US20040054235A1 - Process for oxidation of cyclohexane - Google Patents

Process for oxidation of cyclohexane Download PDF

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US20040054235A1
US20040054235A1 US10/242,544 US24254402A US2004054235A1 US 20040054235 A1 US20040054235 A1 US 20040054235A1 US 24254402 A US24254402 A US 24254402A US 2004054235 A1 US2004054235 A1 US 2004054235A1
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process according
phase
decomposition
cyclohexanol
cyclohexanone
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Ludovic Fodor
Bhagya Sutradhar
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Invista North America LLC
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Priority to TW092118221A priority patent/TW200410924A/en
Priority to PCT/US2003/028261 priority patent/WO2004024657A2/en
Priority to CNB038215535A priority patent/CN1319924C/en
Priority to JP2004536396A priority patent/JP2005539066A/en
Priority to KR1020057004213A priority patent/KR20050044918A/en
Priority to AU2003267072A priority patent/AU2003267072A1/en
Priority to EP03749547A priority patent/EP1539665B1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C07C407/003—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/14—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom belonging to a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a process for the production of cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide from a cyclohexane oxidation process.
  • Oxidation of cyclohexane by air produces a reaction product comprising cyclohexanol (A), cyclohexanone (K) cyclohexyl-hydroperoxide (CHHP) and small amounts of by-products.
  • the reaction product is treated with water followed by separation of organic and aqueous phases.
  • the organic phase comprising A, K and CHHP is further treated to cause decomposition of CHHP to K and A. Therefore, K and A are the main product of the overall process, their mixture is commonly known as “KA-oil”.
  • KA oil is produced from crude KA oil by distillation. All the byproducts, catalysts, additives, corrosion derived metal compounds form what is referred to as the “tails” of the distillation column (U.S. Pat. No. 4,720,592).
  • the KA oil is distilled in the final step.
  • the material that remains after the KA distillation is a viscous material, usually dark in color, comprising the impurities formed during the process, the non-volatile catalysts, and any additives that were used in the process.
  • Non Volatile Residue or “NVR”.
  • the tails stream is often concentrated through evaporation.
  • the concentrated stream commonly known as non-volatile residue (NVR) is often disposed of as boiler fuel.
  • the NVR is an aqueous dispersion.
  • the composition comprises formic acid, acetic acid, butyric acid, valeric acid, caproic acid, 6-hydroxycaproic acid, succinic acid, glutaric acid, adipic acid, phosphoric acid organic esters, chromium salts, and other materials.
  • the amount of NVR formed during KA production is significant, it may represent up to 20% of the amount of KA oil produced and normally it is disposed by burning and getting credit for the fuel value. Because of more demanding environmental regulations the disposal of NVR with high chromium content by burning in boilers will be unacceptable.
  • the object of the present invention is to provide a method for producing KA oil and having NVR by-product with low Cr concentration.
  • FIG. 1 is a schematic flow chart of the process of the present invention, and is provided to aid in the understanding of the process.
  • the Air oxidizer ( 1 ) is used to oxidize the cyclohexane.
  • the water separator ( 2 ) is used to collect the aqueous phase that results from step 1 of the present process.
  • Cyclohexyl hydroperoxide that is present in a second phase is decomposed in a CHHP decomposition reactor ( 3 ) to cyclohexanone and cyclohexanol. These products are distilled in a distillation column ( 4 ) and then KA refined in a refiner ( 5 ).
  • the NVR that remains in the refiner ( 5 ) is then contacted with first, either a dilute acid ( 6 ) or with an aqueous electrolyte solution ( 7 ) to extract chromium. Finally, a phase separator ( 8 ) is used to separate the chromium into the aqueous phase.
  • Cyclohexane is air oxidized in a tower oxidizer ( 1 ) and the oxidizer tails are contacted with water.
  • the water is separated in a decanter ( 2 ) into a first phase and second phase.
  • the first phase comprising substantially aqueous (water-soluble) components and said second phase comprising cyclohexanol and organic components.
  • the water washed organic phase is directed to the CHHP decomposition reactor ( 3 ) where it is treated with chromium octoate and is decomposed in K and A.
  • the cyclohexane is recovered by distillation ( 4 ) and recycled.
