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(12) United States Patent (10) Patent No.: US 8,541,057 B2 Beatty (45) Date of Patent: Sep

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(12) United States Patent (10) Patent No.: US 8,541,057 B2 Beatty (45) Date of Patent: Sep US008541057B2 (12) United States Patent (10) Patent No.: US 8,541,057 B2 Beatty (45) Date of Patent: Sep. 24, 2013 (54) CYCLOHEXANEOXIDATION PROCESS (56) References Cited BYPRODUCT DERVATIVES AND METHODS FORUSING THE SAME U.S. PATENT DOCUMENTS 3,365.490 A 1/1968 Arthur et al. (75) Inventor: Richard P. Beatty, Newark, DE (US) 4,005,051 A * 1/1977 Brunner ........................ 524/310 4,273,179 A 6, 1981 Gardikes (73) Assignee: Invista North America S.A.R.L., 4,525,574 A 6, 1985 Altounian 5,981,769 A * 1 1/1999 Baur et al. .................... 549,266 Wilmington, DE (US) 6,008,418 A * 12/1999 Baur et al. ..... 568/853 6,288,286 B1* 9/2001 Stein et al. ............. ... 568,864 (*) Notice: Subject to any disclaimer, the term of this 6,313.358 B1 * 1 1/2001 Breitscheidel et al. ....... 568,864 patent is extended or adjusted under 35 6,407.294 B1* 6/2002 Breitscheidel et al. ....... 568,864 U.S.C. 154(b) by 124 days. 6,727,395 B1 * 4/2004 Stein et al. .................... 568,864 7,226,895 B2 6/2007 Xiang 2007/0112225 A1 5/2007 Sirch et al. .................... 568,864 (21) Appl. No.: 13/140,065 2008, 0207958 A1* 8, 2008 Haunert et al. 568,862 2009/0048471 A1* 2, 2009 Ii et al. .... 568,884 (22) PCT Filed: Dec. 11, 2009 2011/02O1848 A1* 8, 2011 Ii et al. ........... ... 568,833 2011/0263907 A1* 10, 2011 Abillard et al. 568/852 (86). PCT No.: PCT/US2O09/067634 2012/0101009 A1 * 4/2012 Beatty ........................... 507/103 S371 (c)(1), FOREIGN PATENT DOCUMENTS (2), (4) Date: Oct. 27, 2011 WO WOO2, 16659 2, 2002 (87) PCT Pub. No.: WO2010/071759 * cited by examiner PCT Pub. Date: Jun. 24, 2010 Primary Examiner — Erma Cameron (65) Prior Publication Data (74) Attorney, Agent, or Firm — Robert B. Furr, Jr. US 2012/OO64252A1 Mar. 15, 2012 (57) ABSTRACT Related U.S. Application Data Disclosed are ester compositions, solvents, cleaning formu (60) Provisional application No. 61/138,697, filed on Dec. lations, curing agents, reactive diluent solvents, controlled 18, 2008, provisional application No. 61/148,433, acid function release agents, polyol monomers, drilling mud filed on Jan. 30, 2009, provisional application No. and methods of making and using the same. Disclosed com 61/183,131, filed on Jun. 2, 2009. positions include: a) about 10 to 60 weight percent methyl hydroxycaproate, (51) Int. Cl. b) about 20 to 80 weight percent dimethyl adipate: B05D3/10 (2006.01) c) about 1 to 15 wt % of dimethyl glutarate; (52) U.S. Cl. d) about 0.1 to 5 wt % of dimethyl succinate; USPC ........ 427/344; 427/384; 427/385.5; 427/387: 427/402:524/284 e) about 0.1 to 7 wt % of at least one cyclohexanediot; (58) Field of Classification Search and f) less than about 20 wt % oligomeric esters. None See application file for complete search history. 33 Claims, No Drawings US 8,541,057 B2 1. 2 CYCLOHEXANE OXDATION PROCESS tains various mono- and di-acids, hydroxy-acids, and other BYPRODUCT DERVATIVES AND METHODS oxidation co-products formed during the initial oxidation of FOR USING THE SAME cyclohexane. Regardless of whether water wash is performed as an inter CROSS-REFERENCE TO RELATED mediate step, the stream containing K, A, and CHHP is fur APPLICATIONS ther processed by methods well known in the art, to complete conversion of CHHP to Kand A. The resulting mixture is then This application claims the benefit of the filing dates of refined, again by methods well known in the art, to recover U.S. Provisional Application No. 61/138,697 filed on Dec. unconverted cyclohexane for recycle and to obtain purified K 10 and A for Subsequent oxidation to adipic acid or conversion to 18, 2008; U.S. Provisional Application No. 61/148,433 filed caprolactam. The high-boiling distillation bottoms from this on Jan. 30, 2009; and U.S. Provisional Application No. refining operation are known as non-volatile residue, “NVR. 61/183,131 filed on Jun. 2, 2009; the entire contents of which To Summarize, the co-product streams, sometimes referred are incorporated herein by reference. This application is also to herein as “by-product' streams, available from a cyclohex related by disclosure of related subject matter to PCT Appli 15 ane oxidation process include “Water Wash' (the aqueous cation No. PCT/US2009/067634, filed on Dec. 11, 2009. stream produced by water extraction of cyclohexane oxidate) and “NVR (the high-boiling distillation bottoms from KA BACKGROUND refining). Concentration of Water Wash by removal of at least some of the water produces a stream known as “COP Acid.” As petroleum-based materials escalate in price and envi “Water Wash”, “COP Acid, and “NVR are known to ronmental pressures increase, there is a growing need to contain both mono- and poly-functional materials, mainly responsibly utilize, to the greatest extent possible, all prod with the functional groups comprising acids, peroxides, ucts from petrochemical processes, which includes the ketones, alcohols, and esters. Other functional groups such as desired main products as well as co-products. Co-products aldehyde, lactone, and alkene are also known to be present. are often treated as “waste’ materials of no value. 