CN115304452A - Method for inhibiting byproduct cyclododecane methanol in cyclododecanol hydrogenation preparation process - Google Patents
Method for inhibiting byproduct cyclododecane methanol in cyclododecanol hydrogenation preparation process Download PDFInfo
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- CN115304452A CN115304452A CN202210905531.XA CN202210905531A CN115304452A CN 115304452 A CN115304452 A CN 115304452A CN 202210905531 A CN202210905531 A CN 202210905531A CN 115304452 A CN115304452 A CN 115304452A
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- Prior art keywords
- cyclododecane
- metal
- catalyst
- methanol
- product
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000006227 byproduct Substances 0.000 title claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- JQYWAZNRRQRPNN-UHFFFAOYSA-N cyclododecylmethanol Chemical compound OCC1CCCCCCCCCCC1 JQYWAZNRRQRPNN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 7
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 claims abstract description 34
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VLJLXEKIAALSJE-UHFFFAOYSA-N 13-oxabicyclo[10.1.0]tridecane Chemical compound C1CCCCCCCCCC2OC21 VLJLXEKIAALSJE-UHFFFAOYSA-N 0.000 claims abstract description 13
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- UGUXLOGSIIMVAC-UHFFFAOYSA-N 13-oxabicyclo[10.1.0]trideca-1(12),10-diene Chemical compound C1=CCCCCCCCCC2=C1O2 UGUXLOGSIIMVAC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 229910044991 metal oxide Inorganic materials 0.000 claims description 33
- 150000004706 metal oxides Chemical group 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- -1 lanthanide metal oxide Chemical class 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 4
- 229960001545 hydrotalcite Drugs 0.000 claims description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 150000002602 lanthanoids Chemical group 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 26
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 238000009835 boiling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GMUVJAZTJOCSND-OWOJBTEDSA-N cycloundecene Chemical compound C1CCCC\C=C\CCCC1 GMUVJAZTJOCSND-OWOJBTEDSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000003826 tablet Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- KYTNZWVKKKJXFS-UHFFFAOYSA-N cycloundecane Chemical compound C1CCCCCCCCCC1 KYTNZWVKKKJXFS-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- RZUNIXAGSKNOIB-HSFFGMMNSA-N (1z,3e)-cyclododeca-1,3-diene Chemical compound C1CCCC\C=C/C=C/CCC1 RZUNIXAGSKNOIB-HSFFGMMNSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XLHSVMYMLCFUFU-UHFFFAOYSA-N [1-(hydroxymethyl)cyclododecyl]methanol Chemical compound OCC1(CO)CCCCCCCCCCC1 XLHSVMYMLCFUFU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/83—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 rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Abstract
The invention provides a method for inhibiting cyclododecane methanol as a byproduct in a cyclododecane alcohol hydrogenation preparation process, which comprises the steps of adding one or more components of cyclododecanone, epoxy cyclododecadiene, epoxy cyclododecene and epoxy cyclododecane and a catalyst into a reactor for reaction, and converting the components into cyclododecane alcohol at a certain reaction temperature and pressure. The catalyst of the invention is suitable for one or more of cyclododecanone, epoxy cyclododecadiene, epoxy cyclododecene and epoxy cyclododecane, and the product can be suitable for high-purity downstream products, and the purity of the rectification separation product is more than 99.95%.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and new material preparation, and particularly relates to a method for inhibiting cyclododecane methanol as a byproduct in a cyclododecane alcohol hydrogenation preparation process.
Background
The cyclododecanol synthesis method is a key process for preparing essence, perfume, high-grade lubricating oil and long-carbon polyamide, the cyclododecanol is produced by an air oxidation method at present, ketone/alcohol and a large amount of naphthenic hydroperoxide are produced in a reaction system, and the naphthenic hydroperoxide can be catalyzed and decomposed into ketone/alcohol mixture by molybdenum series, chromium series and vanadium series metal salt or complex; another production process employs an olefin oxidation scheme that employs a common oxidant comprising t-butyl hydroperoxide, cumene hydroperoxide, cyclohexyl hydroperoxide to form an oxa-ternary cyclic product, which is hydrogenated over different types of catalysts to form a ketone/alcohol mixture or a single product.