  • the resulting crude KA oil is refined in the KA refiner ( 5 ) and the KA is distilled of at the top of the column.
  • the NVR is collected at the bottom of refining column.
  • the resulted NVR is contacted with an acidic solution in the acid treatment reactor ( 6 ).
  • the non-volatile residue is further contacted with an electrolyte solution ( 7 ), followed by separation of the aqueous phase from the organic phase ( 8 ).
  • the separated organic phase is the NVR with low Cr concentration ( ⁇ 2 ppm).
  • a process for the production of cyclohexanone and cyclohexanol mixture from cyclohexane together with byproduct recovery comprising: (i) oxidizing cyclohexane to obtain air oxidation tails; (ii) contacting the air oxidation tails with water; (iii) separating the mixture resulting from step (ii) into a first phase and a second phase, said first phase comprising substantially aqueous components and said second phase comprising cyclohexyl hydroperoxide and organic components; (iv) decomposing the cyclohexyl hydroperoxide in the organic phase from step (iii) to cyclohexanone and cyclohexanol; (v) refining of the cyclohexanol and cyclohexanone mixture obtained in step (iv) and (vi) separating chromium from nonvolatile residue.
  • the cyclohexane is contacted with air in the air oxidizer ( 1 ) at temperatures between about 100° C. to about 175° C.
  • the air oxidizer can be an oxidation tower, stirred or non-stirred tank reactor(s), stirred or non-stirred autoclave(s).
  • the air oxidizer tails are contacted with water. The ratio between the air oxidizer tails and water is about 100:1.
  • the cyclohexyl-hydroperoxide is decomposed to K and A ( 3 ).
  • Decomposition of the CHHP may be accomplished using thermal decomposition, catalytic decomposition, catalytic hydrogenation or other catalytic methods such as the use of gold catalyst, for example.
  • Thermal decomposition is carried out at relatively high temperatures, 120-175° C. and long hold-up times.
  • CHHP hydrogenation is carried out with heterogeneous catalysts, at temperatures between about 100 to about 160° C.
  • Hydrogenation catalysts include but not limited to palladium on silica or alumina support.
  • CHHP decomposition may also be accomplished without hydrogen with the use of different heterogeneous catalysts such as gold deposited on silica or alumina at temperatures between 100-160° C.
  • CHHP decomposition may also be accomplished by metal catalyzed decomposition in caustic aqueous solution. This is done by contacting the CHHP with cobalt, chromium, or a mixture thereof, in caustic solutions, preferably sodium hydroxide. When using either or both of these metals for CHHP decomposition the concentration of Co and/or Cr is between 0.1 and 20 ppm.
  • the excess cyclohexane is distilled off ( 4 ) and the resulting KA oil is distilled in KA Refiner at temperatures between from about 90 to about 170° C. ( 5 ).
  • Some of the process steps, such as water washing the AOR tails, are beneficial in reducing deactivation of the catalyst but are not essential.
  • the cyclohexane distillation and KA oil refining can be performed by different unit operations such as vacuum distillation, steam distillation, etc.
  • the NVR remaining in the bottom of the KA Refiner column ( 5 ) is sent to acid treatment reactor ( 6 ).
  • the NVR is contacted in ( 6 ) with diluted acid solutions (0.2-10%) at temperatures between about 60 to about 120° C.
  • the NVR is contacted with an aqueous electrolyte solution ( 7 ) to extract the Cr into the aqueous layer.
  • the extraction step of the Cr in aqueous electrolyte solution can be accomplished at temperatures between about 20 to about 0120° C.
  • the NVR with reduced Cr is separated from the aqueous electrolyte solution in a decanter ( 8 ).
  • the extraction and hydrolysis steps may need to be repeated in order to reduce the Cr to very low levels.
  • the hydrolysis and extraction steps can be reversed in order.
  • the K and A is obtained as a mixture.
  • the product (K and A) is oxidized to produce adipic acid.
  • the oxidizing agent that may be used is nitric acid.
  • the resulting adipic acid may be used in turn to make Nylon products, pharmaceutical additives, food additives, polyurethane, and a host of other applications.

