CN115160127A - Method for preparing long carbon chain dibasic acid through co-oxidation reaction - Google Patents
Method for preparing long carbon chain dibasic acid through co-oxidation reaction Download PDFInfo
- Publication number
- CN115160127A CN115160127A CN202210905524.XA CN202210905524A CN115160127A CN 115160127 A CN115160127 A CN 115160127A CN 202210905524 A CN202210905524 A CN 202210905524A CN 115160127 A CN115160127 A CN 115160127A
- Authority
- CN
- China
- Prior art keywords
- carbon atoms
- reaction
- acid
- dibasic acid
- chain dibasic
- Prior art date
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- Granted
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 68
- 239000002253 acid Substances 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 42
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000003997 cyclic ketones Chemical class 0.000 claims abstract description 14
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 39
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 claims description 36
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 claims description 30
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- HAMFVYJFVXTJCJ-UHFFFAOYSA-N cyclododecane-1,2-diol Chemical compound OC1CCCCCCCCCCC1O HAMFVYJFVXTJCJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- OSOIQJGOYGSIMF-UHFFFAOYSA-N cyclopentadecanone Chemical compound O=C1CCCCCCCCCCCCCC1 OSOIQJGOYGSIMF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyclotetradecone Chemical compound 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 claims description 6
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 claims description 6
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 claims description 6
- OITMBHSFQBJCFN-UHFFFAOYSA-N 2,5,5-trimethylcyclohexan-1-one Chemical compound CC1CCC(C)(C)CC1=O OITMBHSFQBJCFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- WFRBMXFCEAHLGH-UHFFFAOYSA-N cyclodecanol Chemical compound OC1CCCCCCCCC1 WFRBMXFCEAHLGH-UHFFFAOYSA-N 0.000 claims description 4
- SXOZDDAFVJANJP-UHFFFAOYSA-N cyclodecanone Chemical compound O=C1CCCCCCCCC1 SXOZDDAFVJANJP-UHFFFAOYSA-N 0.000 claims description 4
- LXJDKGYSHYYKFJ-UHFFFAOYSA-N cyclohexadecanone Chemical compound O=C1CCCCCCCCCCCCCCC1 LXJDKGYSHYYKFJ-UHFFFAOYSA-N 0.000 claims description 4
- BAUZLFKYYIVGPM-UHFFFAOYSA-N cyclononanone Chemical compound O=C1CCCCCCCC1 BAUZLFKYYIVGPM-UHFFFAOYSA-N 0.000 claims description 4
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 claims description 4
- FFVHXGZXDRXFLQ-UHFFFAOYSA-N cyclopentadecanol Chemical compound OC1CCCCCCCCCCCCCC1 FFVHXGZXDRXFLQ-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 claims description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical compound O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 claims description 2
- NVGYZORHPOIGFP-UHFFFAOYSA-N cyclodecane-1,2-diol Chemical compound OC1CCCCCCCCC1O NVGYZORHPOIGFP-UHFFFAOYSA-N 0.000 claims description 2
- RCIINNRHOWANBV-UHFFFAOYSA-N cyclohexadecanol Chemical compound OC1CCCCCCCCCCCCCCC1 RCIINNRHOWANBV-UHFFFAOYSA-N 0.000 claims description 2
- UDEKCKABZJKCKG-UHFFFAOYSA-N cyclononanol Chemical compound OC1CCCCCCCC1 UDEKCKABZJKCKG-UHFFFAOYSA-N 0.000 claims description 2
- HUSOFJYAGDTKSK-UHFFFAOYSA-N cyclooctane-1,2-diol Chemical compound OC1CCCCCCC1O HUSOFJYAGDTKSK-UHFFFAOYSA-N 0.000 claims description 2
- VCVOSERVUCJNPR-UHFFFAOYSA-N cyclopentane-1,2-diol Chemical compound OC1CCCC1O VCVOSERVUCJNPR-UHFFFAOYSA-N 0.000 claims description 2
- ZJJOMKBDHWVFIU-UHFFFAOYSA-N cyclotetradecanol Chemical compound OC1CCCCCCCCCCCCC1 ZJJOMKBDHWVFIU-UHFFFAOYSA-N 0.000 claims description 2
- IWOZRHJPQVIPNH-UHFFFAOYSA-N cyclotridecanol Chemical compound OC1CCCCCCCCCCCC1 IWOZRHJPQVIPNH-UHFFFAOYSA-N 0.000 claims description 2
- VHUGWUBIUBBUAF-UHFFFAOYSA-N cyclotridecanone Chemical compound O=C1CCCCCCCCCCCC1 VHUGWUBIUBBUAF-UHFFFAOYSA-N 0.000 claims description 2
- WFXNFNGXUAKZAY-UHFFFAOYSA-N cycloundecanol Chemical compound OC1CCCCCCCCCC1 WFXNFNGXUAKZAY-UHFFFAOYSA-N 0.000 claims description 2
- UPOSSYJVWXLPTA-UHFFFAOYSA-N cycloundecanone Chemical compound O=C1CCCCCCCCCC1 UPOSSYJVWXLPTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 41
- 150000002576 ketones Chemical class 0.000 abstract description 34
- 238000007086 side reaction Methods 0.000 abstract description 12
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 85
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 29
- 239000002994 raw material Substances 0.000 description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 22
- 239000006227 byproduct Substances 0.000 description 20
- 239000001361 adipic acid Substances 0.000 description 19
- 235000011037 adipic acid Nutrition 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 14
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- 230000032050 esterification Effects 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229920000572 Nylon 6/12 Polymers 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000001212 derivatisation Methods 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000010724 circulating oil Substances 0.000 description 7
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 6
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OWUVDWLTQIPNLN-GGWOSOGESA-N (4e,8e)-13-oxabicyclo[10.1.0]trideca-4,8-diene Chemical compound C1C\C=C\CC\C=C\CCC2OC21 OWUVDWLTQIPNLN-GGWOSOGESA-N 0.000 description 2
- SFEANFNCRQCRKV-UHFFFAOYSA-N CC1C2CCCCCCCCCC(C(C1)=C=O)C2 Chemical compound CC1C2CCCCCCCCCC(C(C1)=C=O)C2 SFEANFNCRQCRKV-UHFFFAOYSA-N 0.000 description 2
- ALHUZKCOMYUFRB-OAHLLOKOSA-N Muscone Chemical compound C[C@@H]1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-OAHLLOKOSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000911 decarboxylating effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006583 body weight regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011909 oxidative ring-opening Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing long carbon chain dibasic acid by co-oxidation reaction, which comprises the steps of mixing and heating a component A, a component B, an aqueous nitric acid solution and a catalyst to completely react to obtain a reaction solution containing the required long carbon chain dibasic acid, wherein the component A comprises one or more of cyclic alcohol with 8-16 carbon atoms, cyclic ketone with 8-16 carbon atoms, 1, 2-dihydroxycycloalkane with 8-16 carbon atoms and a compound shown as a formula I, and the component B comprises one or more of cyclic alcohol with 4-6 carbon atoms, cyclic ketone with 4-6 carbon atoms and 1, 2-dihydroxycycloalkane with 4-6 carbon atoms. The invention has the following beneficial effects: the addition of the low-carbon cyclic alcohol or ketone can inhibit series decarboxylation side reaction, reduce the amount of nitric acid, reduce reaction temperature, reaction time and other synergistic beneficial factors, promote oxidation reaction to have higher reaction selectivity, improve the yield of long-carbon chain dibasic acid and greatly reduce the separation difficulty.
