CN115301228B - Method for preparing adipic acid by oxidizing cyclohexane and method for preparing metal quasicrystal alloy catalyst - Google Patents
Method for preparing adipic acid by oxidizing cyclohexane and method for preparing metal quasicrystal alloy catalyst Download PDFInfo
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- CN115301228B CN115301228B CN202110500407.0A CN202110500407A CN115301228B CN 115301228 B CN115301228 B CN 115301228B CN 202110500407 A CN202110500407 A CN 202110500407A CN 115301228 B CN115301228 B CN 115301228B
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- adipic acid
- catalyst
- cyclohexane
- alloy
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000001361 adipic acid Substances 0.000 title claims abstract description 87
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 87
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 82
- 239000000956 alloy Substances 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000013079 quasicrystal Substances 0.000 title claims abstract description 43
- 230000001590 oxidative effect Effects 0.000 title abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 18
- 238000010791 quenching Methods 0.000 claims abstract description 18
- 230000000171 quenching effect Effects 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 238000002074 melt spinning Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical group 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 6
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000007306 turnover Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 34
- 239000011572 manganese Substances 0.000 abstract description 24
- 239000010936 titanium Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 3
- -1 alcohol ketone oil Chemical compound 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical compound C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- MGTZCLMLSSAXLD-UHFFFAOYSA-N 5-oxohexanoic acid Chemical compound CC(=O)CCCC(O)=O MGTZCLMLSSAXLD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000003819 Madia Nutrition 0.000 description 1
- 240000004516 Madia sativa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- RPYFZMPJOHSVLD-UHFFFAOYSA-N copper vanadium Chemical compound [V][V][Cu] RPYFZMPJOHSVLD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 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
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing adipic acid by oxidizing cyclohexane and a preparation method of a metal quasicrystal alloy catalyst, wherein the catalyst is prepared by the following steps: (1) Preparing a metal raw material mixture according to the atomic ratio in the molecular formula of the catalyst; (2) melting the raw material mixture to form an alloy; (3) And melting the alloy again, and then quenching the melted alloy to obtain the catalyst. According to the invention, one or two of titanium and zirconium and one or two of cobalt and manganese are mixed according to a proportion, and an alloy smelting and quenching melt-spinning method is adopted to prepare the metal quasicrystal alloy catalyst, so that the problems that the catalyst and a product are difficult to separate, the catalytic reaction flow is long, and the activity and selectivity of the catalyst are low are effectively solved.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a method for preparing adipic acid by oxidizing cyclohexane and a method for preparing a metal quasicrystal alloy catalyst.
Background
Adipic acid (ADIPIC ACID, abbreviated as AA) is an industrially important dicarboxylic acid. AA can undergo various reactions, such as esterification, amidation, salification and the like, and can undergo condensation reaction with polyfunctional compounds to generate high polymer materials, so that the AA has wide application.
The traditional production process of adipic acid is a cyclohexane two-step oxidation method, is the production method with the largest standard in the world, and is developed by the company madia in france in the 20 th century in the 30 th year. The first step of reaction is that cyclohexane is contacted with air to generate incomplete oxidation reaction under the condition of no catalysis, so that a mixture of cyclohexanone and cyclohexanol (namely alcohol ketone oil, also called KA oil) is generated, the conversion rate of the reaction is lower and is generally not more than 10%, the second step of reaction is that KA oil is oxidized with nitric acid under the action of a copper-vanadium catalyst under the condition of slight negative pressure to generate adipic acid, the yield of the adipic acid is about 94%, the main byproduct is C2-C5 dicarboxylic acid, and the adipic acid is effectively separated from the byproduct through a crystallization process. After that, dupont in the united states developed a process for producing adipic acid by using phenol as a raw material and basf in germany by using butadiene as a raw material, but the phenol resources were limited, the cost of the produced adipic acid was too high and no competitive advantage, the process for producing butadiene as a raw material was basically eliminated, and the industrialization has not been generally adopted at present due to factors such as long technological process, many steps, poor running stability, industrial undersaturation, and the like.
