CN102206149A - Method for preparing corresponding diacid by catalytic oxidization of naphthene - Google Patents
Method for preparing corresponding diacid by catalytic oxidization of naphthene Download PDFInfo
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- CN102206149A CN102206149A CN2010101367202A CN201010136720A CN102206149A CN 102206149 A CN102206149 A CN 102206149A CN 2010101367202 A CN2010101367202 A CN 2010101367202A CN 201010136720 A CN201010136720 A CN 201010136720A CN 102206149 A CN102206149 A CN 102206149A
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- acid
- cycloalkanes
- catalyzer
- hydrogen peroxide
- solvent
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 title claims description 30
- 230000003197 catalytic effect Effects 0.000 title abstract description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 81
- 239000002253 acid Substances 0.000 claims description 71
- 230000003647 oxidation Effects 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000011964 heteropoly acid Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- -1 normenthane Natural products 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- SGVUHPSBDNVHKL-UHFFFAOYSA-N 1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical group CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical class [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical class [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 claims description 3
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical class [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 claims description 3
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical class [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- KVZJLSYJROEPSQ-UHFFFAOYSA-N 1,2-dimethylcyclohexane Chemical compound CC1CCCCC1C KVZJLSYJROEPSQ-UHFFFAOYSA-N 0.000 claims 2
- 150000002821 niobium Chemical class 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical group [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000004715 keto acids Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 11
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 10
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 8
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000007520 diprotic acids Chemical class 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010523 cascade reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005587 bubbling Effects 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
- 150000001717 carbocyclic compounds Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical class [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种催化氧化环烷制备相应二酸的方法，其特征在于在温度为0～180℃和压力为0.1～3.0MPa的条件下，将环烷、过氧化氢、溶剂与催化剂接触反应，其中，环烷、过氧化氢与溶剂的摩尔比为1∶1～50∶0～1000，环烷与催化剂的质量比为0.1～500∶1，所说的催化剂为钛硅分子筛与多金属含氧酸或其盐的组合物。该方法环烷转化率高，相应二酸的选择性好，且具有较好的催化活性稳定性。该方法为绿色合成工艺，无特殊生产设备要求，生产过程简单，容易控制，利于工业化生产和应用。A method for catalytically oxidizing cycloalkane to prepare corresponding diacids, characterized in that under the conditions of a temperature of 0-180°C and a pressure of 0.1-3.0 MPa, cycloalkane, hydrogen peroxide, and a solvent are contacted and reacted with a catalyst, wherein, The molar ratio of naphthene, hydrogen peroxide and solvent is 1:1～50:0～1000, the mass ratio of naphthene and catalyst is 0.1～500:1, and said catalyst is titanium silicon molecular sieve and polymetallic oxoacid or a combination of salts thereof. The method has high conversion rate of naphthene, good selectivity of corresponding diacid, and good stability of catalytic activity. The method is a green synthesis process, does not require special production equipment, has a simple production process, is easy to control, and is beneficial to industrial production and application.
Description
Technical field
The invention relates to the method that a kind of catalyzed oxidation cycloalkanes prepares corresponding diacid.
Background technology
Di-carboxylic acid is an important chemical material, and wherein important have Succinic Acid, pentanedioic acid, a hexanodioic acid etc., is the principal monomer of synthon-nylon 66 and the main raw material of nylon engineering plastic as hexanodioic acid.Hexanodioic acid is the main raw material of synthesis of polyurethane foam, synthetic leather (PU), synthetic rubber and film simultaneously.Hexanodioic acid can be used as food acidulant, ester plasticizer and textile treating agent, also can be used for the production of medicine, agricultural chemicals, spices, tackiness agent and soldering flux etc.
In traditional Production Processes of Adipic Acid, mainly be to be the production route of starting raw material with benzene, account for the hydrogenation preparing cyclohexane at first more than 90% of global aggregated capacity, air oxidation of cyclohexane becomes hexalin and pimelinketone (being commonly called as K-A oil) then, then with nitric acid K-A oil is oxidized to hexanodioic acid.The first step cyclohexane oxidation be the transformation efficiency of K-A oil general＜10%, in the selectivity about 80%, particularly intermediate product cyclohexyl hydroperoxide decomposition course, the pimelinketone selectivity is not high; Produce the oxynitrides that environment is had severe contamination in the second step nitric acid oxidation process, equipment corrosion is serious, the operational condition harshness.