Description
Technical Field
The invention belongs to the field of new chemical materials, and particularly relates to a method for preparing long-carbon-chain dibasic acid through co-oxidation reaction.
Background
The long carbon chain dibasic acid is straight chain dicarboxylic acid with more than 8 carbon atoms in the carbon chain, and is an important fine chemical product. The dodecanedioic acid is the long-carbon-chain dibasic acid with the largest market amount, and the dodecanedioic acid is used as an intermediate to synthesize different long-carbon-chain special nylons, such as nylon 612, nylon 1012, nylon 1212 and nylon 12T, according to different amines. Compared with nylon 6 and nylon 66 which are commonly used, the long-carbon-chain nylon has remarkable specificity, small amide group concentration and long carbon chain, so that the long-carbon-chain nylon has most of the universality of common nylon, and also has excellent wear resistance, low moisture absorption rate, excellent hydrolysis resistance, excellent impact strength, dimensional stability, weather resistance, chemical resistance, excellent barrier property, stress cracking resistance, good NVH (noise vibration and harshness) resistance and the like at low temperature. Therefore, the brush is widely applied to a plurality of fields such as automobile manufacturing, submarine cables, industrial brushes and the like. In addition, various fragrances can be prepared from dodecanedioic acid as an intermediate, such as cyclopentadecanone lactone, muscone, 5-cyclohexadecanone, cyclopentadecanone, 12-methyl-14-carbonylbicyclo [9,3,1] pentadecane, and the like.
The synthesis process of the dodecanedioic acid comprises the following steps:
1. biological fermentation method of normal alkane
The biological fermentation method mainly uses C11-C18 normal alkane as raw material, and converts the alkane into a plurality of long-chain binary acid mixtures through Candida fermentation, wherein the long-chain binary acid mixtures comprise sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid and the like. Then, a plurality of long-chain binary acid crystal products are obtained through a plurality of steps of dissolving, decoloring, acidifying, crystallizing, filtering, drying and the like. The reaction conditions of the biological fermentation method are relatively mild, but the purity of the produced monoacid of the dodecanedioic acid is only 97-98.5%, the color is poor, the crystal granularity is uneven, residual mycoprotein is difficult to remove, the product quality is far lower than that of the chemical synthesis method (the purity of the monoacid is more than 99.0%), a large amount of sodium sulfate is needed as a byproduct in the fermentation method, the whole equipment investment is large, the wastewater amount is large, the production cost is high, and the environmental problem is prominent.
2. Cyclohexanone oxidation ring-opening-dimerization process
US2601223 discloses a process for preparing dodecanedioic acid from cyclohexanone by oxidative ring-opening-dimerization with hydrogen peroxide, in particular using methanol as solvent and Fe 2+ Salt is used as a catalyst, cyclohexanone is oxidized by hydrogen peroxide to carry out ring-opening polymerization and then esterification to obtain dodeca-methyl-dicarboxylate, and then saponification-acidification is carried out by NaOH to obtain dodecanedioic acid. US3917687 and US3907883 remove methanol solvent with Fe 2+ The salt is used as a catalyst to catalyze the reaction, and the dodecadicarboxylic acid product can also be obtained. CN104610040A discloses that Fe is not added 2+ Salt catalyst, and ring-opening polymerization reaction of hydrogen peroxide and cyclohexanone under light irradiation. According to the patent reports of the prior publication, the yield of the dodecanedioic acid obtained by the process is low and is only 40-60%, and the catalyst Fe is used 2+ The using amount of the salt and the hydrogen peroxide is larger and is respectively 30-50 times and 8-10 times of the molar mass of the cyclohexanone, on one hand, the iron content is difficult to completely remove through later-stage purification, the molecular weight regulation and control of the subsequent polymerization reaction and the performance of a polymer product are seriously influenced, and on the other hand, huge potential safety hazards are easily caused by decomposition in the excessive hydrogen peroxide post-treatment process. Therefore, such a process is not technically and cost-advantageous for industrial production.
3. Oxidation ring-opening process for large cyclic olefin
EP0438143B1 discloses the treatment of cancer by RuO 4 -Ce(SO 3 CH 3 ) 4 And the-methanesulfonic acid is used as a catalytic system to realize the heterogeneous oxidation ring opening of the cyclododecene to prepare the dodecanedioic acid. Lipophilic RuO 4 Oxidizing cyclododecene to dodecanedioic acid in the organic phase; the reduced ruthenium has limited solubility in the organic phase, is easy to form precipitates to be extracted or dissolved into the aqueous phase to be Ce 4+ Ionic oxidation to RuO 4 ，RuO 4 Redissolved in the organic phaseAnd reacts with additional cyclododecene to form a catalytic cycle. Ce in aqueous phase 3+ The ions are electrolytically oxidized again to convert Ce into 3+ Conversion of ions to Ce 4+ Ions. The loss of Ru can be reduced as much as possible by oil-water two phases, the cyclododecene conversion rate is 95%, and the selectivity of the dodecanedioic acid is 87-88%. From the published information, the process requires higher levels of Ce 4+ The molar addition amount of the ions is 4-12 times that of cyclododecene, so that the full oxidation of Ru is ensured; and the catalytic circulation of Ce needs to be assisted by electrolytic oxidation, thereby further increasing the equipment investment. Furthermore, the patent does not disclose the catalytic results of the catalytic system after multiple cycles, which is critical to reduce the cost of the noble metal catalyst.
