²⁺, Fe ³⁺, Ni²⁺, or Cu²⁺. In some embodiments, the additive may be a metal hydroxide salt, a metal chloride salt, or a metal sulfate salt.

[0032] Other embodiments of the additives include silica, silicone oil, a silica containing material, or a combination of two or more thereof. Another embodiment of the additive includes silica, silicone oil, a silica containing material, or a combination of two or more thereof. In further embodiments, silica, silicone oil, and/or silica containing material is added with a metal salt having a metal source with valency of one or greater to aid in the separation of the waste stream. In other embodiments, the additive comprises a compound comprising Si and O. In some embodiments, the additive comprises SiR'a(OR²)4-a, where a is 0, 1, 2, or 3, and R¹ and R² may each independently be H, alkyl, or aryl. In some embodiments where the additive includes Si, the Si is polymeric.

[0033] The addition of such additives to the waste stream prevents the components of the waste stream from adhering to materials commonly used for processing vessels such as glass or steel. The additives described herein prevent components of the waste stream from adhering to the distillation apparatus and/or other components involved with delivery of the waste stream into the distillation apparatus such as mixers, mixer shafts, piping, or columns in the event of process upset. Further, the additive reduces waste stream volume during distillation.

[0034] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.

EXAMPLES

[0035] Titanium tetrachloride recovery in the presence of select donor species leads to the decomposition of donors to create surfactant species that make separation difficult. Post TiCk recovery process solvent needs removal of decomposition species for TiCh recovery distillation to remain functional. Donor decomposition rich process solvent can be neutralized for additional solvent recovery.

[0036] Examples of donor species leading to difficult separation are shown below:

[0037] wherein: R³, R⁴, R⁵, R⁶, R⁷, and R⁸ are each independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0038] wherein: R¹⁰-R¹³ are each independently selected from H, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, alkylaryl, or an -OR¹⁵ where R¹⁵ is C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl, or C6-C20 alkylaryl; R⁹ and R¹⁴ are each independently selected from F, Cl, Br, I, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, alkylaryl, -OR¹⁶, or -NR2¹⁷; R¹⁶ is C1-C20 alkyl, C6-C20 aryl, or alkylaryl; X¹ and X² are each O, S, or NR¹⁸; R¹⁷ is H, C1-C20 alkyl, C6-C20 aryl, or C6-C20 aralkyl; and R¹⁸ is H, C1-C20 alkyl, C6-C20 aryl, or C6-C20 aralkyl;

[0039] where each of R¹⁹ through R³² is independently H, F, Cl, Br, I, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0040] wherein: each of R³³ through R³⁸ is independently H, F, Cl, Br, I, NR2³⁹, SiR⁴⁰3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; q is an integer from 0 to 12; each R³⁹ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; and each R⁴⁰ is independently C1-C20 alkyl, C5-C20 cycloalkyl, C1-C20 alkoxy, cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0041] wherein: each of R⁴¹ through R⁴⁶ is independently H, F, Cl, Br, I, NR2⁴⁷, SiR⁴⁸3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; r is an integer from 0 to 12; each R⁴⁷ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; and each R⁴⁸ is independently C1-C20 alkyl, cycloalkyl, C1-C20 alkoxy, cycloalkylalkyl, aryl, aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0042] wherein: each of R⁴⁹ through R⁵⁴ is independently H, F, Cl, Br, I, NR2⁵⁵, SiR⁵⁶3, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; t is an integer from 0 to 12; each R⁵⁵ is independently selected from H, C1-C20 alkyl, C6-C20 aryl or alkylaryl; each R⁵⁶ is independently C1-C20 alkyl, cycloalkyl, alkoxy, cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and each E¹ and E² is independently O, S, or NR57, where R57 is H, C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl;

[0043] wherein: each of R⁵⁸ through R⁶⁵ are independently H, F, Cl, Br, I, a heteroatom, Ci- C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl;

[0044] wherein each R⁶⁶ through R⁷⁹ is independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 aralkyl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl; and each X³ and X⁴ is independently O, S, or NRso, where Rso is H, C1-C20 alkyl, C6-C20 aryl, C6-C20 aralkyl; and

[0045] wherein: R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, and R⁸⁶ are each independently H, F, Cl, Br, I, a heteroatom, C1-C20 alkyl, C5-C20 cycloalkyl, C5-C20 cycloalkylalkyl, C6-C20 aryl, C6-C20 alkylaryl, heterocyclyl, heterocyclylalkyl, heteroaryl, or heteroarylalkyl.