Abstract

Disclosed herein is a process for the production of a mixture of cyclohexanone and cyclohexanol by oxidation of cyclohexane and decomposition of cyclohexyl hydroperoxide.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a process for the production of cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide from a cyclohexane oxidation process. [0001]
    • BACKGROUND OF THE INVENTION
  • Oxidation of cyclohexane by air produces a reaction product comprising cyclohexanol (A), cyclohexanone (K) cyclohexyl-hydroperoxide (CHHP) and small amounts of by-products. The reaction product is treated with water followed by separation of organic and aqueous phases. The organic phase comprising A, K and CHHP is further treated to cause decomposition of CHHP to K and A. Therefore, K and A are the main product of the overall process, their mixture is commonly known as “KA-oil”. [0002]
  • Several byproducts formed during the above processes remain as impurities mixed with KA oil (crude) along with unreacted cyclohexane. Refined KA oil is produced from crude KA oil by distillation. All the byproducts, catalysts, additives, corrosion derived metal compounds form what is referred to as the “tails” of the distillation column (U.S. Pat. No. 4,720,592). In order to eliminate the by-products produced during the process, the KA oil is distilled in the final step. The material that remains after the KA distillation is a viscous material, usually dark in color, comprising the impurities formed during the process, the non-volatile catalysts, and any additives that were used in the process. Collectively these materials are referred to as “Non Volatile Residue” or “NVR”). The tails stream is often concentrated through evaporation. The concentrated stream, commonly known as non-volatile residue (NVR) is often disposed of as boiler fuel. [0003]
  • Corrosion in process vessels made of stainless steel adds chromium to NVR. In addition, for a CHHP decomposition process using chromium catalyst (U.S. Pat. No. 4,465,861), the chromium ends up in the NVR. Typically, a concentration of chromium in the range of 2-100 ppm is observed in NVR. Upon combustion in a boiler, the chromium forms a part of the emission through boiler stack gas. In order to comply with environmental regulations, the stack gas needs expensive treatment for chromium reduction. Alternative routes to disposal of NVR are also expensive. [0004]
  • It is, therefore, desirable to have process of oxidation of cyclohexane to produce KA oil, the said process comprising one or more steps to reduce chromium content of NVR so the stack gas corresponding to its combustion will contain an acceptable low concentration of chromium. [0005]
  • The NVR is an aqueous dispersion. Typically, the composition comprises formic acid, acetic acid, butyric acid, valeric acid, caproic acid, 6-hydroxycaproic acid, succinic acid, glutaric acid, adipic acid, phosphoric acid organic esters, chromium salts, and other materials. [0006]
  • The amount of NVR formed during KA production is significant, it may represent up to 20% of the amount of KA oil produced and normally it is disposed by burning and getting credit for the fuel value. Because of more demanding environmental regulations the disposal of NVR with high chromium content by burning in boilers will be unacceptable. [0007]
  • There are known procedures to eliminate hexavalent chromium from heavy metal sludge or waste liquid, involving reducing the hexavalent chromium in acidic solution to trivalent (JP 2001058192 A 20010306). This procedure is not applicable for Cr elimination from NVR because all the NVR will be solubilized during treatment in water. [0008]
  • There are also treatment systems available to eliminate chromium from plating operations (U.S. Pat. No. 5,932,109) by precipitating using hydrazine or Al and Cu shavings (RU 2,023,674) by adding calcium hydroxide to specified pH value then barium hydroxide to further increase pH (SU 1323537). [0009]
  • The object of the present invention is to provide a method for producing KA oil and having NVR by-product with low Cr concentration.[0010]
    • BRIEF DESCRIPTION OF THE DRAWING
  • FIG. 1 is a schematic flow chart of the process of the present invention, and is provided to aid in the understanding of the process. The Air oxidizer ([0011] 1) is used to oxidize the cyclohexane. The water separator (2) is used to collect the aqueous phase that results from step 1 of the present process. Cyclohexyl hydroperoxide that is present in a second phase is decomposed in a CHHP decomposition reactor (3) to cyclohexanone and cyclohexanol. These products are distilled in a distillation column (4) and then KA refined in a refiner (5). The NVR that remains in the refiner (5) is then contacted with first, either a dilute acid (6) or with an aqueous electrolyte solution (7) to extract chromium. Finally, a phase separator (8) is used to separate the chromium into the aqueous phase.