US3461160A reports OsO 4 And V 2 O 5 Catalyzing the oxidation reaction of cyclododecene and nitric acid to prepare the dodecanedioic acid. The reaction needs to obtain about 70 percent of yield when the mass ratio of the Os to the cyclododecene raw material is 1.5,4.0, the dosage of the catalyst is huge, the Os element belongs to a noble metal element, the cost of the catalyst is extremely high, and the patent does not mention the problem of recycling of a catalytic system.
4. Macrocyclic ketol oxidation ring-opening reaction process
CN101970392A discloses that cyclododecanone/alcohol mixture with 30-70% cyclododecanone content is used as raw material, and the dodecadioic acid is obtained by nitric acid oxidation under the action of copper and vanadium catalyst, with the yield of 88%. CN108017533A reports the preparation of dodecanedioic acid by oxidation of cyclododecanone with excess nitric acid by controlling the particle size distribution of the product dodecanedioic acid by means of reactive crystallization. The reaction adopts 65-90wt% concentrated nitric acid as oxidant, and the molar ratio of nitric acid/raw material is up to (10-15): 1. the process adopts a process flow similar to that of adipic acid, but the nitric acid needs to be greatly excessive due to the difference of molecular structures, the molar ratio of the nitric acid to raw materials is far higher than that of the adipic acid process, and needs to reach (15-20): 1 or more, so that the large amount of nitric acid can increase the total reaction volume and greatly increase the energy consumption for concentrating and recycling the nitric acid; secondly, the nitric acid oxidation cyclododecanone/alcohol reaction mechanism is very complex, the main and side reactions are series reactions, and dibasic acid products of C11, C10, C9 and below can be generated in the reaction process. These by-products cause great technical difficulty in subsequent separation and purification, seriously affect the purity and quality of the product, and indirectly cause adverse effects on the performance of the polymer taking the dodecanedioic acid as a monomer. However, it is hardly mentioned in the literature and patent reports at present how to suppress the occurrence of side reactions and provide an effective industrial technical means. In addition, the patent reports disclosed at present only use cyclododecanol/ketone as raw material to carry out oxidation reaction to prepare dodecanedioic acid.
Compared with low-carbon dicarboxylic acid such as adipic acid, the synthesis process of long-carbon-chain dicarboxylic acid with high carbon number has the following technical difficulties: (1) complexity of the reaction: the reaction mechanism of the preparation method is that the reaction mechanism is subjected to a 6-oximido-6-nitrohexanoic acid intermediate process, the intermediate is directly converted into by-products glutaric acid and succinic acid, the main reaction and the side reaction belong to parallel reaction, and the addition of the catalyst and the control of the temperature are beneficial to improving the main reaction proportion. When the macrocyclic precursor of dodecanedioic acid is subjected to oxidative ring opening in a nitric acid solution, the macrocyclic precursor of dodecanedioic acid needs to undergo a diacid molecule carboxyl alpha-nitro or nitroso diacid intermediate, and then the intermediate is further oxidized into a dibasic acid with a shorter carbon chain through decarboxylation, and decarboxylation is performed in series, so that byproducts of the macrocyclic precursor of dodecanedioic acid comprise C11, C10, C9, C8, C7, C6 and the following dibasic carboxylic acids. How to avoid the occurrence of such series side reactions, so that the oxidation reaction only stays at C12 or a small amount of C11, and the further decarboxylation and oxidation are prevented from generating dibasic acid with lower carbon number, which is a great technical difficulty faced by the current nitric acid oxidation process. (2) Separation difficulty of reaction: compared with the adipic acid synthesis process in which only two byproducts of glutaric acid and succinic acid exist, the solubility curves of the main and side products in water are obviously different, and the purification of high-purity adipic acid can be realized through cooling crystallization; during the synthesis of the high-carbon-number dodecanedioic acid, dicarboxylic acids of C11, C10, C9, C8, C7, C6 and below are present. The dibasic acids, especially long carbon chain dibasic acids, have very similar structures, have small solubility difference in solvents and have great difficulty in crystallization and separation.
In order to overcome the limitations of the prior art and the technical difficulties of the preparation of the long carbon chain dicarboxylic acid, the following problems need to be mainly solved: (1) and a new process technology is developed to realize the preparation and production of the long carbon chain dicarboxylic acid. By controlling the reaction process conditions, the product is prevented from further carrying out series decarboxylation to form a low-carbon diacid byproduct; (2) the separation difficulty of reaction products is reduced, particularly the generation of low-carbon dicarboxylic acid and other high-boiling by-products is reduced, and the reaction selectivity is improved; (3) the production cost is reduced, the production efficiency is improved, and the technical competitiveness is improved to the maximum extent.
Summary of the invention
In view of this, the invention aims to provide a method for preparing long carbon chain dibasic acid by co-oxidation reaction, so as to reduce production cost, improve product yield, reduce nitric acid consumption and reduce separation difficulty.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing long carbon chain dibasic acid by co-oxidation reaction comprises the following steps: the mixture composed of at least one high-carbon macrocyclic alcohol or ketone and at least one low-carbon cyclic alcohol or ketone and nitric acid aqueous solution are subjected to a co-oxidation reaction under the action of a catalyst to generate a dicarboxylic acid mixture containing long-carbon-chain dicarboxylic acid in one step, and the required long-carbon-chain dicarboxylic acid is obtained after separation.
The higher-carbon macrocyclic alcohol or ketone in the mixture according to the present invention is selected from the group consisting of one or more of a cyclic alcohol having 8 to 16 carbon atoms, a cyclic ketone having 8 to 16 carbon atoms, a 1, 2-dihydroxycycloalkane having 8 to 16 carbon atoms and an oligomer of a macrocyclic diol as shown in formula I.
Further, the cyclic alcohol having 8 to 16 carbon atoms is selected from one or more of cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol, cyclododecanol, cyclotridecanol, cyclotetradecanol, cyclopentadecanol, cyclohexadecanol, 3, 5-trimethylcyclohexanol, preferably one or more of cyclooctanol, cyclodecanol, cyclododecanol and 3, 5-trimethylcyclohexanol, particularly preferably cyclododecanol; the cyclic ketone with 8-16 carbon atoms is selected from one or more of cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecone, cyclopentadecanone, cyclohexadecanone and 3, 5-trimethylcyclohexanone; preferably one or more of cyclooctanone, cyclodecanone, cyclododecanone and 3, 5-trimethylcyclohexanone, particularly preferably cyclododecanone; the 1, 2-dihydroxycycloalkane having 8 to 16 carbon atoms is selected from one or more of 1, 2-dihydroxycyclooctane, 1, 2-dihydroxycyclodecane and 1, 2-dihydroxycyclododecane, particularly preferably 1, 2-dihydroxycyclododecane; m in the oligomer of the macrocyclic diol shown in the formula I is 3-11, preferably 3,5 or 7, and particularly preferably m =7; n is 1-5.