All the three methods have the problems of longer catalytic reaction flow, difficult separation of the catalyst and the product, low activity and selectivity of the catalyst, and the like.
In order to solve the problems of longer flow and poor economy of the two-step oxidation method, a process for preparing adipic acid by one-step oxidation of cyclohexane is also developed, and mainly comprises the following steps: the free radical catalysis method, japanese university of Guangxi Yasutaka Ishi in 2006 developed a solvent-free cyclohexane oxidation process, and uses fat-soluble N-hydroxyphthalimide (NHPI) with higher solubility in cyclohexane as a catalyst, the process simultaneously greatly reduces the dosage of the catalyst, succinic acid contained in separation byproducts can be used for preparing the catalyst NHPI for production, and the indirect recycling form greatly improves the production economy. According to a supported nano gold catalytic method, 2012, A.Alshammari and the like prepare a series of supported nano gold catalysts for preparing adipic acid by oxidizing cyclohexane with molecular oxygen, and researches show that when an initiator tert-butyl hydroperoxide exists, the nano gold catalyst shows good catalytic activity, and although the nano gold catalyst achieves a certain result in the research of preparing adipic acid by cyclohexane in one step, the problems of gold particle loss, aggregation and other inactivation existing at present still need to be solved. In 1997, P.Ratnasamy et al reported in patent that a solid catalyst using metal phthalocyanine and metalloporphyrin as matrix is applied to oxidation reaction of cyclohexane and air, so as to realize the preparation of adipic acid by one-step reaction in a liquid phase environment. She Yuan is equivalent to select metallophthalocyanine, mononuclear metalloporphyrin or mu-oxo-dinuclear metalloporphyrin compound with similar structure to biological enzyme as catalyst to prepare adipic acid from cyclohexane, but the catalyst of the method is difficult to synthesize and has longer reaction time, and related patent CN1535947A, CN1231449C, CN1247501C, CN105884598A discloses metalloporphyrin as catalyst to catalyze cyclohexane to be oxidized into adipic acid.
Still other processes for preparing adipic acid from cyclohexane, such as reported in patent CN102329222A, CN102329223a, using heteropolyacids as phase transfer catalysts, such as catalyst [ C 18H37N(CH3)3]5[IMo6O24 ]; patent CN1086803A、CN1071304C、CN1195657A、CN1430593A、CN13339021A、CN1444555A、CN1511132、CN100338005C、CN100422130C uses organic acid as solvent, and uses cobalt acetylacetonate, cobalt acetate, chromium acetate, iron acetylacetonate, manganese acetylacetonate and other catalytic cyclohexane to synthesize adipic acid by oxidation; however, the above methods have the problems of high price, complex preparation method, difficult separation, possibly caused residues of metal ions and ligands in the product and the like due to the adoption of the homogeneous catalyst.
Patent CN101204662A discloses a nano catalyst for cyclohexane liquid phase oxidation, which adopts a mesoporous pore full-silicon molecular sieve SBA-15 as a carrier, and one or more transition metal (cobalt, copper, manganese, silver, chromium and nickel) oxides as active components are loaded on the carrier, wherein the loading capacity is 1% -3.5%. Cyclohexane conversion was 21.1% and selectivity to polyacids (succinic, glutaric, adipic, etc.) was 45.4%. Low cyclohexane conversion rate, low adipic acid yield and the like.