  • Cyclohexane is air oxidized in a tower oxidizer ([0012] 1) and the oxidizer tails are contacted with water. The water is separated in a decanter (2) into a first phase and second phase. The first phase comprising substantially aqueous (water-soluble) components and said second phase comprising cyclohexanol and organic components. The water washed organic phase is directed to the CHHP decomposition reactor (3) where it is treated with chromium octoate and is decomposed in K and A. The cyclohexane is recovered by distillation (4) and recycled. The resulting crude KA oil is refined in the KA refiner (5) and the KA is distilled of at the top of the column. The NVR is collected at the bottom of refining column. The resulted NVR is contacted with an acidic solution in the acid treatment reactor (6). The non-volatile residue is further contacted with an electrolyte solution (7), followed by separation of the aqueous phase from the organic phase (8). The separated organic phase is the NVR with low Cr concentration (˜2 ppm).
    • SUMMARY OF THE INVENTION
  • Disclosed herein is a process for the production of cyclohexanone and cyclohexanol mixture from cyclohexane together with byproduct recovery, said process comprising: (i) oxidizing cyclohexane to obtain air oxidation tails; (ii) contacting the air oxidation tails with water; (iii) separating the mixture resulting from step (ii) into a first phase and a second phase, said first phase comprising substantially aqueous components and said second phase comprising cyclohexyl hydroperoxide and organic components; (iv) decomposing the cyclohexyl hydroperoxide in the organic phase from step (iii) to cyclohexanone and cyclohexanol; (v) refining of the cyclohexanol and cyclohexanone mixture obtained in step (iv) and (vi) separating chromium from nonvolatile residue. [0013]
    • DETAILED DESCRIPTION OF THE INVENTION
  • Disclosed herein is a method for oxidizing cyclohexane, which subsequently will produce NVR by-product with low Cr content. In the method of the present invention the cyclohexane is contacted with air in the air oxidizer ([0014] 1) at temperatures between about 100° C. to about 175° C. The air oxidizer can be an oxidation tower, stirred or non-stirred tank reactor(s), stirred or non-stirred autoclave(s). The air oxidizer tails are contacted with water. The ratio between the air oxidizer tails and water is about 100:1. After the aqueous phase is separated (2) the cyclohexyl-hydroperoxide is decomposed to K and A (3).
  • Decomposition of the CHHP may be accomplished using thermal decomposition, catalytic decomposition, catalytic hydrogenation or other catalytic methods such as the use of gold catalyst, for example. Thermal decomposition is carried out at relatively high temperatures, 120-175° C. and long hold-up times. [0015]
  • CHHP hydrogenation is carried out with heterogeneous catalysts, at temperatures between about 100 to about 160° C. Hydrogenation catalysts include but not limited to palladium on silica or alumina support. [0016]
  • CHHP decomposition may also be accomplished without hydrogen with the use of different heterogeneous catalysts such as gold deposited on silica or alumina at temperatures between 100-160° C. [0017]
  • CHHP decomposition may also be accomplished by metal catalyzed decomposition in caustic aqueous solution. This is done by contacting the CHHP with cobalt, chromium, or a mixture thereof, in caustic solutions, preferably sodium hydroxide. When using either or both of these metals for CHHP decomposition the concentration of Co and/or Cr is between 0.1 and 20 ppm. [0018]
  • After the CHHP is transformed to K&A the excess cyclohexane is distilled off ([0019] 4) and the resulting KA oil is distilled in KA Refiner at temperatures between from about 90 to about 170° C. (5). Some of the process steps, such as water washing the AOR tails, are beneficial in reducing deactivation of the catalyst but are not essential. Also the cyclohexane distillation and KA oil refining can be performed by different unit operations such as vacuum distillation, steam distillation, etc.
  • The NVR remaining in the bottom of the KA Refiner column ([0020] 5) is sent to acid treatment reactor (6). The NVR is contacted in (6) with diluted acid solutions (0.2-10%) at temperatures between about 60 to about 120° C. After the first hydrolysis stage the NVR is contacted with an aqueous electrolyte solution (7) to extract the Cr into the aqueous layer. The extraction step of the Cr in aqueous electrolyte solution can be accomplished at temperatures between about 20 to about 0120° C. The NVR with reduced Cr is separated from the aqueous electrolyte solution in a decanter (8). Depending on actual process parameters, the extraction and hydrolysis steps may need to be repeated in order to reduce the Cr to very low levels. The hydrolysis and extraction steps can be reversed in order.