The second industrial route of cyclododecanol is to prepare epoxycyclododecane by reacting cyclododecene with an oxidant, followed by a hydrogenation process. The patent of US 4469860 reports that the conversion rate of raw materials and the selectivity of products are both lower than 85 percent by using metal borate as a catalyst and oxygen as an oxygen source to perform the epoxidation reaction process of cyclododecane; JP2004002234 uses vanadium carrier to catalyze cyclododecene epoxidation reaction, and the selectivity is more than 90%, but the conversion rate of raw material is low. In EP1411050, a 20% excess of hydrogen peroxide is reacted with cyclododecene to form epoxycyclododecane. CN10465007 based on the reaction of tert-butyl hydroperoxide with cyclododecene to prepare epoxycyclododecane, although it is possible to prepare epoxycyclododecane with high selectivity and high conversion, there is still a high risk of using organic peroxide.
The hydrogenation process is followed byAnd the service integration company Degussa and winning and creating deep research on hydrogenation technology, and the novel hydrogenation process gradually replaces the air oxidation process. In 2015, duPont (Invidant) quits the business of twelve-carbon chemicals, and indirectly proves that the market competitiveness of the air oxidation process is insufficient, in recent years, a new hydrogenation process gradually becomes a mainstream process of cyclododecanol industry, the new process is more green and low-carbon compared with the traditional process, and the development of a novel process meets the large environment of the domestic double-carbon policy.
However, researchers find that tail gas containing CO and related byproducts are generated in the reaction process, the byproducts can be judged to be undecane and corresponding carbonylation hydrogenation products, namely, cyclododecane methanol through analysis, the boiling points of n-undecane and cyclododecanol are respectively 196.3 ℃ and 272.7 ℃ under normal pressure, the physical difference is large, the separation is easy, and the separation influence of the cracking byproducts on the products is small. Although the boiling point of the cyclododecanol methanol is 298.7 ℃ under normal pressure, the cyclododecanol has a very close boiling point to a product in a high vacuum rectification process, the qualification rate of a finished cyclododecanol product is low, more seriously, a byproduct influences that the laurolactam cannot meet the requirement of a polymerization grade, a PA12 polymerization product is yellowish, and the difference of mechanical properties of the product prepared from the high-purity raw material is large.
CN1541762A describes that in the catalytic reaction of carbonyl-containing compounds, carbon monoxide is often generated due to the side reaction of decarboxylation, and if a catalyst is used in the reaction, the generated carbon monoxide is strongly adsorbed on the surface of the active metal to cause poisoning of the catalyst, thereby reducing the activity of the catalyst; simultaneously, the catalyst and cyclododecene which is a dehydration byproduct generate cyclododecanedimethanol. The raw material of the invention is cyclododecanone or epoxy product with single structure or multiple components, the hydrogenation reaction mechanism is C-O bond and active metal adsorption, and the generation of cyclododecane methanol is solved from the source through inhibiting cracking and catalyst carbonylation performance. The patent CN112166098 describes cyclododecanone preparation reaction to form cycloundecane and cycloundecene, which can form 1mol% to 2mol% of cycloundecene and undecene during the reaction, corresponding to the formation of equimolar amount of carbon monoxide. Depending on the amount of gas metered into the apparatus, the carbon monoxide ratio can thus be up to a few percent of the gas phase composition, in the example the nitrogen flow is 2NL/h, the feed is 65g/h, the CO content in the offgas reaches 6.8mol% and the high-boiling by-product (cyclododecylcarbinol) can reach 17mol%.
Disclosure of Invention
In view of the above, the present invention is directed to a method for suppressing cyclododecyl methanol as a byproduct in a cyclododecyl alcohol hydrogenation preparation process, so as to reduce the generation of cyclododecyl methanol.