Patent CN101239899a discloses a solid catalyst with RuO 2 supported on carbon nanotubes to catalyze cyclohexane to synthesize adipic acid; CN101337878a discloses that RuO 2 is not supported, and the multiwall carbon nanotube also has better catalytic performance; CN102001931a uses nitrogen doped carbon nanotubes as catalyst; CN102040504a reports the use of carbon nanotubes filled with magnetic nano-iron particles as catalysts; in the patent CN110538668A, a multi-wall carbon nano tube is subjected to oxidation treatment in a mixed acid solution of HNO 3 and H 2SO4 to obtain a catalyst with the content of peroxy groups not lower than 3 multiplied by 10 -5 mol/g; CN110538671a discloses that a carbon nanotube supported group VIII transition metal is used as a catalyst; the heterogeneous catalyst prepared by using the carbon nano tube as a carrier in the catalytic system has high activity and good adipic acid selectivity, but the carbon nano tube has poor strength, is easy to break in the reaction process, and is not beneficial to the separation of the subsequent catalyst and the product.
Patent CN102816054B discloses an active carbon supported nano gold catalyst; patent CN108855087a discloses a catalyst composite with porous Pd-Co 3O4-CeO2 (Pd: co: ce=5:30:65); patent CN109095493A discloses a method for preparing adipic acid by catalyzing cyclohexane oxidation with two-dimensional ultrathin CuO@SAPO-34 molecular sieve material. Patent CN110872224a discloses that the specific surface area and the overall catalytic performance of the catalyst are improved by using acid modified sepiolite to significantly change the surface structure. The catalyst system has the problems of high price, complex preparation and the like.
Patent CN101264446B discloses that more than two metals from Ti, zr, co, fe, ni, cu metals are mixed, and an alloy smelting method is adopted to prepare a metal alloy catalyst for oxidizing cyclohexane by oxygen to synthesize KA oil; patent CN104226317B discloses TiZrTM' RE metal alloy catalyst for oxidation of cyclohexane by oxygen to synthesize KA oil, but has problems of poor tolerance of catalyst to solvent, low cyclohexane conversion and low adipic acid selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, which aims to solve the problems of poor tolerance of the catalyst to solvents, low conversion rate of cyclohexane and low selectivity of adipic acid in the prior art.
The invention also aims to provide a method for preparing adipic acid by oxidizing cyclohexane.
In order to achieve the above purpose, the present invention provides a method for preparing a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the catalyst has a composition as shown in general formula (I), (II) or (III):
Tix1Zry1Mz1 (I)
wherein x1, y1 and z1 represent the atomic number, x1+y1=50-95, y1=5-20 and z1=5-50, and the conditions that x1+y1+z1=100 are satisfied, and M is transition metal Co and/or Mn;
Tix2My2 (II)
wherein x2 and y2 represent atomic numbers, x2=50-95, y2=5-50, and x2+ y2=100 is satisfied, and M is transition metal Co and/or Mn;
Zrx3My3 (III)
wherein x3 and y3 represent atomic numbers, x3=50-95, y3=5-50, and x 3+y3=100 is satisfied, and M is transition metal Co and/or Mn;
The catalyst is prepared by the following method:
(1) Preparing a metal raw material mixture according to the atomic ratio in the molecular formula of the catalyst;
(2) Melting the raw material mixture to prepare an alloy;
(3) And melting the alloy again, and then quenching the melted alloy to obtain the catalyst.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein a high-temperature electric arc is adopted to melt a raw material mixture in the step (2).
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the current range in the step (2) is 150-250A, preferably 200-240A, and the vacuum degree is 10 -3～10-1 Pa, preferably 10 -3～10-2 Pa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein in the step (2), a raw material mixture is subjected to overturn smelting for 2-4 times, and each smelting time is 2-5 min; preferably 3 to 4 minutes.