  • The K and A is obtained as a mixture. The product (K and A) is oxidized to produce adipic acid. The oxidizing agent that may be used is nitric acid. The resulting adipic acid may be used in turn to make Nylon products, pharmaceutical additives, food additives, polyurethane, and a host of other applications. [0021]

Claims (10)

1. A process for the production of cyclohexanone and cyclohexanol mixture from cyclohexane together with byproduct recovery, said process comprising:
(i) oxidizing cyclohexane to obtain air oxidation tails;
(ii) contacting the air oxidation tails with water;
(iii) separating the mixture resulting from step (ii) into a first phase and a second phase, said first phase comprising substantially aqueous components and said second phase comprising cyclohexyl hydroperoxide and organic components;
(iv) decomposing the cyclohexyl hydroperoxide in the organic phase from step (iii) to cyclohexanone and cyclohexanol;
(v) refining of the cyclohexanol and cyclohexanone mixture obtained in step (iv) and
(vi) separating chromium from nonvolatile residue.
2. A process according to claim 1 wherein said process further comprises;
(i) contacting non-volatile residue or at least a portion of the organic content of the non-volatile residue with an acidic compound;
(ii) contacting the non-volatile residue or at least a portion of the organic content of the non-volatile residue with an aqueous electrolyte solution, followed by separation of the aqueous phase from the organic phase;
(iii) repeating steps (i) and (ii) in any order.
3. A process according to claims 1 and 2 wherein the decomposition of CHHP is accomplished by thermal decomposition, by catalytic decomposition, or catalytic hydrogenation.
4. A process according to claim 3 wherein the decomposition of CHHP is accomplished by metal catalyzed decomposition in caustic solution.
5. A process according to claim 3 wherein the catalyst comprises Co, Cr, or both.
6. A process according to claim 4 wherein the catalyst comprises Au and Pd.
7. A process according to claims 1 and 2 wherein the decomposition of CHHP is carried out at a temperature between about 100° C. to about 175° C.
8. A process according to claim 1 refining of the cyclohexanol and cyclohexanone mixture is accomplished by distillation.
9. A process according to claim 1 wherein the air oxidation tails is washed with water.
10. A process according to claim 1 wherein the cyclohexanol and cyclohexanone product obtained are used to produce adipic acid.
US10/242,544 2002-09-12 2002-09-12 Process for oxidation of cyclohexane Expired - Lifetime US6703529B1 (en)

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US10/242,544 US6703529B1 (en) 2002-09-12 2002-09-12 Process for oxidation of cyclohexane
TW092118221A TW200410924A (en) 2002-09-12 2003-07-03 Process for oxidation of cyclohexane
PCT/US2003/028261 WO2004024657A2 (en) 2002-09-12 2003-09-09 Process for oxidation of cyclohexane
CNB038215535A CN1319924C (en) 2002-09-12 2003-09-09 Process for oxidation of cyclohexane
JP2004536396A JP2005539066A (en) 2002-09-12 2003-09-09 Cyclohexane oxidation process
KR1020057004213A KR20050044918A (en) 2002-09-12 2003-09-09 Process for oxidation of cyclohexane
AU2003267072A AU2003267072A1 (en) 2002-09-12 2003-09-09 Process for oxidation of cyclohexane
EP03749547A EP1539665B1 (en) 2002-09-12 2003-09-09 Process for oxidation of cyclohexane

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WO2012174451A1 (en) 2011-06-17 2012-12-20 Invista Technologies S.A.R.L. Use of hydrolases to increase monomer content in waste stream
WO2012173938A1 (en) 2011-06-13 2012-12-20 Invista Technologies S.A.R.L. Aliphatic polyester polyols from cyclohexane oxidation byproduct streams as precursors for polyurethane and polyisocyanurate polymers