So as to solve the disadvantages of the hydrogenation process, in particular the side reactions in the following 5 aspects. (1) cyclododecanol is catalytically hydrogenated to generate cyclododecane; (2) dehydrating target product cyclododecanol to generate cyclododecene; (3) Eleven-carbon derivatives from cracking of the feedstock with concomitant production of carbon monoxide; (4) The carbon monoxide generated by cracking and the raw material generate cyclododecane methanol and the like; (5) The carrier acidity causes polymerization of the starting material, mainly derivatives of tetracosan. Aiming at 5 types of side reactions, the side reactions (2), (3) and (5) are related to the property of the carrier; the reactivity of the side reactions (1) and (4) is related to the activity of the metal.
In order to reduce 5 different types of side reactions, in particular the side reaction (3) cracking reaction with the formation of carbon monoxide, it is known in the art that carbon monoxide poisons metal catalysts, the activity of hydrogenation catalysts is limited by the interference of carbon monoxide, and the production instability is caused by the gradual reduction of the catalytic activity with an unacceptable consequence. In order to realize stable production of high-purity cyclododecanol and maintain high selectivity level in industry, the generation of cyclododecane methanol byproduct is solved from the source.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a process for suppressing the by-product cyclododecanol in the hydrogenating process of cyclododecanol includes such steps as adding one or more of cyclododecanone, cyclododecadiene epoxy, cyclododecene epoxy and cyclododecane epoxy, and reaction at particular temp and pressure to obtain cyclododecanol.
The raw material of the invention is cyclododecanone or epoxy with single structure or multi-component product, the hydrogenation reaction mechanism is C-O bond and active metal adsorption, hydrogen is also adsorbed at the center of the active metal, and the subsequent reaction of the hydrogen and the raw material containing C-O single bond or double bond is realized, and the invention can realize hydrogenation of various raw materials due to the consistency of the mechanism. During the course of the examination of the continuous conversion of the starting material, by-products may be formed. Some of these by-products have such a high boiling point that they cannot be detected by means of gas chromatography. In order to take into account all possible impurities when calculating the selectivity, the reaction mixture was analyzed by means of Gas Chromatography (GC) with the addition of a known amount of n-dodecane as external standard. For all known substances present in reactions such as epoxycyclododecane (tetradecane, cycloundecane, cycloundecene, cyclododecane, cyclododecene, cyclododecanone, cyclododecanol, epoxycyclododecane), the GC factor can be determined with a predetermined reference solution. Thus, by adding a known amount of n-decane to each reaction sample, the mass-based proportion of each substance in each reaction mixture can be calculated. From the GC chromatogram, the proportion of all substances visible in the chromatogram can be calculated. By the difference between 100% and the sum of all materials in the GC chromatogram, the proportion of high boiling by-products not detected in the GC can be calculated, ensuring accurate reaction data results.
The reactor can be a fixed bed, a fluidized bed, a slurry bed or a circulating tube reactor; preferably, the reactor is a slurry bed reactor. The fixed bed process is filled with 1-5mm pills, clover, annular and other shaped catalysts, and the fluidized bed, slurry bed and circulating tube reactor are filled with 20-300 mesh powder catalysts. The one-time filling amount of the fixed bed, the circulating pipe and the fluidized bed reactor is larger than that of a slurry bed, and the slurry bed reactor is mostly adopted in industrial implementation from the viewpoint of production economic benefit, and the using amount of the catalyst is 0.3-10% of the weight of a single batch of materials.
Converting into products under specific temperature and pressure, wherein the reaction temperature is 200-280 ℃; preferably, the reaction temperature is 200 to 260 ℃. The reaction pressure is 0.1-15MPaG; preferably, the reaction pressure is 2.0 to 4.0MPaG. Surprisingly, it has been found that during the conversion of the feedstock to the product, no by-products of eleven and thirteen carbons are significantly detected, and no CO is significantly detected in the off-gas after the hydrogenation reaction, thereby ensuring that the present technology is effective in suppressing cyclododecane methanol.
The preparation method of the catalyst adopts a low-content supported metal catalyst, the carrier is a metal oxide or two mixed metal oxide carriers, the carrier modification auxiliary agent is IA alkali metal and IIA alkaline earth metal, and the metal dispersion auxiliary agent is lanthanide metal oxide.
The metal of the catalyst system is preferably selected from nickel, ruthenium, rhodium, palladium, iridium and platinum, of which nickel, ruthenium, palladium and platinum are preferred and nickel is particularly preferred. The metal may be present as a powder (unsupported) or supported. Suitable powder forms are, for example, elemental metals or their oxides.