The preparation method of the metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, disclosed by the invention, further comprises a crushing step before the alloy is remelted, wherein the crushing particle size is 2.5-9 meshes, and the preferable crushing mode is mechanical crushing.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, which comprises the following specific steps: and (3) filling the alloy into a quartz tube, vacuumizing, then filling argon, adjusting current to melt the alloy, spraying the alloy liquid onto a rotating copper roller by using the argon, controlling the quenching belt-throwing speed, throwing into a metal alloy thin belt, crushing and screening to obtain the metal quasicrystal alloy catalyst.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the vacuum degree in the step (3) is 3X 10 -3～10-2 Pa, preferably 5X 10 -3～8×10-3 Pa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the argon pressure in the step (3) is 0.01-0.1 MPa, preferably 0.02-0.4 MPa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the quenching melt-spinning speed in the step (3) is 20-40 m/s.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x1 = 60-80; y1=10 to 15; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x2 = 60-80; y2=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x3 = 60-80; y3=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
In order to achieve the above purpose, the invention also provides a method for preparing adipic acid by oxidizing cyclohexane, which uses the catalyst, and specifically comprises the following steps:
Adding cyclohexane and a catalyst into a reaction kettle, continuously introducing oxygen to maintain constant pressure under the conditions of the reaction temperature of 120-150 ℃ and the pressure of 0.8-3.0 MPa and the reaction time of 5-12h, and stirring and reacting to obtain a reaction product mixture.
The reaction mixture is subjected to liquid phase and solid phase separation, separation of solid products and heterogeneous catalyst, the products comprising adipic acid, glutaric acid, succinic acid, KA oil and cyclohexyl hydroperoxide intermediate, and/or reaction by-products and unreacted cyclohexane.
The beneficial effects of the invention are as follows:
According to the invention, one or two of titanium and zirconium and one or two of cobalt and manganese are mixed according to a proportion, and an alloy smelting and quenching melt-spinning method is adopted to prepare the metal quasicrystal alloy catalyst, so that the problems that the catalyst and a product are difficult to separate, the catalytic reaction flow is long, and the activity and selectivity of the catalyst are low are effectively solved. The catalyst can be used for preparing adipic acid by cyclohexane one-step oxygen oxidation; the catalyst has good catalytic activity in common solvents such as ethanol, acetonitrile and the like, and has good tolerance to byproducts and water; the cyclohexane conversion rate and adipic acid selectivity of the recycled catalyst are basically unchanged, the catalyst deactivation rate is low, the activity is high, and the selectivity is good. The catalyst does not contain rare earth elements, so that the selectivity of adipic acid is improved, and the generation amount of byproducts is reduced; the quenching and melt-spinning process can rapidly cool the liquid metal mixture to form more quasi-crystal active phases, thereby improving the activity of the catalyst.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
A preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the catalyst has a composition shown in a general formula (I), (II) or (III):
Tix1Zry1Mz1 (I)
wherein x1, y1 and z1 represent the atomic number, x1+y1=50-95, y1=5-20 and z1=5-50, and the conditions that x1+y1+z1=100 are satisfied, and M is transition metal Co and/or Mn;
Tix2My2 (II)
wherein x2 and y2 represent atomic numbers, x2=50-95, y2=5-50, and x2+ y2=100 is satisfied, and M is transition metal Co and/or Mn;
Zrx3My3 (III)
wherein x3 and y3 represent atomic numbers, x3=50-95, y3=5-50, and x 3+y3=100 is satisfied, and M is transition metal Co and/or Mn;
The catalyst is prepared by the following method:
(1) Preparing a metal raw material mixture according to the atomic ratio in the molecular formula of the catalyst;
(2) Melting the raw material mixture to prepare an alloy;
(3) And melting the alloy again, and then quenching the melted alloy to obtain the catalyst.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein a high-temperature electric arc is adopted to melt a raw material mixture in the step (2).
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the current range in the step (2) is 150-250A, preferably 200-240A, and the vacuum degree is 10 -3～10-1 Pa, preferably 10 -3～10-2 Pa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein in the step (2), a raw material mixture is subjected to overturn smelting for 2-4 times, and each smelting time is 2-5 min; preferably 3 to 4 minutes.