[0046] Catalyst compositions including a donor species that leads to difficult separation can be prepared as described, for example, in WO 2023/034334, WO 2022/197491, WO 2010/078494, and/or U.S. Pat. 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 in U.S. Patent Publication No. 2013/0338321.

[0047] Distillation of a neutralized titanium tetrachloride containing waste stream was found to be difficult at higher concentrations of process solvent. The presence of titanium alkoxides and decomposition products of donor species lead to the inability to distill neutralized solvent. Distillation can lead to an uncontrollable expansion in volume.

[0048] Addition of species bearing metals ions with valency of one or greater can lead to the chelation of the metal ion in the decomposed donor species. The resulting donor metal species enables the separation of process solvent. The metal species can be added at any place in the process to achieve this effect. Any metal species bearing a metal with a valency of one or greater could achieve this effect.

[0049] Addition of salt additives reduces the solvent volume during the distillation of neutralized process solvent. Salt additives can include group 2 metal sources of magnesium and calcium ions. The addition of these salts was found to help prevent materials from adhering to equipment in addition to reducing the volume needed for distillation.

[0050] Table 1. Examples of salt additives.

[0051] This effect can be used in combination with other additives to affect the ability to separate the materials.

[0052] Table 2. Examples of other additives.

[0053] The process solvent may contain one or more organic components or the decomposition products of these organic components. The organic components may be present in the process solvent resulting from the synthesis of the solid catalyst component.

Table 3. Examples of organic component mixtures

[0054] A divalent or greater salt can be used so that the neutralization of process solvent does not form problematic surfactant species. Here, the metal source can be added before or during the neutralization, or as a hydroxide source.

Table 5. Examples of additives added during neutralization

Table 5. Donors used in the organic component mixtures of Table 3 and in the neutralization of process solvents of Table 4.

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

[0056] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been 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 claimed technology. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0057] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art.

Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, or compositions, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

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

[0059] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0060] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference 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 that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

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

Claims

WHAT IS CLAIMED IS:

1. A method for concentrating a waste stream, the method comprising: adding an additive to the waste stream to form an additive mixture, wherein the waste stream comprises a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation products thereof; and concentrating the additive mixture to form a concentrated waste stream having a lower volume compared to a volume of the waste stream.

2. A method for recovering a solvent from a waste stream, the method comprising: adding the waste stream comprising a process solvent, titanium tetrachloride, titanium alkoxides, an organic compound, and/or degradation 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 the solvent exhibiting an increased purity compared to the waste stream.

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

4. The method any one of claims 1-3, 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. The method of claim 3 or claim 4, wherein the metal salt comprises a sodium ion, a magnesium ion, a calcium ion, an iron ion, a nickel ion, a copper ion, or a combination of two or more thereof.

6. The method of any one of claims 3-5, wherein the additive further comprises silica, silicone oil, a silica containing material, or a combination of two or more thereof.

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

8. The method of any of the preceding claims further comprising neutralizing the waste stream with a neutralizing agent before adding the additive.

9. The method of any of claims 1-7 further comprising neutralizing the waste stream during addition of the additive.

10. The method of any of the preceding claims, wherein the additive neutralizes the waste stream.

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

12. The method of any of claims 8-10, wherein the waste stream is fully neutralized.

13. The method of claim any of the preceding claims, wherein the additive is added as an aqueous solution.

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

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

16. The method of any of the preceding claims, 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. The method any of the preceding claims, wherein the organic compound is an internal donor.

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

19. The method of claim 18, wherein the internal donor decomposition product is formed from neutralization of the waste stream.

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

21. The method of any of claims 1-20, wherein the additive reduces waste stream volume during distillation.

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