Further, the 1, 2-dihydroxycyclododecane and cyclododecanol oligomer with m =7 represented by the formula I can be obtained by separating 1, 2-epoxy-5, 9-cyclododecadiene as a by-product in the production of 1, 2-epoxy-5, 9-cyclododecadiene by an arbitrary epoxidation reaction of 1,5, 9-cyclododecatriene. On one hand, the part of byproducts can be used as raw materials to synthesize the long carbon chain dicarboxylic acid, so that the economic value of the byproducts is fully developed, the production cost is reduced, and the economic benefit is maximized; on the other hand, the problem of low yield of the dodecanedioic acid prepared by directly oxidizing and ring-opening the epoxy macrocyclic olefin is avoided (US 3657335).
The lower cyclic alcohol or ketone of the invention is selected from one or more of cyclic alcohol with 4-6 carbon atoms, cyclic ketone with 4-6 carbon atoms and 1, 2-dihydroxycycloalkane with 4-6 carbon atoms.
Further, the cyclic alcohol having 4 to 6 carbon atoms is selected from one or more of cyclobutanol, cyclopentanol and cyclohexanol, preferably one or two of cyclopentanol and cyclohexanol, and particularly preferably cyclohexanol; the cyclic ketone with 4-6 carbon atoms is selected from one or more of cyclobutanone, cyclopentanone and cyclohexanone, preferably one or two of cyclopentanone and cyclohexanone, and particularly preferably cyclohexanone; the 1, 2-dihydroxycycloalkane having 4 to 6 carbon atoms is selected from one or both of 1, 2-dihydroxycyclopentane and 1, 2-dihydroxycyclohexane, and is preferably 1, 2-dihydroxycyclohexane.
Further, one or more of cyclododecanol, cyclododecanone, 1, 2-dihydroxycyclododecane or an oligomer of cyclododecanol represented by the formula I and one or more of cyclohexanol, cyclohexanone or 1, 2-dihydroxycyclohexane are used as a mixture.
According to the invention, researches show that under the same reaction conditions, when high-carbon macrocyclic alcohol or ketone is used as a reaction raw material, another low-carbon cyclic alcohol or ketone is added in a certain proportion to form a mixture, and then the mixture and nitric acid are subjected to a co-oxidation reaction to prepare long-carbon chain dicarboxylic acid, unexpected effects can be brought: taking cyclododecanol or cyclododecanone as an example, under the same reaction conditions, after a certain proportion of cyclohexanol or cyclohexanone is added, the selectivity of the product dodecanedioic acid is improved, and the proportion of low-carbon dibasic acid, particularly dibasic acid with carbon numbers of C9 and below is obviously reduced, possibly because the side reaction of the serial decarboxylation of the dodecanedioic acid by the dibasic acid with carbon numbers of C6 and below in a reaction system of the cyclohexanol or the cyclohexanone after the adipic acid is generated, particularly the generation of the dibasic acid with carbon numbers of C9 and below plays an obvious inhibiting role, which is obviously beneficial to the improvement of the reaction selectivity of the dodecanedioic acid.
Further, the mass ratio of the higher macrocyclic alcohol or ketone to another lower cyclic alcohol or ketone in the mixture of the higher macrocyclic alcohol or ketone and at least one lower cyclic alcohol or ketone is 1.
The introduction of the low-carbon cyclic alcohol or ketone can realize the flexible switching production of the long-carbon chain dicarboxylic acid and the short-carbon chain dicarboxylic acid: for example, when a small amount of low carbon cyclic alcohol or ketone is added into high carbon macrocyclic alcohol or ketone, mainly long carbon chain dibasic acid such as dodecanedioic acid is produced, and simultaneously a small amount of adipic acid can be co-produced, the selectivity and yield of the dodecanedioic acid product are improved compared with those of the product without the low carbon cyclic alcohol or ketone, byproducts of the whole reaction can migrate to higher carbon chain byproducts such as undecanedioic acid and sebacic acid, and the economic value of the byproducts is higher than that of the dibasic acid with a shorter carbon chain, so that the economic value and market competitiveness of the whole product line are enhanced; on the contrary, in order to obtain a smaller amount of dodecanedioic acid product, the proportion effect of a larger amount of adipic acid product can be utilized to realize the method, i.e. no more additional investment is needed, for example, in the existing adipic acid device, a small amount of dodecanedioic acid product can be produced in addition to the production of adipic acid, so that the differentiation competitiveness of the product is improved, and the method is very beneficial to the realization of technical upgrading and updating of the existing adipic acid production enterprises.
Further, the concentration of the aqueous nitric acid solution is 50 to 70wt%, preferably 55 to 65wt%. The nitric acid solution with too high concentration can cause too severe thermal effect of the reaction, the reaction temperature is difficult to control, and the over-oxidation products and the series decarboxylation side reaction products are obviously increased, which is obviously unfavorable for the selectivity, yield and product quality of the long carbon chain dibasic acid.
Further, the molar ratio of nitric acid in the aqueous nitric acid solution to the mixture is 3 to 15, preferably 5 to 10:1.
according to the invention, through research, under the same reaction conditions, high-carbon macrocyclic alcohol or ketone is used as a reaction raw material, after a certain proportion of low-carbon cyclic alcohol or ketone is added to form a mixture, the amount of nitric acid required for carrying out co-oxidation reaction is obviously lower than the amount of nitric acid (the molar ratio of nitric acid to the mixture is 10-20). The reason for this favorable result is not clear, and it is possible that a certain synergistic effect is produced by adding a certain proportion of a lower cyclic alcohol or ketone.
Further, the catalyst is a conventional copper catalyst or vanadium catalyst, typically a mixture of 0.1 to 2wt% copper catalyst and 0.1 to 0.5wt% vanadium catalyst. The copper catalyst can be one or more of copper powder, copper oxide and copper nitrate; the vanadium catalyst may be vanadium pentoxide and/or ammonium metavanadate.
Further, the temperature of the co-oxidation reaction of the invention is 35-90 ℃, and the preferable reaction temperature is 40-60 ℃; the reaction time is 20-120min, preferably 30-60min.