" method of oxidation synthesis of adipic acid by epoxy cyclohexane " of CN101177390A, the method that relates to a kind of oxidation synthesis of adipic acid by epoxy cyclohexane, this method is a catalyzer with tungsten, molybdenum multi-metal oxygen hydrochlorate, and aqueous hydrogen peroxide solution is made oxygenant, the catalysis oxidation synthesis of adipic acid by epoxy cyclohexane.The principal feature of this method is no longer with an organic solvent to make reaction medium, avoids the pollution of using nitric acid as oxidant that environment is produced.
" method of a kind of synthesizing cyclohexanol, pimelinketone, hexanodioic acid " of CN1062718A, disclosing a kind of organic high conductivity polymer molecular clustering of transition metal catalyzer is applied to the hexanaphthene is the method for initial feed synthesizing cyclohexanol, pimelinketone, hexanodioic acid.
CN1193009A disclosed " a kind of method of obtaining hexanodioic acid and diprotic acid ", produce in pimelinketone and the hexalin process with air oxidation of cyclohexane, the washing sour water that mainly contains the caproic acid organic hydroper oxide, heating evaporation concentrates under normal pressure or decompression, concentrated solution is to carry out thermolysis between 90 ℃～105 ℃ or is that catalyzer carries out cartalytic decomposition effect with the variable valency metal ions in normal pressure, temperature, mixed solution after the decomposition, in normal pressure or decompression, temperature is to carry out oxidizing reaction with nitric acid under 35 ℃～78 ℃ conditions, generates hexanodioic acid and diprotic acid mixed solution.Obtain smart hexanodioic acid through enrichment, crystallization, filtration, drying and activated carbon treatment again; Crystalline mother solution gets diprotic acid through enrichment, crystallization.
CN101337879A discloses technology and the equipment that a kind of catalytic air oxidation hexanaphthene prepares hexanodioic acid.In hexanaphthene, be dissolved with the mixed catalyst that the catalyzer monometallic porphyrin of 1-50ppm or M-oxygen bimetallic porphyrin or they and transition metal salt or oxide compound constitute, in having the multi-stage oxidizing reactor of gas distributor, the air of feeding 5-12atm or oxygen enrichment, oxygen-denuded air, control reaction temperature was 140-160 ℃, with cyclohexane oxidation 45-120 minute; Oxidation mixtures enters flash separator, and at temperature 78-155 ℃, flash distillation under the pressure 0.1-1.0atm condition makes low-boiling products hexanaphthene, hexalin and pimelinketone become gas, surpasses 80% hexanodioic acid with content and separates; Again with the continuous cyclic oxidation of low-boiling products, with the separation and purification of high boiling point oxidation products: carry out purifies and separates by prior art, obtain smart adipic acid product.
CN1556088A relates to the method that a kind of bionically catalyzing and oxidizing hexanaphthene prepares hexanodioic acid, select for use metal phthalocyanine, monokaryon metalloporphyrin or μ-oxygen-dinuclear metalloporphyrin compounds with the biological enzyme structural similitude as catalyzer, its consumption is 0.1 of hexanaphthene weight～1 ‰, with hexanaphthene itself as solvent, feed the oxygen of 0.5～3.5MPa, control reaction temperature is 110～160 ℃, reaction times 4～32h.
CN1535947A discloses the method for atmospheric oxidation hydrogenation of six carbocyclic compound hexanodioic acid, relates under catalysis of metalloporphyrin, and the mixture oxidation by air of hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone becomes the novel process of hexanodioic acid.Under the 1-20atm air conditions, temperature of reaction is 50-200 ℃, select for use μ-oxygen-bimetallic porphyrin and monometallic porphyrin or their immobilized thing to make catalyzer separately, also can select for use metalloporphyrin or their immobilized thing as Primary Catalysts, as co-catalyst, metalloporphyrin can be efficient as biological enzyme under biological concentration, the highly selective catalytic air directly becomes hexanodioic acid with cyclohexane oxidation with transition metal salt or oxide compound.