The preparation method of the metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, disclosed by the invention, further comprises a crushing step before the alloy is remelted, wherein the crushing particle size is 2.5-9 meshes, and the preferable crushing mode is mechanical crushing.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, which comprises the following specific steps: and (3) filling the alloy into a quartz tube, vacuumizing, then filling argon, adjusting current to melt the alloy, spraying the alloy liquid onto a rotating copper roller by using the argon, controlling the quenching belt-throwing speed, throwing into a metal alloy thin belt, crushing and screening to obtain the metal quasicrystal alloy catalyst.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the vacuum degree in the step (3) is 3X 10 -3～10-2 Pa, preferably 5X 10 -3～8×10-3 Pa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the argon pressure in the step (3) is 0.01-0.1 MPa, preferably 0.02-0.4 MPa.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein the quenching melt-spinning speed in the step (3) is 20-40 m/s.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x1 = 60-80; y1=10 to 15; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x2 = 60-80; y2=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
The invention relates to a preparation method of a metal quasicrystal alloy catalyst for preparing adipic acid from cyclohexane, wherein x3 = 60-80; y3=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
The method for preparing adipic acid by oxidizing cyclohexane uses the catalyst, and specifically comprises the following steps:
Adding cyclohexane and a catalyst into a reaction kettle, continuously introducing oxygen to maintain constant pressure under the conditions of the reaction temperature of 120-150 ℃ and the pressure of 0.8-3.0 MPa and the reaction time of 5-12h, and stirring and reacting to obtain a reaction product mixture.
The reaction mixture is subjected to liquid phase and solid phase separation, separation of solid products and heterogeneous catalyst, the products comprising adipic acid, glutaric acid, succinic acid, KA oil and cyclohexyl hydroperoxide intermediate, and/or reaction by-products and unreacted cyclohexane.
Example 1
(1) Catalyst preparation
Firstly, preparing a metal raw material mixture according to an atomic ratio Ti 60Zr10Co30 of a metal quasicrystal alloy catalyst; weighing the powdery metal raw materials Ti, zr and Co, pressing into slices by using a powder tablet press, and cutting for use; and then placing the metal raw material mixture on a copper bed in a vacuum arc furnace, repeatedly vacuumizing to a vacuum degree of 5X 10 -3 Pa, and finally introducing argon gas to maintain negative pressure. Under the condition of argon pressure of 10 -2 Pa, adopting high-temperature electric arc to heat the raw materials into a molten state, wherein the smelting current range is 200A, extinguishing arc after 5 minutes of each smelting, and enabling circulating water under a copper bed to rapidly cool the raw materials to form the alloy ingot. The sample was subjected to 3 times of turnover smelting. Cooling and taking out; mechanically crushing the cooled alloy to obtain a 2.5-9 mesh alloy catalyst;
And loading the obtained alloy catalyst into a quartz tube, and then installing the quartz tube in a furnace chamber of a vacuum quenching and casting integrated machine. And (3) vacuumizing the furnace chamber by using a mechanical pump, vacuumizing to 5 multiplied by 10 -3 Pa by using a molecular pump after the vacuum degree is lower than 0.1Pa, and charging argon, wherein the pressure of the argon in the furnace chamber is kept to be 0.06MPa. The temperature of the smelting metal is changed by adjusting variable frequency current, so that the alloy is melted again in the quartz tube, the alloy is kept to be red and hot liquid in the quartz tube at high temperature, and the alloy liquid is sprayed from a small opening below the quartz tube to a copper roller rotating at high speed below the quartz tube by using argon gas higher than the pressure in the quartz tube, so that a metal alloy thin strip is formed by throwing. The rotation speed of the copper roller is regulated, and the quenching speed is controlled to be 30m/s. The thrown alloy thin belt is crushed by using a stainless steel mortar and manual impact, and the crushed alloy thin belt is screened to obtain the metal quasicrystal alloy catalyst with the particle size of 100-200 meshes.