The temperature of the co-oxidation reaction provided by the invention is obviously lower than that of the prior art: taking cyclododecanol or cyclododecanone as an example for preparing dodecanedioic acid, because the molecular structure of the dodecanedioic acid is a long and flexible carbon ring, the reaction activity and the solubility in a nitric acid solution are lower than those of cyclohexanol or cyclohexanone, in the prior art, the oxidation reaction temperature needs to reach more than 65 ℃ to initiate the reaction, and the reaction rate is very slow within the range of 35-60 ℃ and needs to be more than 2-3h. Meanwhile, the reaction temperature is too high, so that the reaction is too violent, the reaction temperature is difficult to control, and the products of over-oxidation products and series decarboxylation side reactions are obviously increased. After a certain proportion of cyclohexanol or cyclohexanone is added, the cyclohexanol or cyclohexanone can react with nitric acid at a lower temperature due to higher reaction activity and solubility, so that cyclododecanol or cyclododecanone can also undergo oxidation reaction at the temperature, and the similar synergistic initiation effect is achieved. The inventor finds that cyclododecanol or cyclododecanone can be completely reacted within 2h even after cyclohexanol or cyclohexanone is added at a low reaction temperature (such as 35-60 ℃), the reaction time is obviously shorter than that when cyclohexanol or cyclohexanone is not added, and the reaction rate is improved to a certain extent. The addition of the low-carbon cyclic alcohol or ketone has a certain synergistic effect, and the oxidation temperature and the oxidation time of the high-carbon macrocyclic alcohol or ketone can be unexpectedly reduced. The reduction of the reaction temperature and the shortening of the reaction time can effectively inhibit the generated long carbon chain dibasic acid from further decarboxylating in series in the reaction system for a long time at a higher temperature on one hand, and on the other hand, the long carbon chain dibasic acid has limited solubility at a lower temperature, can be separated out from the reaction system in a solid form in time, and further reduces the occurrence degree of side reactions. After the low-carbon cyclic alcohol or ketone is added, the oxidation reaction is promoted to have higher reaction selectivity and yield, in some embodiments of the invention, the yield of the dodecanedioic acid can reach 90-93%, byproducts of the dodecanedioic acid mainly comprise undecanedioic acid and sebacic acid, and the content of dicarboxylic acid with lower carbon number is extremely low. The separation difficulty of the reaction is greatly reduced, and the dodecanedioic acid product with the purity of over 99.0 percent can be obtained by cooling and crystallizing in a proper solvent.
Further, the co-oxidation reaction according to the present invention is carried out in a continuous or discontinuous reaction system, preferably continuously; the reactor of the co-oxidation reaction is one of a loop reactor, a reaction kettle and a micro-channel reactor, and is preferably a loop reactor.
Further, the diacid mixture obtained by the co-oxidation reaction of the present invention may be subjected to purification means including distillation, chromatography, crystallization or combination thereof. In some embodiments of the present invention, after the mixture of dodecanedioic acid and adipic acid is prepared by the co-oxidation reaction, by utilizing the difference in solubility of each component at high temperature, the mixture is subjected to high temperature section cooling crystallization to obtain long carbon chain dibasic acid mainly containing dodecanedioic acid, and after centrifugal separation, the mother liquor is heated again and then cooled for crystallization to obtain short carbon chain dibasic acid mainly containing adipic acid.
The long carbon chain dicarboxylic acid prepared by the invention can be used for producing long carbon chain special nylon, such as nylon 612, nylon 1012 and nylon 1212; higher synthetic perfumes such as cyclopentadecanone lactone, muscone, 5-cyclohexadecanone, cyclopentadecanone, 12-methyl-14-carbonylbicyclo [9,3,1] pentadecane, etc.; high-end aviation lubricating oil, industrial cutting fluid and the like are applied to a plurality of fields of automobile manufacturing, submarine cables, industrial brushes, aviation manufacturing and the like.
Compared with the prior art, the method for preparing the long-carbon-chain dibasic acid by the co-oxidation reaction has the following advantages:
(1) The method for preparing the long carbon chain dibasic acid by the co-oxidation reaction is characterized in that the mixture of high-carbon macrocyclic alcohol or ketone and another low-carbon cyclic alcohol or ketone is subjected to the co-oxidation reaction with nitric acid, and compared with the method that the high-carbon macrocyclic alcohol or ketone is used as a single raw material, the addition of the low-carbon cyclic alcohol or ketone has the following functions: (1) in an oxidation reaction system, the short carbon chain dibasic acid generated by the low-carbon cyclic alcohol or ketone has an obvious inhibiting effect on the series decarboxylation side reaction of the long carbon chain dibasic acid, particularly the generation of the dibasic acid with the carbon number of C9 or below, which is obviously beneficial to the improvement of the reaction selectivity and the yield of the dodecanedioic acid; (2) the amount of nitric acid required by the oxidation reaction is reduced to be between that of adipic acid and that of dodecanedioic acid reported in the prior art, and the product quality of long-carbon-chain dibasic acid is not influenced; (3) the addition of the low-carbon cyclic alcohol or ketone has a certain synergistic effect, and can reduce the oxidation temperature and the oxidation time of the high-carbon macrocyclic alcohol or ketone. The reduction of the reaction temperature and the shortening of the reaction time can effectively inhibit the generated long carbon chain dibasic acid from further decarboxylating in series in the reaction system for a long time at a higher temperature on one hand, and on the other hand, the long carbon chain dibasic acid has limited solubility at a lower temperature, can be separated out from the reaction system in a solid form in time, and further reduces the occurrence degree of side reactions. After the low-carbon cyclic alcohol or ketone is added, multiple synergistic and beneficial factors are achieved, and the oxidation reaction is promoted to have higher reaction selectivity and yield;
(2) The method for preparing the long-carbon-chain dibasic acid by the co-oxidation reaction has the advantages that the oxidation reaction has higher reaction selectivity due to multiple synergistic beneficial factors after the low-carbon cyclic alcohol or ketone is added, the yield of the long-carbon-chain dibasic acid can reach 90-94%, byproducts mainly comprise undecanedioic acid and sebacic acid, the content of the dibasic acid with lower carbon number is extremely low, the separation difficulty of the reaction is greatly reduced, and a dodecanedioic acid product with the purity of over 99.0 percent can be obtained by cooling and crystallizing in a proper solvent;
(3) The method for preparing the long-carbon-chain dicarboxylic acid through the co-oxidation reaction can realize flexible switching production of the long-carbon-chain dicarboxylic acid and the short-carbon-chain dicarboxylic acid, and can improve the differentiated competitiveness of products without more additional investment;
(4) The method for preparing the long carbon chain dibasic acid by the co-oxidation reaction has lower production cost and higher atom economy, and the 1, 2-dihydroxycycloalkane in the raw material high carbon macrocyclic alcohol or ketone and the oligomer of the macrocyclic diol shown in the formula I are preferably obtained by separating the macrocyclic alkene in a byproduct mode when the macrocyclic alkene is prepared into the epoxidized macrocyclic alkene through the epoxidation reaction. The existing byproducts are used as raw materials and are converted into the long carbon chain dicarboxylic acid with higher economic value, so that the atom economy is improved, the waste is changed into valuable, the production cost is reduced, the economic benefit is maximized, and the competitiveness of the whole long carbon chain product industrial chain is enhanced;
(5) After the low-carbon cyclic alcohol or ketone is added in the method for preparing the long-carbon-chain dibasic acid by the co-oxidation reaction, the melting point of the whole raw material mixture can be reduced when the long-carbon-chain dibasic acid is mixed with the high-carbon cyclic alcohol or ketone due to the lower melting point, the requirements on the transportation of the raw materials and the heat preservation of pipelines are lower, the liquid feeding can be basically realized without melting and heating the raw materials, the continuous operation is convenient, the energy consumption required by the reaction is obvious in advantage, the production efficiency is high, and the method is suitable for industrial production. The method is suitable for preparing the long carbon chain dicarboxylic acid with 8-16 carbon atoms and has stronger applicability.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention will be described in detail with reference to the following examples.
