CA1128032A - Oxydation catalytique des cycloparaffines - Google Patents

Oxydation catalytique des cycloparaffines

Info

Publication number: CA1128032A
Authority: CA; Canada
Prior art keywords: catalyst; heavy metal; pyridine; cobalt; oxidation
Prior art date: 1978-09-19
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired

Application number

CA335,958A

Other languages

English (en)

Inventor

Ronald A. Zelonka

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

DuPont Canada Inc

Original Assignee

DuPont Canada Inc

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1978-09-19

Filing date

1979-09-19

Publication date

1982-07-20

1979-09-19 Application filed by DuPont Canada Inc filed Critical DuPont Canada Inc

1981-01-30 Priority claimed from US06/229,873 external-priority patent/US4341907A/en

1982-07-20 Application granted granted Critical

1982-07-20 Publication of CA1128032A publication Critical patent/CA1128032A/fr

Status Expired legal-status Critical Current

Links

238000007254 oxidation reaction Methods 0.000 title claims abstract description 77
230000003647 oxidation Effects 0.000 title claims abstract description 76
230000003197 catalytic effect Effects 0.000 title claims abstract description 9
239000003054 catalyst Substances 0.000 claims abstract description 67
JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 66
238000000034 method Methods 0.000 claims abstract description 56
XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 48
229910001385 heavy metal Inorganic materials 0.000 claims abstract description 39
229910017052 cobalt Inorganic materials 0.000 claims abstract description 37
239000010941 cobalt Substances 0.000 claims abstract description 37
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 33
150000002736 metal compounds Chemical class 0.000 claims abstract description 29
125000000217 alkyl group Chemical group 0.000 claims abstract description 24
239000000203 mixture Substances 0.000 claims abstract description 18
239000003446 ligand Substances 0.000 claims abstract description 15
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims abstract description 10
MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
229910001882 dioxygen Inorganic materials 0.000 claims abstract description 8
ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 7
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
229910052802 copper Inorganic materials 0.000 claims abstract description 6
239000010949 copper Substances 0.000 claims abstract description 6
229910052759 nickel Inorganic materials 0.000 claims abstract description 6
PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims abstract description 5
CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 5
229910052742 iron Inorganic materials 0.000 claims abstract description 5
WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
229910052799 carbon Inorganic materials 0.000 claims abstract description 3
LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 3
125000004432 carbon atom Chemical group C* 0.000 claims description 19
229910019142 PO4 Inorganic materials 0.000 claims description 16
239000010452 phosphate Substances 0.000 claims description 16
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
239000007788 liquid Substances 0.000 claims description 10
239000007789 gas Substances 0.000 claims description 8
DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 7
SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 6
125000000753 cycloalkyl group Chemical group 0.000 claims description 5
239000012188 paraffin wax Substances 0.000 claims 2
238000004519 manufacturing process Methods 0.000 abstract description 6
239000011261 inert gas Substances 0.000 abstract description 4
229960003903 oxygen Drugs 0.000 abstract 1
239000000047 product Substances 0.000 description 23
JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
235000021317 phosphate Nutrition 0.000 description 12
239000004215 Carbon black (E152) Substances 0.000 description 11
229930195733 hydrocarbon Natural products 0.000 description 11
150000002430 hydrocarbons Chemical class 0.000 description 11
-1 for example Substances 0.000 description 10
150000001869 cobalt compounds Chemical class 0.000 description 8
238000006243 chemical reaction Methods 0.000 description 7
HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 7
235000011037 adipic acid Nutrition 0.000 description 6
239000001361 adipic acid Substances 0.000 description 6
QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 5
QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 4
230000000052 comparative effect Effects 0.000 description 4
150000001875 compounds Chemical class 0.000 description 4
229910052751 metal Inorganic materials 0.000 description 4
239000002184 metal Substances 0.000 description 4
239000000243 solution Substances 0.000 description 4
239000002904 solvent Substances 0.000 description 4
LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 3
229940011182 cobalt acetate Drugs 0.000 description 3
GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 3
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
239000008346 aqueous phase Substances 0.000 description 2
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
239000012141 concentrate Substances 0.000 description 2
238000003869 coulometry Methods 0.000 description 2
125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
230000000694 effects Effects 0.000 description 2
SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
230000003993 interaction Effects 0.000 description 2
229910017604 nitric acid Inorganic materials 0.000 description 2
239000001301 oxygen Substances 0.000 description 2
229910052760 oxygen Inorganic materials 0.000 description 2
238000012545 processing Methods 0.000 description 2
GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 1
241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 0.000 description 1
DSPNACKJHMJMGK-UHFFFAOYSA-N C1=CC=NC=C1.CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC Chemical compound C1=CC=NC=C1.CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC DSPNACKJHMJMGK-UHFFFAOYSA-N 0.000 description 1
JEHNRVIUAWGROA-UHFFFAOYSA-N CC1=CC=NC=C1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC Chemical compound CC1=CC=NC=C1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC JEHNRVIUAWGROA-UHFFFAOYSA-N 0.000 description 1
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
JIOYPDFWTUIMRB-UHFFFAOYSA-N N#CC1=CC=NC=C1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC Chemical compound N#CC1=CC=NC=C1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC JIOYPDFWTUIMRB-UHFFFAOYSA-N 0.000 description 1
239000004677 Nylon Substances 0.000 description 1
239000002253 acid Substances 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
ZUOIOPMGAYBEIC-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphate 2-methoxypyridine Chemical compound COC1=CC=CC=N1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC ZUOIOPMGAYBEIC-UHFFFAOYSA-N 0.000 description 1
WQQUZAUGADJYGV-UHFFFAOYSA-N bis(2-ethylhexyl) hydrogen phosphate pyridine-4-carboxamide Chemical compound NC(=O)C1=CC=NC=C1.CCCCC(CC)COP(O)(=O)OCC(CC)CCCC WQQUZAUGADJYGV-UHFFFAOYSA-N 0.000 description 1
FMDGHSLOUMJGBC-UHFFFAOYSA-N bis(3-methylbutyl) hydrogen phosphate pyridine Chemical compound N1=CC=CC=C1.C(CC(C)C)OP(=O)(OCCC(C)C)O FMDGHSLOUMJGBC-UHFFFAOYSA-N 0.000 description 1
239000006227 byproduct Substances 0.000 description 1
229910000152 cobalt phosphate Inorganic materials 0.000 description 1
ATFHQVJTPHERNM-UHFFFAOYSA-L cobalt(2+);hexanedioate Chemical group [Co+2].[O-]C(=O)CCCCC([O-])=O ATFHQVJTPHERNM-UHFFFAOYSA-L 0.000 description 1
238000010960 commercial process Methods 0.000 description 1
229940125898 compound 5 Drugs 0.000 description 1
230000002844 continuous effect Effects 0.000 description 1
238000010924 continuous production Methods 0.000 description 1
OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical class C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 description 1
WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
239000004914 cyclooctane Substances 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
230000018044 dehydration Effects 0.000 description 1
238000006297 dehydration reaction Methods 0.000 description 1
YQHVEGTZGGQQMV-UHFFFAOYSA-N dicyclohexyl hydrogen phosphate Chemical compound C1CCCCC1OP(=O)(O)OC1CCCCC1 YQHVEGTZGGQQMV-UHFFFAOYSA-N 0.000 description 1
150000005690 diesters Chemical class 0.000 description 1
FGAUTLMPHANOHJ-UHFFFAOYSA-N diethyl hydrogen phosphate;pyridine Chemical compound C1=CC=[NH+]C=C1.CCOP([O-])(=O)OCC FGAUTLMPHANOHJ-UHFFFAOYSA-N 0.000 description 1
239000012895 dilution Substances 0.000 description 1
238000010790 dilution Methods 0.000 description 1
LNCMKYNSMRIYQP-UHFFFAOYSA-N diphenyl phosphate;pyridin-1-ium Chemical compound C1=CC=[NH+]C=C1.C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 LNCMKYNSMRIYQP-UHFFFAOYSA-N 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
239000002360 explosive Substances 0.000 description 1
239000008246 gaseous mixture Substances 0.000 description 1
DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
238000011065 in-situ storage Methods 0.000 description 1
239000003999 initiator Substances 0.000 description 1
239000000543 intermediate Substances 0.000 description 1
150000002500 ions Chemical class 0.000 description 1
239000007791 liquid phase Substances 0.000 description 1
GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
125000005609 naphthenate group Chemical group 0.000 description 1
229910052757 nitrogen Inorganic materials 0.000 description 1
229920001778 nylon Polymers 0.000 description 1
239000012071 phase Substances 0.000 description 1
CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
SNNUITYRDWJDLO-UHFFFAOYSA-N phosphoric acid;pyridin-4-amine Chemical compound OP(O)(O)=O.NC1=CC=NC=C1 SNNUITYRDWJDLO-UHFFFAOYSA-N 0.000 description 1
238000011084 recovery Methods 0.000 description 1
238000011179 visual inspection Methods 0.000 description 1