(2) Cyclohexane catalytic oxidation reaction
The reaction is carried out in a 600mL stainless steel high-pressure reaction kettle, the mass ratio of the catalyst to cyclohexane is 1:1200, the volume ratio of the acetone solvent to cyclohexane is 0.67, the cyclohexane is 120mL, the high-pressure kettle is heated to 140 ℃ after feeding, oxygen is filled to the pressure of 2MPa, the oxygen is continuously filled in the reaction process to maintain the constant pressure, and the reaction is carried out under mechanical stirring for 5 hours.
(3) Reactant separation
After the reaction is finished, cooling in ice water bath, and carrying out liquid phase and solid phase centrifugal separation to obtain a liquid phase product A and a solid phase product B. The solid-phase product B comprises a dibasic acid product and a catalyst. The liquid phase product A comprises mainly unreacted cyclohexane, cyclohexanone, cyclohexanol and cyclohexyl peroxide.
(4) Catalyst separation
Adding hot water into the solid phase product to dissolve the generated dibasic acid solid, and obtaining a dibasic acid product water solution and a solid catalyst respectively through centrifugal separation and filtration. Compared with the traditional process, the metal quasicrystal alloy catalyst can realize one-step catalytic oxidation of cyclohexane to obtain adipic acid products, the reaction products can realize separation of the catalyst and the products only by simple separation and filtration, and no metal ion residues exist.
(5) Purification of adipic acid
Recrystallizing the dibasic acid aqueous solution obtained in the step (4) to obtain white adipic acid solid.
(6) Analysis of the products
The liquid phase product A separated in the above (3) was directly analyzed on GC-2010 gas chromatograph, with column Rtx-50, FID detector. And quantifying by an internal standard method, and calculating the conversion rate and the selectivity. Selectivity of product (%) = number of moles of certain product/total moles of product x 100%.
The aqueous dibasic acid solution separated in the above (4) was subjected to content analysis by using Shimadzu LC-20AB liquid chromatography, and the column temperature was 35℃in a detector RI detector (Shimadzu RID-10A), chromatographic column 5C 18 -PAQ. The selectivity of the product was calculated by the internal standard method. Selectivity of product (%) = number of moles of certain product/total moles of product x 100%.
(7) Cyclohexane conversion calculation
Analysis was performed on GC-2010 gas chromatograph with a column Rtx-50, FID detector. Quantification was performed using an internal standard method, total conversion (%) of cyclohexane=total moles of product/moles of cyclohexane charge x 100%.
The products obtained by the above analysis are mainly adipic acid, succinic acid, glutaric acid, KA oil, while other products detected are cyclohexyl peroxide, levulinic acid, 5-oxohexanoic acid, adipic acid hexanediol oxide, etc. Cyclohexane conversion was 42% and adipic acid selectivity was 67%.
(8) Catalyst reuse
The above recovered solid catalyst was repeated as steps (2), (3) and (4), the cyclohexane conversion was 41%, and the adipic acid selectivity was 69%.
Examples 2 to 3
The catalyst preparation method is the same as in example 1, except that the quenching melt-spinning method is adopted to prepare the metal quasicrystal alloy catalyst, and different melt-spinning speeds are adopted. The conditions for catalyzing the cyclohexane oxidation reaction are the same as in example 1, the implementation results are shown in Table 1, and the product analysis method is the same as in example 1.