In the following examples, the main and side products of the co-oxidation reaction dicarboxylic acid were subjected to esterification and derivatization, followed by gas chromatography, and the contents of the main product and the side products were quantified by the normalized normalization method.
The esterification derivatization method comprises the following steps:
weighing about 1.0g of solid sample, placing the solid sample in a flask, respectively adding 10g of anhydrous methanol, 10g of cyclohexane and 2-3 drops of concentrated sulfuric acid, respectively heating at 60-65 ℃ for esterification reaction, and simultaneously removing water in time by using a water separator. After 1h of reaction, the reaction mixture was cooled to room temperature for GC detection by gas chromatography.
The gas chromatographic conditions were as follows:
a chromatographic column: agilent DB-Wax (specification is 30m multiplied by 0.32mm multiplied by 0.25 mm); sample inlet temperature: 300 ℃; the split ratio is as follows: 30; column flow rate: 1.5mL/min; column temperature: 0.5min at 100 ℃; temperature rising procedure: raising the temperature to 300 ℃ at a speed of 15 ℃/min, and keeping the temperature for 8min; detector temperature: 300 ℃, hydrogen flow rate: 35mL/min, air flow: 350mL/min.
Example 1
In a 1L reaction vessel, 60wt% nitric acid was added so that the molar ratio of nitric acid to the mixture raw material (the mass ratio of cyclododecanol to cyclohexanol was 95. 100g of a mixture of cyclododecanol and cyclohexanol (the mass ratio of cyclododecanol to cyclohexanol is 95. The obtained reaction solution was filtered while hot, and the obtained solid a was vacuum-dried and weighed 117.9g; the filtrate was further cooled to room temperature and the solid B obtained weighed 7.0g after vacuum drying, and the conversion and selectivity of the reaction were determined by esterification derivatization. The results are shown in Table 1.
Comparative example 1
In a 1L reaction kettle, 60wt% of nitric acid is added so that the molar ratio of nitric acid to cyclododecanol raw material is 8. 100g of cyclododecanol is pumped into a reaction kettle in a molten state, the reaction temperature is kept constant by controlling the temperature of a circulating oil bath, so that the feeding time is controlled to be 20min, a solid product is separated out in the reaction process, the reaction conversion rate is only 73.6% by detection after the cyclododecanol is continuously stirred for 10min at the temperature, and the reaction is finished after the cyclododecanol is continuously reacted for 30 min. The reaction solution was filtered while hot, and the obtained solid a was dried in vacuo and weighed 123.8g, and the conversion and selectivity of the reaction were determined by esterification derivatization. The results are shown in Table 1.
TABLE 1 analysis of the reaction products
In Table 1, C12 is dodecanedioic acid, C11 is undecanedioic acid, C10 is sebacic acid, C9-C4 are dibasic acids having 9-4 carbons, C6 is adipic acid, C5 is glutaric acid, and C4 is succinic acid.
As can be seen from example 1 and comparative example 1, after cyclohexanol is added as a co-oxidized raw material, the reaction rate is obviously higher after cyclohexanol is added at the same reaction temperature, and the selectivity of dodecanedioic acid in the reaction product is obviously higher than that of comparative example 1; adipic acid and the like in the solid B obtained from the filtrate in example 1 almost completely resulted from oxidation with cyclohexanol, and cyclododecanol was subjected to co-oxidation after adding cyclohexanol as a raw material to obtain a C9 to C4 low-carbon dicarboxylic acid of which the content of the oxidation reaction liquid was only about 0.3%. The addition of cyclohexanol can effectively inhibit the side reaction of series decarboxylation of long carbon chain dibasic acid, and especially has obvious inhibiting effect on the generation of dibasic acid with carbon number of C9 or below.
Example 2
In a 1L reaction vessel, 55wt% nitric acid was added so that the molar ratio of nitric acid to the raw materials of the mixture was 5, copper powder and ammonium metavanadate were added so that the contents of Cu and V were 0.8wt% and 0.2wt%, respectively, of the raw materials of the mixture, and the reaction system was heated to 40 ℃ by a circulating oil bath. 100g of a mixture of cyclododecanone and cyclohexanone (the mass ratio of cyclododecanone to cyclohexanone is 90. And (3) further cooling the solid A obtained by filtering the reaction liquid while the reaction liquid is hot and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 2.
Example 3
In a 1L reaction vessel, 50wt% nitric acid was added so that the molar ratio of nitric acid to the mixture raw materials was 10. 100g of a mixture of 1, 2-dihydroxycyclododecane and the cyclododecanol represented by the general formula (I) and cyclohexanol (the mass ratio of the oligomer of 1, 2-dihydroxycyclododecane and the cyclododecanol represented by the general formula (I) to cyclohexanol is 80) is pumped into a reaction kettle in a liquid or molten state, the reaction temperature is kept constant by controlling the temperature of a circulating oil bath, so that the feeding time is controlled to be 20min, a solid product is separated out in the reaction process, and the reaction is finished after the mixture is continuously stirred at the temperature for 20 min. And (3) further cooling the solid A obtained by filtering the hot reaction liquid and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 2.