CN101337878A discloses a kind of method of directly producing adipic acid by cyclohexane catalytic oxidation, and this method forms mixed suspension with hexanaphthene, solvent, initiator and carbon material catalyst mix, and the carbon material catalyzer is carbon nanotube, graphite or gac; Mixing suspension is warming up to 50-250 ℃ again, aerating oxygen or air are as oxygenant, and the maintenance reacting kettle inner pressure is 0.1-5MPa, reaction 0.1-20h; To obtain reaction mixture and separate, can obtain the product hexanodioic acid.
CN101239899A discloses a kind of method of preparing adipic acid by using cyclohexane catalytic oxidation one-step, and this method first just hexanaphthene, solvent, initiator join in the reactor with the solid catalyzer and mix, and form mixed suspension; Then the gained mixing suspension is warming up to 50-250 ℃, the oxygen of feeding sufficient quantity or air are as oxygenant, and reactor pressure is 0.1-5MPa, reaction 0.1-20h; And reaction mixture separated, obtain solid catalyst and contain the liquid mixture of reaction product, unreacted reactant and solvent; Isolate hexanodioic acid in the last isolated liquid phase mixture.
CN1157605A is direct oxidation into the method for recycling cobalt-containing catalyst in the reaction of hexanodioic acid at hexanaphthene, it is characterized in that comprising that a processing becomes the step of the reaction mixture that generates in the hexanodioic acid process at cyclohexane oxidation, this step comprises that extraction is at least partially in the pentanedioic acid and the Succinic Acid that produce in the reaction.
CN1850756A discloses the method for a kind of cyclohexane air dioxide prepare cyclohexanol, pimelinketone and hexanodioic acid: in the reactive system of the bubbling column reactor cascade reaction system of the tank reactor cascade reaction system of a 4-8 level belt stirrer or the outer circulation of 3-7 band or 2-6 dissimilar reactors in series, feeding is dissolved with hexanaphthene that the 1-100ppm metalloporphyrin is a catalyzer and air or oxygen or oxygen-rich air or the oxygen-denuded air of 0.1-2.0ppm, temperature 120-160 ℃ of reaction 45-120 minute down.
A kind of catalyzed oxidation material that is called as HTS (TS-1) is disclosed in USP4410501, document (J Catal, 1995,157:631-635) its catalyzed oxidation hexanaphthene has been carried out a series of research, draw: hexanaphthene initial oxidation on TS-1 is a hexalin, reoxidizes to be pimelinketone.Selecting the shape selectivity makes hexalin will be oxidized to pimelinketone further in the TS-1 zeolite cages.
Do not see the composition catalyst that utilizes HTS and multiple-metal oxygen-containing acid and salts substances thereof so far, be the research report that oxidizer catalytic oxidation cycloalkanes prepares corresponding diacid aspect with the hydrogen peroxide.
Summary of the invention
The purpose of this invention is to provide the method that a kind of oxidation cycloalkanes that is different from existing catalyst system prepares corresponding diacid.
Oxidation cycloalkanes provided by the invention prepares the method for corresponding diacid, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.2～50: 0～1000, the mass ratio of cycloalkanes and catalyzer is 0.1～500: 1, and said catalyzer is the composition of HTS and multiple-metal oxygen-containing acid or its salt.
In the method provided by the invention, said HTS can be selected from one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48, wherein preferred HTS is TS-1, and this molecular sieve has the MFI crystalline structure.