In addition, at least one metal oxide may be included as a further component of the catalyst system. The metal oxide of the catalyst system carrier comprises aluminum oxide, silicon dioxide, mg-Al hydrotalcite, titanium dioxide and zirconium dioxide; preferably, the support is silica and titania, or consists of at least one of the oxides mentioned above. For example, the metal oxide of the catalyst system may comprise a mixed oxide, wherein the mixed oxide comprises silica and titania; the mixed oxide is formed by kneading 5-15% of silica sol or aluminum sol, and is formed by columnar grain cutting or ball rolling.
The metal oxides of the catalyst system and also the substitute support can be present as powder or as shaped bodies. Suitable shaped bodies are beads, extrudates, tablets, granules and granules. Preferably, the metal support is present as a shaped body. It is also preferred that the metal oxide of the catalyst system, if it does not act as a support, is present as shaped body.
Suitable titanium dioxides as metal oxides for the catalyst system can be obtained by the sulfate process, the chloride process or by the flame hydrolysis (pyrogenic) process of titanium tetrachloride. All methods of alumina, silica, mg-Al hydrotalcite, zirconia are known to the person skilled in the art. The metal oxide of the catalyst system may have a concentration of 0.5 to 1.5g/cm 3 The bulk density test is a well known method in the art. The BET surface area of the metal oxide of the catalyst system according to the invention is from 80 to 250m 2 (ii) in terms of/g. The BET surface area is measured in accordance with DIN 66131 and DIN ISO 9277. Greater than 300m 2 The BET surface area/g leads to a lower selectivity. The carrier modification auxiliary agent is IA alkali metal and IIA alkaline earth metal; preferably, the metals are sodium and potassium.
The catalyst preparation method adopts a low-content supported metal catalyst. The weight ratio of the metal to the oxide carrier is 0.05-1.5%; preferably, the metal content is 0.3% to 0.6%. The metal dispersing aid is a lanthanide metal oxide, preferably, the metal oxide is cerium oxide. Each impregnation method known to the person skilled in the art can be used, such as applying a metal solution to the support. The method generally adopts a roasting method to realize the firm combination of various metal oxides, the roasting temperature range is 350-550 ℃, and the gas atmosphere is air.
Compared with the prior art, the method for inhibiting the byproduct cyclododecane methanol in the cyclododecane alcohol hydrogenation preparation process has the following beneficial effects:
(1) The alkali metal and alkaline earth metal modified carrier inhibits the cracking of the raw material, and avoids the generation of eleven-carbon byproducts; the other cracking by-product has a lower carbon monoxide content, thus essentially solving the generation of cyclododecane methanol.
(2) The carrier modified by alkali metal and alkaline earth metal inhibits the generation of polymerization products under the acidic condition of raw materials, avoids blocking catalyst pore channels, prolongs the service life of the catalyst, and reduces the by-products with high boiling point to 0.01-0.1%.
(3) The activity of the metal catalyst with dispersed lanthanide metal is high, and the adverse phenomenon that carbon monoxide poisons the catalyst does not appear in the reaction system.
(4) The catalyst of the present invention is suitable for one or more of cyclododecanone, epoxy cyclododecadiene, epoxy cyclododecene and epoxy cyclododecane, and the product may be used in high purity downstream product with purity over 99.95% as the separation product. The selectivity of the byproduct cyclododecane methanol of the catalytic hydrogenation process can be reduced to 0.01-0.05%. The cyclododecanol prepared by the method can be used in the fields of nylon 12, nylon 612, nylon 1212, nylon 12T, nylon elastomer, macrocyclic spice and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to examples.
A process for suppressing the cyclododecyl methanol as by-product in the hydrogenating process of cyclododecanol includes such steps as adding one or more of cyclododecanone, epoxy cyclododecadiene, epoxy cyclododecene and epoxy cyclododecane to reactor, and reaction under specific temp and pressure to obtain cyclododecanol.