25 Multiple functional groups may be combined in a single It is known in the manufacture of adipic acid or caprolac molecule. Such as in a hydroxyacid, for example hydroxyca tam from cyclohexane that co-product streams result because proic acid or hydroxyvaleric acid. In general, the acid func the chemical transformations do not proceed perfectly in tional group is at one end of a linear hydrocarbyl chain, and 100% yield. These co-product streams contain a variety of the hydroxy group may be present in various positions along molecules having functionalities which include, among oth 30 the chain. Known examples of hydroxyacids include 6-hy ers, the alcohol, alkene, carboxylic acid, lactone, ester, and droxycaproic acid, 5-hydroxyvaleric acid, 3-hydroxyvaleric ketone groups. It is known to use some co-product streams for acid, and 3-hydroxypropionic acid. Similarly, known their fuel value. In Such uses, there is no recognition or recov examples of simple mono-acids include formic acid, acetic ery of value for the functionality present in the co-product acid, propionic acid, butyric acid, Valeric acid, and caproic stream. As a result, most of the co-product stream from adipic 35 acid. Known examples of diacids include Succinic acid, glu acid manufacture remains underutilized. taric acid, and adipic acid. Known examples of keto-acids include 4-oxo Valeric acid (also known as levulinic acid) and Manufacture of adipic acid from cyclohexane generally 5-oxo caproic acid. Known examples of alcohols include involves two steps. First, cyclohexane is oxidized using air to cyclohexanol. 1-propanol. 1-butanol. 1-pentanol, and various a mixture of cyclohexanol (A) and cyclohexanone (K), the 40 diols such as 1.2- 1.3-, and 1.4-cyclohexanediols, various mixture being referred to as KA. Second, KA is oxidized butanediol isomers, and various pentanediol isomers. using nitric acid to adipic acid. The current disclosure is The chemical complexity of “Water Wash”, “COP Acid', focused on utilization of co-product streams from the first of and “NVR’ introduce difficulties to obtain pure, commer these two steps, the oxidation of cyclohexane to K.A. This cially-useful chemicals from these streams. Efforts to “cyclohexane oxidation' step is also performed in manufac 45 develop processes to obtain useful materials from these ture of caprolactam from cyclohexane. streams are known and varied. In the known cyclohexane oxidation processes, cyclohex In view of the foregoing disclosures, it would be desirable ane is generally oxidized with oxygen or a gas containing to provide a simple process for the recovery of ester-based oxygen, at low conversion, to produce an intermediate stream solvents from “Water Wash”, “COP Acid, and/or “NVR containing cyclohexanol (A), cyclohexanone (K), and cyclo 50 which uses economically sound and practical high recovery hexyl hydroperoxide (CHHP) in cyclohexane. CHHP is an means. It would also be desirable to provide an effective important intermediate in oxidation of cyclohexane to KA solvent or novel chemical intermediate. and various processes are known in the art to optimize con version of CHHP to K.A. in order to maximize yield of KA. In SUMMARY addition to K, A, and CHHP, cyclohexane oxidation produces 55 co-products. In some cases, it has been found that these co Embodiments of the present disclosure provide for ester products interfere with Subsequent processing to convert compositions, solvents, cleaning formulations, curing agents, CHHP to K.A. It is known that at least some of the interfering reactive diluent solvents, controlled acid function release co-products can be removed by contacting the intermediate agents, polyol monomers, drilling mud, methods of making stream containing K, A, and CHHP with water or caustic, for 60 each of the above, methods of using each of the above, meth example as described in U.S. Pat. No. 3,365,490, which is ods for hardening a friable substrate, and the like. incorporated herein by reference. This contacting, or extrac Embodiments of the composition, among others, include tion results in a two-phase mixture that, after phase separa obtaining a composition from a process applied to a starting tion, yields a purified cyclohexane stream containing K. A. material, the starting material is a portion of products from a and CHHP (which can be subjected to known high-yield 65 cyclohexane oxidation process, wherein the portion of prod processes to convert CHHP to KA) and a co-product water ucts has free acid functional groups, wherein the starting stream.
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