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6814867B2 (en) * 2002-09-12 2004-11-09 Inuista North America S.à.r.l. Process for reducing chromium in nonvolatile residue resulting from air oxidation of cyclohexane
FR2878847B1 (en) * 2004-12-07 2007-01-05 Rhodia Chimie Sa PROCESS FOR THE PREPARATION OF CYCLOHEXANONE
CN100460374C (en) * 2006-01-06 2009-02-11 中国石油天然气股份有限公司 Method for prolonging alkali wash period of alcohol ketone device
EP2051788A1 (en) * 2006-08-18 2009-04-29 Invista Technologies S.à.r.l. Extraction process using an ionic liquid
EP2384344B1 (en) * 2009-01-30 2019-10-16 INVISTA Textiles (U.K.) Limited Aromatic polyesterpolyols, isocyanuratemodified polyurethane foams, and methods of making them
RU2458903C1 (en) * 2010-12-23 2012-08-20 Открытое акционерное общество "Щекиноазот" Method of producing cyclohexanone and cyclohexanol and apparatus for realising said method
US20160176813A1 (en) 2012-07-19 2016-06-23 Invista North America S.A R.L. Process for the oxidation of cyclohexane
JP2015522609A (en) * 2012-07-19 2015-08-06 インヴィスタ テクノロジーズ エスアエルエル Process for purification of cyclohexane air oxidation product stream
WO2014014466A1 (en) 2012-07-19 2014-01-23 Invista Technologies S.A R.L. Regeneration of a hydrogenation catalyst
JP2015522610A (en) * 2012-07-19 2015-08-06 インヴィスタ テクノロジーズ エスアエルエル Cyclohexane oxidation method
JP2016502969A (en) 2012-12-18 2016-02-01 インヴィスタ テクノロジーズ エスアエルエル Hydrogen cyanide production and hydrogen recovery process
CN104557497A (en) * 2013-10-09 2015-04-29 中国石油化工股份有限公司 Method for raising ketone-alcohol ratio of cyclohexyl hydroperoxide decomposition
CN104945213B (en) * 2014-07-07 2017-01-11 山东勇智化工有限公司 Negative pressure drying process for drying tower
KR20180050757A (en) 2015-10-01 2018-05-15 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 Nanoparticle catalysts that convert cyclohexanol to cyclohexanone
CN105315128B (en) * 2015-10-28 2017-04-12 江西科苑生物药业有限公司 Method for preparing KA oil through cyclohexane oxidation
CN106995463B (en) * 2017-03-31 2019-11-08 中国石油化工股份有限公司 A kind of different monooctyl ester catalyst system of oil-soluble chromic acid
RU2673541C1 (en) * 2017-10-13 2018-11-28 Открытое акционерное общество "Щекиноазот" Method for producing cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide, installation for its implementation and a device for the adsorption of reactive gases and preliminary cyclohexane oxidation

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1590958A (en) * 1976-12-31 1981-06-10 Ici Ltd Oxidation of cyclohexane
SU1323537A1 (en) 1982-01-22 1987-07-15 Рубежанский филиал Ворошиловградского машиностроительного института Method of removing sexivalent chromium from waste water
US4465861A (en) 1983-04-11 1984-08-14 E. I. Du Pont De Nemours And Company Process for producing a mixture containing cyclohexanol and cyclohexanone
US4720592A (en) 1986-09-05 1988-01-19 E. I. Du Pont De Nemours And Company Preparation of cyclohexanone and cyclohexanol
RU2023674C1 (en) 1991-07-15 1994-11-30 Ляпкин Александр Александрович Method of sewage treatment from chrome compounds
US5932109A (en) 1994-06-02 1999-08-03 Griffin Chemical Company Plating rinse water treatment
JP3632233B2 (en) * 1995-03-10 2005-03-23 三菱化学株式会社 Method for producing α-olefin low polymer
JP3572811B2 (en) * 1996-06-17 2004-10-06 東ソー株式会社 Treatment method for spent catalyst containing chromium
US5780683A (en) * 1996-09-11 1998-07-14 Abb Lummus Global Inc. Cyclohexane oxidation
JP2001058192A (en) 1999-08-23 2001-03-06 Matsushita Sangyo Kk Removal of hexavalent chromium
US6814867B2 (en) * 2002-09-12 2004-11-09 Inuista North America S.à.r.l. Process for reducing chromium in nonvolatile residue resulting from air oxidation of cyclohexane

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