The raw material of the invention is cyclododecanone or epoxy with single structure or multicomponent product, the hydrogenation reaction mechanism is C-O bond and active metal adsorption, hydrogen is also adsorbed at the center of the active metal, and the subsequent reaction of the hydrogen and the raw material containing C-O single bond or double bond is realized, therefore, the invention can realize hydrogenation of various raw materials due to the consistency of the mechanism. During the course of the examination of the continuous conversion of the starting material, by-products may be formed. Some of these by-products have such a high boiling point that they cannot be detected by means of gas chromatography. In order to take into account all possible impurities when calculating the selectivity, the reaction mixture was analyzed by means of Gas Chromatography (GC) with the addition of a known amount of n-dodecane as external standard. For all known substances present in reactions such as epoxycyclododecane (tetradecane, cycloundecane, cycloundecene, cyclododecane, cyclododecene, cyclododecanone, cyclododecanol, epoxycyclododecane), the GC factor can be determined with a predetermined reference solution. Thus, by adding a known amount of n-decane to each reaction sample, the mass-based proportion of each substance in each reaction mixture can be calculated. From the GC chromatogram, the proportion of all substances visible in the chromatogram can be calculated. By the difference between 100% and the sum of all substances in the GC chromatogram, the proportion of high boiling by-products not detected in the GC can be calculated, ensuring accurate reaction data results.
The reactor can be a fixed bed, a fluidized bed, a slurry bed or a circulating tube reactor; preferably, the reactor is a slurry bed reactor. The fixed bed process is filled with 1-5mm pills, clover, annular and other shaped catalysts, and the fluidized bed, slurry bed and circulating tube reactor are filled with 20-300 mesh powder catalysts. The one-time filling amount of the fixed bed, the circulating pipe and the fluidized bed reactor is larger than that of a slurry bed, and the slurry bed reactor is mostly adopted in industrial implementation from the production economic benefit, and the using amount of the catalyst is 0.3-10% of the weight of a single batch of materials.
Converting into products under specific temperature and pressure, wherein the reaction temperature is 200-280 ℃; preferably, the reaction temperature is 200-260 ℃. The reaction pressure is 0.1-15MPaG; preferably, the reaction pressure is 2.0 to 4.0MPaG. Surprisingly, it has been found that during the conversion of the feedstock to the product, no by-products of eleven and thirteen carbons are significantly detected, and no CO is significantly detected in the off-gas after the hydrogenation reaction, thereby ensuring that the present technology is effective in suppressing cyclododecane methanol.
The preparation method of the catalyst adopts a low-content supported metal catalyst, the carrier is a metal oxide or two mixed metal oxide carriers, the carrier modification auxiliary agent is IA alkali metal and IIA alkaline earth metal, and the metal dispersion auxiliary agent is lanthanide metal oxide.
The metal of the catalyst system is preferably selected from nickel, ruthenium, rhodium, palladium, iridium and platinum, of which nickel, ruthenium, palladium and platinum are preferred and nickel is particularly preferred. The metal may be present as a powder (unsupported) or supported. Suitable powder forms are, for example, elemental metals or oxides thereof.
Furthermore, at least one metal oxide may be included as a further component of the catalyst system. The metal oxide of the catalyst system carrier comprises aluminum oxide, silicon dioxide, mg-Al hydrotalcite, titanium dioxide and zirconium dioxide; preferably, the support is silica and titania, or consists of at least one of the oxides mentioned above. For example, the metal oxide of the catalyst system may comprise a mixed oxide, wherein the mixed oxide comprises silica and titania; the mixed oxide is kneaded and formed by 5-15% of silica sol or aluminum sol, and is formed by columnar grain cutting or ball rolling.
The metal oxides of the catalyst system and also the substitute support can be present as powder or as shaped bodies. Suitable shaped bodies are beads, extrudates, tablets, granules and granules. Preferably, the metallic support is present as a shaped body. It is also preferred that the metal oxide of the catalyst system, if it does not act as a support, is present as a shaped body.