Example 4
In a 1L reaction vessel, 58wt% was added so that the molar ratio of nitric acid to the raw materials of the mixture was 4. 100g of a mixture of 1, 2-dihydroxycyclododecane and the oligomer of cyclododecanol represented by the general formula (I) and 1, 2-dihydroxycyclohexane (the mass ratio of the oligomer of 1, 2-dihydroxycyclododecane and the cyclododecanol represented by the general formula (I) to 1, 2-dihydroxycyclohexane is 65) is pumped into a reaction kettle in a liquid or molten state, the reaction temperature is kept constant by controlling the temperature of a circulating oil bath, so that the feeding time is controlled to be 30min, a solid product is precipitated in the reaction process, and the reaction is finished after continuously stirring at the temperature for 30 min. And (3) further cooling the solid A obtained by filtering the hot reaction liquid and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 2.
TABLE 2 analysis of the reaction products
In Table 1, C12 is dodecanedioic acid, C11 is undecanedioic acid, C10 is sebacic acid, C9-C4 are dibasic acids having 9-4 carbons, C6 is adipic acid, C5 is glutaric acid, and C4 is succinic acid.
Example 5
In a 1L reaction vessel, 65wt% was added so that the molar ratio of nitric acid to the raw materials of the mixture was 6. 100g of a mixture of the cyclooctanol and the cyclopentanone (the mass ratio of the cyclooctanol to the cyclopentanone is 92). And (3) further cooling the solid A obtained by filtering the reaction liquid while the reaction liquid is hot and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 3.
TABLE 3 analysis of the reaction products
In Table 1, C8 is suberic acid, C7 is pimelic acid, C6 is adipic acid, C5 is glutaric acid, and C4 is succinic acid.
Example 6
In a 1L reaction vessel, 55wt% was charged so that the molar ratio of nitric acid to the raw materials of the mixture was 8.5, copper powder and ammonium metavanadate were added so that the contents of Cu and V were 0.8wt% and 0.3wt%, respectively, of the raw materials of the mixture, and the reaction system was heated to 40 ℃ by a circulating oil bath. 100g of a mixture of 3, 5-trimethylcyclohexanol and cyclopentanol (the mass ratio of the 3, 5-trimethylcyclohexanol to the cyclopentanol is 89: 11) is pumped into a reaction kettle in a liquid form, the reaction temperature is kept constant by controlling the temperature of a circulating oil bath, so that the feeding time is controlled to be 20min, a solid product is separated out in the reaction process, and the reaction is finished after continuously stirring at the temperature for 35 min. And (3) further cooling the solid A obtained by filtering the hot reaction liquid and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 4.
TABLE 4 analysis of the reaction products
In Table 1, C9 in the solid A component is 2, 4-trimethyladipic acid and 2, 4-trimethyladipic acid, C8 is 2, 4-trimethylglutaric acid, C7 is 2, 2-dimethylglutaric acid, C6 to C5 are 2, 2-dimethylsuccinic acid and 2, 2-dimethylmalonic acid; c5 in the solid component B is glutaric acid, and C4 is succinic acid.
Example 7
And carrying out continuous co-oxidation reaction in four-stage series reaction kettles, wherein each stage of reaction kettle is heated and removes heat through a circulating oil bath, and the reaction temperature is controlled at 55 ℃. Adding a 55wt% nitric acid solution prepared with a copper/vanadium catalyst into a first-stage reaction kettle, wherein the total feeding amount of nitric acid is 3.75kg/h, and the total residence time of co-oxidation is controlled to be 60min; cyclododecanol and cyclohexanone mixture (the mass ratio of cyclododecanol to cyclohexanone is 95. The molar ratio of nitric acid to the mixture starting materials was 6. And (3) further cooling the solid A obtained by filtering the hot reaction liquid and the filtrate to room temperature, filtering the obtained solid B, drying the obtained solid B in vacuum, and determining the conversion rate and selectivity of the reaction through esterification and derivatization. The results are shown in Table 5.
TABLE 5 analysis of the reaction products
In Table 1, C12 is dodecanedioic acid, C11 is undecanedioic acid, C10 is sebacic acid, C9-C4 are dibasic acids having 9-4 carbons, C6 is adipic acid, C5 is glutaric acid, and C4 is succinic acid.
The solid A is subjected to simple temperature reduction crystallization in a proper solvent such as methanol or acetic acid to obtain a high-quality dodecanedioic acid product, wherein the actual yield of the dodecanedioic acid is 92.8%, the purity of the monoacid is 99.5%, the moisture content is 0.041%, the total nitrogen content is 25ppm, the Fe ion content is 0.1ppm, and the ash content is 12ppm.
Examples of polymerization Process
500g of the above-mentioned refined dodecanedioic acid is dissolved in anhydrous ethanol of 4 to 8 times by mass, and heated to 80 ℃ to dissolve all the dodecanedioic acid. A70% hexamethylenediamine-ethanol solution is added with stirring to form a salt (equimolar proportions of hexamethylenediamine and dodecanedioic acid). In the salifying process, the temperature is maintained at about 85 ℃, the pH value at the end point is 7.3, the mixture is cooled to room temperature, and 750g of white crystalline nylon 612 salt is obtained after filtration and drying. Adding the nylon 612 salt, 120g of water, 1.8g of molecular regulator and 0.5g of antioxidant into a polymerization reaction kettle, starting to heat to 210 ℃ after nitrogen replacement, increasing the pressure in the kettle to 1.5MPa, and maintaining the reaction for 2-3h. Then the pressure is reduced to the atmospheric pressure, the temperature is increased to 250 ℃, and the atmospheric pressure is vented for 2 hours. Finally, after the air release is finished, the vacuum pumping is carried out for 20 to 60min, and the vacuum degree is 0.5 to 0.6MPa. After the reaction is finished, the molten polymer is extruded, cooled and cut into particles to obtain the nylon 612 resin, and the product performance is shown in table 6.
TABLE 6 comparison of product Performance of nylon 612 prepared by polymerization of example 7 with commercially available nylon 612
| Test items | Commercially available nylon 612 | Example 7 preparation of Nylon 612 |
| Density (g/cm) 3 ) | 1.07 | 1.066 |
| Melting Point (. Degree.C.) | 218 | 218.2 |
| Tensile Strength (MPa) | 74 | 72.3 |
| Modulus of elasticity (MPa) | 1900 | 2058 |
| Elongation at break 23 ℃ (%) | ≥200 | 234 |
| Flexural Strength (MPa) | 82 | 80.9 |
| Flexural modulus of elasticity (MPa) | 2900 | 2982 |
| Notched impact strength (J/m) | 75 | 76.2 |
| Heat distortion temperature 0.46MPa (. Degree.C.) | 180 | 181.2 |
| Rockwell hardness (R) | 114 | 113 |
| Water absorption (23 ℃,24h in Water) (%) | 0.25 | 0.27 |
From example 7, it is understood that the dodecanedioic acid can be obtained with high selectivity and yield by carrying out the co-oxidation reaction of a mixture of cyclododecanol and cyclohexanone with nitric acid. The polymer-grade long carbon chain diacid product can be obtained through simple crystallization, and various product performance parameters of the nylon 612 resin obtained through melt polymerization with the hexamethylene diamine are consistent with those of the products sold in the market at present.