In the method provided by the invention, said multiple-metal oxygen-containing acid or salt can be heteropllyacids or heteropoly blue class.Said heteropolyacid is well known to those skilled in the art, and the class that heteropolyacid is made up of by the oxygen atom ligand bridging by certain structure heteroatoms (as P, Si, Fe, Co etc.) and polyatom (as Mo, W, V, Nb, Ta etc.) contains the oxygen polyacid.Heteropoly blue is the general name of the transition metal heteropolyacid salt of a big class lower valency.Heteropoly blue is obtained by heteropolyacid salt reduction usually, and for example phosphato-molybdic heteropolyacid reduces bluely with tin protochloride the phosphorus molybdenum blue.Reduzate generally still keeps original structure, and the delocalized electron that reduction obtains makes its blueness with different depths, therefore again such electronics is called " blue electronics ".[SiWO for example
39]
8-Can under low temperature and inert atmosphere, be reduced to [SiWO
40]
6-Blue compound, tungsten wherein be+5 with the mixed valence of+6 valencys.P
3+, Fe
3+And Cr
3+The position that also can replace a tungsten atom.In the method provided by the invention, said heteropolyacid or heteropoly blue can be phosphorus tungsten class heteropolyacid or heteropoly blue, molybdenum tungsten class heteropolyacid or heteropoly blue, phosphorus vanadium class heteropolyacid or heteropoly blue, molybdenum vanadium class heteropolyacid or heteropoly blue, tungsten silicon class heteropolyacid or heteropoly blue etc.
In the method provided by the invention, said multiple-metal oxygen-containing acid or salt also can be isopoly-acid or isopoly-acid salt.Said isopoly-acid is well known to those skilled in the art, and the class acid that isopoly-acid is made up of identical acid anhydrides also can be thought: the acid that two or more simple oxygen acid molecule of the same race condensations form.What easily form isopoly-acid in transition metal has elements such as Mo, W, V, Cr, for example a H
4V
2O
7, H
6V
4O
13, H
7V
5O
16, H
6V
10O
28H
6M
7O
24, H
4Mo
8O
26, H
10Mo
12O
41Deng.Factors such as the concentration of their formation condition and solution, temperature, acidity are relevant, and generally along with the increase of acidity, the degree of condensation increases.Hydrogen ion in the isopoly-acid is replaced by metal ion can generate corresponding isopoly-acid salt, or is called with how blue.
In the method provided by the invention, the mass ratio of HTS and multiple-metal oxygen-containing acid or salt is 0.01～150 in the said catalyzer, preferred 0.1～50.
In the method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 1～10: 0～200, and the mass ratio of cycloalkanes and catalyzer is 0.1～100: 1.
In the method provided by the invention, cycloalkanes can be hexanaphthene, pentamethylene or their substituent, said substituent is methylcyclopentane, normenthane, 1 for example, 2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1-methyl-4-tertiary butyl hexanaphthene etc.
In the method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In the method provided by the invention, said solvent is selected from alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, or ketones such as acetone, butanone, or nitrile such as acetonitrile, or multiple mixing in the above-mentioned alcohol, ketone, nitrile, preferred solvent is one or more the mixing in methyl alcohol, acetonitrile, the acetone.
In the method provided by the invention, preferred embodiment be to be that 30～130 ℃ and pressure are under the condition of 0.2～1.5MPa in temperature, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.5～20: 0～50, the mass ratio of cycloalkanes and catalyzer is 5～80: 1, the ratio 0.1～50 of the acid of HTS and multiple-metal oxygen-containing or its salt in the catalyzer.
Catalyzed oxidation cycloalkanes provided by the invention prepares the method for diacid, has following advantage:
1, reaction conditions gentleness;
2, its catalytic oxidation activity and stability of catalytic activity are better;
3, be green synthesis process, the whole process of production environmental friendliness, no special producing equipment requirements, production process is simple, and control is beneficial to suitability for industrialized production and application easily.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent, and used titanium-silicon molecular sieve TS-1 is that TS-2 prepares according to the CN1167081A method by the preparation of prior art (Zeolites, 1992, the 943rd～950 page of Vol.12) method.Ti-MCM-41 prepares according to document (Chem.Commun., 1994,147～148) method.
In Comparative Examples and embodiment:
Comparative Examples
Is 1: 2: 10 with hexanaphthene, hydrogen peroxide and solvent acetone according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.React after 2 hours, conversion of cyclohexane is 0%.React after 15 hours, conversion of cyclohexane is 0%.
Embodiment 1
Is 1: 2: 20 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 100) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 20, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 36%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 35%; The hexanodioic acid selectivity is 91%.
Embodiment 2
Is 1: 2: 27 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 0.1) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 30, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 13%; The hexanodioic acid selectivity is 91%.The result who reacts 15 hours is as follows: cyclohexane conversion is 15%; The hexanodioic acid selectivity is 90%.