TABLE 1 evaluation results of catalyst reactivity prepared at different melt-spinning speeds
| Catalyst | Melt-spun speed (m/s) | Conversion (%) | Adipic acid selectivity (%) |
| Example 2 | 20 | 40 | 66 |
| Example 3 | 40 | 43 | 67 |
Examples 4 to 8
The catalyst preparation method is the same as in example 1, catalysts with different composition ratios are prepared, the conditions for catalyzing the cyclohexane oxidation reaction are the same as in example 1, the implementation results are shown in Table 2, and the product analysis method is the same as in example 1
TABLE 2 evaluation results of catalyst reactivity at different composition ratios
| Catalyst composition | Conversion (%) | Adipic acid selectivity (%) | |
| Example 4 | Ti60Zr10Mn30 | 39 | 68 |
| Example 5 | Ti60Zr10Mn15Co15 | 44 | 62 |
| Example 6 | Ti70Zr10Co20 | 40 | 65 |
| Example 7 | Ti70Co30 | 36 | 69 |
| Example 8 | Zr80Co20 | 34 | 71 |
| Example 9 | Ti60Mn40 | 35 | 68 |
| Example 10 | Zr60Mn40 | 37 | 67 |
Examples 11 to 13
The direct catalytic oxidation of cyclohexane to make dibasic acid can be carried out in different solvents, examples 11-13 are reactions carried out in different solvents, the composition and preparation method of the catalyst used are the same as those of example 1, the catalytic reaction results are shown in Table 3, and the product analysis method is the same as that of example 1.
TABLE 3 influence of different solvents on the catalyst reactivity
| Solvent(s) | Conversion (%) | Adipic acid selectivity (%) | |
| Example 11 | Acetone (acetone) | 42 | 67 |
| Example 12 | Ethanol | 28 | 54 |
| Example 13 | Acetonitrile | 43 | 62 |
Examples 14 to 17
The preparation method and the composition ratio of the catalyst are the same as those of example 1, the conditions and the reaction results of the cyclohexane oxidation reaction are shown in Table 4, and the analysis method of the product is the same as that of example 1
TABLE 4 influence of different reaction conditions on the reactivity of the catalysts
Comparative example 1
Preparing a metal raw material mixture according to the atomic ratio Ti 60Zr10Co30 of the metal quasicrystal alloy catalyst; weighing the powdery metal raw materials Ti, zr and Co, pressing into slices by using a powder tablet press, and cutting for use; and then placing the metal raw material mixture on a copper bed in a vacuum arc furnace, repeatedly vacuumizing to a vacuum degree of 3X 10 -3～10-2 Pa, and finally introducing argon gas to maintain negative pressure. Under the condition of argon pressure of 10 -2 Pa, adopting high-temperature electric arc to heat the raw materials into a molten state, wherein the smelting current range is 200A, extinguishing arc after 5 minutes of each smelting, and enabling circulating water under a copper bed to rapidly cool the raw materials to form the alloy ingot. Carrying out 3 times of turnover smelting on the sample, cooling and taking out; mechanically crushing the cooled alloy to obtain the alloy catalyst Ti 60Zr10Co30 with the size of 2.5-9 meshes.
Conditions for catalyzing cyclohexane oxidation reaction and a method for analyzing a product are the same as in example 1. The cyclohexane conversion was 19% and the adipic acid selectivity was 47%.
Comparative example 2
The catalyst composition and preparation method were the same as in example 45 of CN201310239182.3, cyclohexane oxidation conditions and product analysis method were the same as in example 1, cyclohexane conversion was 38% and adipic acid selectivity was 62% in the presence of acetonitrile solvent.
Comparative example 3
The reaction process is free from adding catalyst, and the cyclohexane oxidation reaction conditions and the product analysis method are the same as in example 1. The cyclohexane conversion was 6% and the adipic acid selectivity was 14%.