Landscapes

Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Catalysts (AREA)

CA335,958A 1978-09-19 1979-09-19 Oxydation catalytique des cycloparaffines Expired CA1128032A (fr)

Applications Claiming Priority (4)

Application Number	Priority Date	Filing Date	Title
GB7837305		1978-09-19
GB37305/78		1978-09-19
US06/229,873 US4341907A (en)	1978-09-19	1981-01-30	Catalytic oxidation of cycloparaffins
US229,873		1981-01-30

Publications (1)

Publication Number	Publication Date
CA1128032A true CA1128032A (fr)	1982-07-20

Family

ID=26268897

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA335,958A Expired CA1128032A (fr)	1978-09-19	1979-09-19	Oxydation catalytique des cycloparaffines

Country Status (1)

Country	Link
CA (1)	CA1128032A (fr)

1979
- 1979-09-19 CA CA335,958A patent/CA1128032A/fr not_active Expired

Legal Events

Date	Code	Title	Description
1999-07-20	MKEX	Expiry

Publication	Publication Date	Title
US4341907A (en)	1982-07-27	Catalytic oxidation of cycloparaffins
US5057631A (en)	1991-10-15	Process for continuous production of octa-2,7-dien-1-ol
US3404185A (en)	1968-10-01	Chromium amine complex catalyzed oxidation of cyclic hydrocarbons to ketones
US4169956A (en)	1979-10-02	Manufacture of butanedicarboxylic acid esters
US4658056A (en)	1987-04-14	Catalytic oxidation of liquid cycloparaffins
US3917708A (en)	1975-11-04	Production of cycloalkanols and cycloalkanones
US4965406A (en)	1990-10-23	Process for the manufacture of benzoic acid and salts thereof
US6762319B1 (en)	2004-07-13	Hydrocarbon, alcohol and/or ketone oxidation method
CA1128032A (fr)	1982-07-20	Oxydation catalytique des cycloparaffines
EP0017183B1 (fr)	1984-04-25	Milieu d'hydroformylation, procédé de préparation et utilisation dudit milieu d'hydroformylation dans la préparation d'aldéhydes
US2800504A (en)	1957-07-23	Production of lower aliphatic acids
US4877903A (en)	1989-10-31	Cyclohexanol/cyclohexanone mixtures produced from cyclohexane
CN109092357B (zh)	2021-05-28	环己烷直接氧化合成己二酸的催化剂
EP0675870B1 (fr)	1997-08-13	Procede de preparation d'un aldehyde
US7507856B2 (en)	2009-03-24	Method of oxidising hydrocarbons to acids
US4160107A (en)	1979-07-03	Process for the preparation of esters of oxalic acid
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CN109092375B (zh)	2021-06-22	环己烷直接氧化制己二酸的自由基稳定剂
US4473705A (en)	1984-09-25	Process for producing oxalate diester
EP0112171A1 (fr)	1984-06-27	Procédé de production de dihydrocarbyle oxalates
CN117324002B (zh)	2026-03-24	一种催化剂及其制备方法和环己烷氧化的方法
JP7438945B2 (ja)	2024-02-27	環状ヘミアセタール化合物の製造方法
CA1096880A (fr)	1981-03-03	Procede d'obtention d'esters d'oxalates
JP3796901B2 (ja)	2006-07-12	シクロアルキルヒドロペルオキシドの製造方法
DE2716170C2 (de)	1986-01-09	Verfahren zur Herstellung von Oxalsäuredialkylestern