Embodiment 3
Is 1: 6: 18 with hexanaphthene, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 50) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 12, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 84%; The hexanodioic acid selectivity is 91%.The result who reacts 15 hours is as follows: cyclohexane conversion is 72%; The hexanodioic acid selectivity is 90%.
Embodiment 4
Is 1: 8: 16 with hexanaphthene, hydrogen peroxide, solvent tertiary butanol and catalyzer (mass ratio of TS-1 and phosphato-molybdic heteropolyacid is 10) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 80, is that 40 ℃ of pressure are to react under the 0.2MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 82%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 78%; The hexanodioic acid selectivity is 91%.
Embodiment 5
Is 1: 3: 5 with hexanaphthene, hydrogen peroxide, aqueous solvent and catalyzer (mass ratio of Ti-MCM-41 and phosphorus tungsten heteropoly blue is 20) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 180, is that 90 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 19%; The hexanodioic acid selectivity is 96%.The result who reacts 15 hours is as follows: cyclohexane conversion is 16%; The hexanodioic acid selectivity is 92%.
Embodiment 6
Is 3: 1 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and tungsten isopoly-acid is 40) according to the mol ratio of hexanaphthene and hydrogen peroxide, and the mass ratio of hexanaphthene and catalyzer is 25, is that 130 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 13%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 12%; The hexanodioic acid selectivity is 90%.
Embodiment 7
Is 1: 8 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and phosphorus molybdenum heteropoly blue is 0.5) according to the mol ratio of hexanaphthene and hydrogen peroxide, and the mass ratio of hexanaphthene and catalyzer is 15, is that 60 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 64%; The hexanodioic acid selectivity is 95%.The result who reacts 15 hours is as follows: cyclohexane conversion is 62%; The hexanodioic acid selectivity is 92%.
Embodiment 8
Is 1: 2 with hexanaphthene, hydrogen peroxide and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) according to the mol ratio of hexanaphthene and hydrogen peroxide, and the mass ratio of hexanaphthene and catalyzer is 5, is that 60 ℃ of pressure are to react under the 0.8MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 78%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 76%; The hexanodioic acid selectivity is 93%.
Embodiment 9
Is 8: 1: 32 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-2 and molybdenum isopoly-acid is 20) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 10, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 12%; The hexanodioic acid selectivity is 94%.The result who reacts 15 hours is as follows: cyclohexane conversion is 11%; The hexanodioic acid selectivity is 91%.
Embodiment 10
Is 10: 1: 20 with hexanaphthene, hydrogen peroxide, solvent acetone and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 15) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 80, is that 40 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 9%; The hexanodioic acid selectivity is 96%.The result who reacts 15 hours is as follows: cyclohexane conversion is 8.5%; The hexanodioic acid selectivity is 93%.
Embodiment 11
Is 2: 1: 30 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 50) according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 40, is that 30 ℃ of pressure are to react under the 1.5MPa in temperature.The result who reacts 2 hours is as follows: cyclohexane conversion is 11%; The hexanodioic acid selectivity is 93%.The result who reacts 15 hours is as follows: cyclohexane conversion is 9%; The hexanodioic acid selectivity is 91%.
Embodiment 12
Is 1: 1: 15 with methylcyclohexane, hydrogen peroxide, solvent methanol and catalyzer (mass ratio of TS-1 and tungsten sila polyacid is 0.3) according to the mol ratio of cycloalkanes, hydrogen peroxide and solvent, the mass ratio of cycloalkanes and catalyzer is 60, is that 60 ℃ of pressure are to react under the 1.0MPa in temperature.The result who reacts 2 hours is as follows: the methylcyclohexane transformation efficiency is 13%; The diacid selectivity is 94%.The result who reacts 15 hours is as follows: the methylcyclohexane transformation efficiency is 12%; The diacid selectivity is 91%.
Embodiment 13
The process that the present embodiment explanation utilizes catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 10) to react in the tank reactor of sealing.