The results of activity and selectivity investigation of the catalysts prepared in the examples are shown in tables 1-4, and it can be seen from the tables that the metal quasicrystal alloy catalyst prepared by alloy smelting and quenching and melt-spinning has basically no change in cyclohexane conversion rate and adipic acid selectivity, low catalyst deactivation rate, high activity and good selectivity under the conditions that the mass ratio of the catalyst to the reactant cyclohexane is 1:1200-1:2000, the reaction temperature is 120-150 ℃, the pressure is 0.8-3.0 MPa, the volume ratio of acetone to cyclohexane is 0.3-1.5 and the reaction time is 5 hours on a 600ml kettle type evaluation device. The reaction results of the catalyst prepared in the example in different solvents for catalyzing and oxidizing cyclohexane are shown in table 3, and it can be seen from the table that the catalyst has better catalytic activity in common solvents such as acetone, ethanol, acetonitrile and the like, and has good tolerance to byproducts and water. Under the same experimental conditions, the catalysts prepared in comparative examples 1-3 were inferior in activity and selectivity, wherein comparative examples 1-2 did not remelt and quench the alloy catalyst to form more quasicrystal phases, resulting in poor catalytic activity of the catalyst.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (15)
1. The method for preparing adipic acid by one-step oxidation of cyclohexane is characterized by comprising the following steps of:
Adding cyclohexane, a metal quasicrystal alloy catalyst and a solvent into a reaction kettle, continuously introducing oxygen to maintain constant pressure under the conditions of the reaction temperature of 120-150 ℃ and the pressure of 0.8-3.0 MPa and the reaction time of 5-12h, and stirring and reacting to obtain a reaction product mixture, wherein the solvent is acetone or acetonitrile;
The catalyst has a composition shown in a general formula (I), (II) or (III):
Tix1Zry1Mz1 （I）
wherein x1, y1 and z1 represent the atomic number, x1+y1=50 to 95, y1=5 to 20, z1=5 to 50, and x 1+y1+z1=100 is satisfied, and M is transition metal Co and/or Mn;
Tix2My2 （II）
Wherein x2 and y2 represent atomic numbers, x2=50-95, y2=5-50, and x2+ y2=100 is satisfied, and m is transition metal Co and/or Mn;
Zrx3My3 （III）
wherein x3 and y3 represent atomic numbers, x3=50-95, y3=5-50, and x 3+y3=100 is satisfied, and M is transition metal Co and/or Mn;
The catalyst is prepared by the following method:
(1) Preparing a metal raw material mixture according to the atomic ratio in the molecular formula of the catalyst;
(2) Melting the raw material mixture to prepare an alloy;
(3) Melting the alloy again, and then quenching the melted alloy to obtain a catalyst;
The specific steps of the step (3) are as follows: and (3) filling the alloy into a quartz tube, vacuumizing, then filling argon, adjusting current to melt the alloy, spraying the alloy liquid onto a rotating copper roller by using the argon, controlling the quenching belt-throwing speed, throwing into a metal alloy thin belt, crushing and screening to obtain the metal quasicrystal alloy catalyst.
2. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein the raw material mixture is melted by high-temperature arc in step (2).
3. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 2, wherein the current in the step (2) ranges from 150 to 250A, and the vacuum degree is 10 -3~10-1 Pa.
4. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 3, wherein the current in the step (2) ranges from 200 to 240A, and the vacuum degree is 10 -3~10-2 Pa.
5. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 3, wherein the raw material mixture is subjected to 2-4 times of turnover smelting in the step (2), each time of smelting for 2-5 minutes.
6. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 5, wherein each smelting step in the step (2) is performed for 3-4 min.
7. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, further comprising a crushing step, wherein the crushed particles have a size of 2.5 to 9 mesh, before remelting the alloy in step (3).
8. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein the vacuum degree in the step (3) is 3 x 10 -3 ~10-2 Pa.
9. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein the vacuum degree in the step (3) is 5 x 10 -3~8×10-3 Pa.
10. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 6, wherein the argon pressure in the step (3) is 0.01-0.1 MPa.
11. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 6, wherein the argon pressure in the step (3) is 0.02-0.1 MPa.
12. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein the quenching and melt-spinning speed in the step (3) is 20-40 m/s.
13. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein x1=60 to 80; y1=10 to 15; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
14. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein x2=60 to 80; y2=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
15. The method for preparing adipic acid by one-step oxidation of cyclohexane according to claim 1, wherein x3=60 to 80; y3=20 to 40; m is Co and Mn, and the atomic number ratio of Co to Mn is 2-5:1.
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