Claims (10)
1. A method for preparing long carbon chain dibasic acid through co-oxidation reaction is characterized by comprising the following steps: mixing and heating a component A, a component B, an aqueous nitric acid solution and a catalyst to completely react to obtain a reaction liquid containing the required long-carbon-chain dibasic acid, wherein the component A comprises one or more of cyclic alcohol with 8-16 carbon atoms, cyclic ketone with 8-16 carbon atoms, 1, 2-dihydroxycycloalkane with 8-16 carbon atoms and a compound shown in formula I, and the component B comprises one or more of cyclic alcohol with 4-6 carbon atoms, cyclic ketone with 4-6 carbon atoms and 1, 2-dihydroxycycloalkane with 4-6 carbon atoms,
2. the method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the cyclic alcohol having 8 to 16 carbon atoms includes one or more of cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol, cyclododecanol, cyclotridecanol, cyclotetradecanol, cyclopentadecanol, cyclohexadecanol, 3, 5-trimethylcyclohexanol; the cyclic ketone with 8-16 carbon atoms comprises one or more of cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecone, cyclopentadecanone, cyclohexadecanone, 3, 5-trimethylcyclohexanone; the 1, 2-dihydroxycycloalkane having 8 to 16 carbon atoms includes one or more of 1, 2-dihydroxycyclooctane, 1, 2-dihydroxycyclodecane and 1, 2-dihydroxycyclododecane; preferably, the cyclic alcohol having 8 to 16 carbon atoms includes one or more of cyclooctanol, cyclodecanol, cyclododecanol, and 3, 5-trimethylcyclohexanol; the cyclic ketone having 8 to 16 carbon atoms includes one or more of cyclooctanone, cyclodecanone, cyclododecanone, and 3, 5-trimethylcyclohexanone; the 1, 2-dihydroxycycloalkane having 8 to 16 carbon atoms is 1, 2-dihydroxycyclododecane; m is 3,5 or 7; further preferably, the cyclic alcohol having 8 to 16 carbon atoms is cyclododecanol, the cyclic ketone having 8 to 16 carbon atoms is cyclododecanone, and m =7.
3. The method for preparing long carbon chain dibasic acid through co-oxidation according to claim 1, wherein: the cyclic alcohol having 4 to 6 carbon atoms includes one or more of cyclobutanol, cyclopentanol, cyclohexanol; the cyclic ketone with 4-6 carbon atoms comprises one or more of cyclobutanone, cyclopentanone and cyclohexanone; the 1, 2-dihydroxycycloalkane having 4 to 6 carbon atoms includes one or both of 1, 2-dihydroxycyclopentane and 1, 2-dihydroxycyclohexane; preferably, the cyclic alcohol having 4 to 6 carbon atoms is one or both of cyclopentanol or cyclohexanol; the cyclic ketone with 4-6 carbon atoms is one or two of cyclopentanone or cyclohexanone; the 1, 2-dihydroxycycloalkane having 4 to 6 carbon atoms is 1, 2-dihydroxycyclohexane; further preferably, the cyclic alcohol having 4 to 6 carbon atoms is cyclohexanol, and the cyclic ketone having 4 to 6 carbon atoms is cyclohexanone.
4. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the mass ratio of the component A to the component B is 1; preferably 50; more preferably from 90.
5. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the concentration of the nitric acid aqueous solution is 50-70wt%; preferably 55-65wt%.
6. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the ratio of the molar weight of the nitric acid in the nitric acid aqueous solution to the sum of the molar weights of the component A and the component B is 3-15; preferably 5 to 10.
7. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the reaction temperature is 35-90 ℃, and the reaction time is 20-120min; preferably, the reaction temperature is 30-60 ℃ and the reaction time is 30-60min.
8. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: the catalyst comprises a copper catalyst or a vanadium catalyst; preferably, the copper catalyst comprises one or more of copper powder, copper oxide and copper nitrate, and the vanadium catalyst comprises vanadium pentoxide and/or ammonium metavanadate; further preferably, the mass of the copper catalyst is 0.1-2% of the mass sum of the component A and the component B, and the mass of the vanadium catalyst is 0.1-0.5% of the mass sum of the component A and the component B.
9. The method for preparing long carbon chain dibasic acid through co-oxidation according to claim 1, further comprising the following steps: and filtering and drying the reaction liquid containing the required long carbon chain dibasic acid to obtain the required long carbon chain dibasic acid.
10. The method for preparing long carbon chain dibasic acid through the co-oxidation reaction according to claim 1, wherein: one or more of cyclododecanol, cyclododecanone, 1, 2-dihydroxy cyclododecane or a compound shown as the formula I and one or more of cyclohexanol, cyclohexanone or 1, 2-dihydroxy cyclohexane are used as a mixture to be mixed with a nitric acid aqueous solution and a catalyst and heated to be reacted completely, so as to obtain a reaction solution containing the needed long carbon chain dibasic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB876335A (en) * | 1959-03-02 | 1961-08-30 | Exxon Research Engineering Co | Preparation of 1, 12-dodecanedioic acid |
| SU1171453A1 (en) * | 1983-05-31 | 1985-08-07 | Предприятие П/Я Р-6603 | Method of producing 1,10-decandicarboxylic acid |
| CN102892741A (en) * | 2010-05-10 | 2013-01-23 | 罗地亚经营管理公司 | Process for preparing dicarboxylic acids |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB876335A (en) * | 1959-03-02 | 1961-08-30 | Exxon Research Engineering Co | Preparation of 1, 12-dodecanedioic acid |
| SU1171453A1 (en) * | 1983-05-31 | 1985-08-07 | Предприятие П/Я Р-6603 | Method of producing 1,10-decandicarboxylic acid |
| CN102892741A (en) * | 2010-05-10 | 2013-01-23 | 罗地亚经营管理公司 | Process for preparing dicarboxylic acids |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375986A (en) * | 2023-02-24 | 2023-07-04 | 广西科学院 | All-wood cellulose-based polyester and preparation method thereof |
| CN116375986B (en) * | 2023-02-24 | 2024-04-02 | 广西科学院 | All-wood cellulose-based polyester and preparation method thereof |
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