Is 1: 5: 20 with pentamethylene, hydrogen peroxide, solvent acetone and catalyzer according to the mol ratio of cycloalkanes, hydrogen peroxide and solvent, and the mass ratio of cycloalkanes and catalyzer is 50, is that 60 ℃ of pressure are to react under the 0.6MPa in temperature.The result who reacts 2 hours is as follows: the pentamethylene transformation efficiency is 26%; The pentanedioic acid selectivity is 95%.The result who reacts 12 hours is as follows: the pentamethylene transformation efficiency is 65%, and the pentanedioic acid selectivity is 88%.
Embodiment 14
The process that the present embodiment explanation utilizes catalyzer (mass ratio of TS-1 and phosphorus heteropoly tungstic acid is 40) to react in the tank reactor of sealing.
Is 1: 2: 50 with hexanaphthene, hydrogen peroxide, solvent methanol and catalyzer according to the mol ratio of hexanaphthene, hydrogen peroxide and solvent, and the mass ratio of cycloalkanes and catalyzer is 20, and temperature is that 80 ℃ of pressure are to react under the 1.5MPa.The result who reacts 2 hours is as follows: cyclohexane conversion is 17%, and the hexanodioic acid selectivity is 94%.The result who reacts 12 hours is as follows: cyclohexane conversion is 48%; The hexanodioic acid selectivity is 90%.
From embodiment and Comparative Examples as can be seen: method catalytic activity height provided by the invention, selectivity is good, and especially stability of catalytic activity is better.
Claims (10)
1. a catalyzed oxidation cycloalkanes prepares the method for corresponding diacid, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.2～50: 0～1000, the mass ratio of cycloalkanes and catalyzer is 0.1～500: 1, and said catalyzer is the composition of HTS and multiple-metal oxygen-containing acid or its salt.
2. according to the method for claim 1, it is characterized in that said HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
3. according to the method for claim 1, it is characterized in that said multiple-metal oxygen-containing acid is heteropolyacid or isopoly-acid, said multiple-metal oxygen-containing hydrochlorate is a heteropoly blue or with many salt.
4. according to the method for claim 3, wherein, said multiple-metal oxygen-containing acid is selected from phosphorus tungsten class heteropolyacid, the Phosphorus heteropolyacid of molybdenum, phosphorus vanadium class heteropolyacid, molybdenum vanadium class heteropolyacid, tungsten silicon class heteropolyacid, and said multiple-metal oxygen-containing hydrochlorate is selected from phosphorus tungsten class heteropoly blue, the Phosphorus heteropoly blue of molybdenum, phosphorus vanadium class heteropoly blue, molybdenum vanadium class heteropoly blue, tungsten silicon class heteropoly blue.
5. according to the method for claim 3, wherein said isopoly-acid class is molybdenum, tungsten, tantalum, niobium class isopoly-acid.
6. according to the process of claim 1 wherein, the mass ratio of the acid of HTS and multiple-metal oxygen-containing or its salt is 0.01～150 in the said catalyst composition.
7. according to the method for claim 1, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 1～10: 0～200, and the mass ratio of cycloalkanes and catalyzer is 0.1～100: 1.
8. according to the process of claim 1 wherein, said temperature of reaction is 20～120 ℃, and reaction pressure is 0.1～2.5MPa.
9. according to the method for claim 1, it is characterized in that said cycloalkanes is hexanaphthene, pentamethylene or their substituent, wherein substituent is methylcyclopentane, normenthane, 1,2-dimethyl cyclohexane, 1,3-dimethyl cyclohexane, 1-methyl-4-tertiary butyl hexanaphthene.
10. according to the method for claim 1, it is characterized in that being 30～130 ℃ in temperature is under the condition of 0.2～1.5MPa with pressure, with cycloalkanes, hydrogen peroxide, solvent and catalyzer contact reacts, wherein, the mol ratio of cycloalkanes, hydrogen peroxide and solvent is 1: 0.5～20: 0～50, the mass ratio of cycloalkanes and catalyzer is 5～80: 1, the ratio 0.1～50 of the acid of HTS and multiple-metal oxygen-containing or its salt in the catalyzer.
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| CN111099572A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon |
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| CN103373915A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Method for preparing dicarboxylic acid through catalytic oxidization reaction |
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| CN111099572A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Carbon oxide-based material, method for oxidizing carbon-based material, and method for catalytically oxidizing cyclic hydrocarbon |
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