Suitable titanium dioxides as metal oxides for the catalyst system can be obtained by the sulfate process, the chloride process or by the flame hydrolysis (pyrogenic) process of titanium tetrachloride. All processes of alumina, silica, mg-Al hydrotalcites, zirconium dioxide are known to the person skilled in the art. The metal oxide of the catalyst system may have a concentration of 0.5 to 1.5g/cm 3 The average bulk density of (a), the bulk density test, is a method well known in the art. The BET surface area of the metal oxide of the catalyst system according to the invention is from 80 to 250m 2 (iv) g. The BET surface area is measured in accordance with DIN 66131 and DIN ISO 9277. Greater than 300m 2 The BET surface area/g leads to a lower selectivity. The carrier modification auxiliary agent is IA alkali metal and IIA alkaline earth metal; preferably, the metals are sodium and potassium.
The catalyst preparation method adopts a low-content supported metal catalyst. The weight ratio of the metal to the oxide carrier is 0.05-1.5%; preferably, the metal content is 0.3% to 0.6%. The metal dispersing aid is a lanthanide metal oxide, preferably, the metal oxide is cerium oxide. Each impregnation method known to the person skilled in the art can be used, such as applying the metal solution to the support. The method generally adopts a roasting method to realize the firm combination of various metal oxides, the roasting temperature range is 350-550 ℃, and the gas atmosphere is air.
Example 1
Preparation of the catalyst:
200g of a silica carrier having a BET parameter of 125m were introduced into a jacket-heated glass drum 2 (ii) in terms of/g. 100g of an aqueous solution containing 10% Na was added thereto, and the mixture was slowly dropped and uniformly dispersed on the surface of the carrier at a jacket temperature of 110 ℃. The prepared carrier is dried for 2 hours at 125 ℃ in the atmosphere of air. The carrier has a code number of 5% Na&SiO 2 。
100g of aqueous solution with the contents of Ce (cerium nitrate) and Ru (ruthenium nitrate) of 2 percent and 2 percent respectively is slowly dripped and uniformly dispersed on the surface of the carrier, and the temperature of a jacket is 110 ℃. The prepared carrier is dried for 2h at 125 ℃, roasted for 4h at 350 ℃ and roasted for 4h at 550 ℃, and the gas atmosphere is air. Preparation of the catalyst into 1% Ru1% Ce-5% Na&SiO 2
Catalyst examples were prepared in the same manner as described above as follows.
Example 9
In a 500mL high-pressure hydrogenation reactor, adding cyclododecanone 112g, adding catalyst 1%&SiO 2 3.5g (catalyst prepared in example 1), the reaction temperature was raised to 200 ℃, hydrogen was charged to maintain the pressure at 15MPaG, the rotation speed of the stirrer was 600 rpm, the reaction was carried out for 4 hours at this temperature and pressure, the conversion of the reaction raw material was 99.3% by sampling analysis after the reaction was completed, and the content of unreacted cyclododecanone was 0.7%. The selectivity to cyclododecanol was 96.9%.
The same process examples as above are as follows.
Example 17
In a tubular reactor having an internal diameter of 10mm, 1% by addition of Ru1% by weight of Ce-5% by weight&SiO 2 (catalyst is pressed into tablets and is crushed, and then the formed catalyst with the grain diameter of 0.5-1 mm is screened) 10mL, the temperature of a catalyst bed layer is raised to 220 ℃, the hydrogen flow is introduced into the catalyst bed layer with the flow rate of 100sccm, the pressure is maintained at 4MPaG, and the catalyst is reduced for 12 hours under the constant condition.
The hydrogen flow under the reaction condition is 50sccm, 500g of cyclododecanone is continuously fed into the catalyst bed layer from the top end of the catalyst by using a high-pressure circulating pump, and the circulating of liquid materials from top to bottom is realized by the circulating pump after the materials at the bottom end of the catalyst bed layer are collected. The reaction bed layer is controlled at 235 ℃, and after continuous reaction for 8 hours, the conversion rate of the reaction raw material is 99.7 percent, and the content of the unreacted cyclododecanone is 0.3 percent. Cyclododecanol was chosen to be 0.01% and cyclododecanol was chosen to be 98.9%. The purity of the product after rectification and separation is 99.98 percent.
Comparative example 1
Adding 1% of Ru/SiO 2 (catalyst self-made, catalyst tablet forming, crushing and screening out the catalyst with the particle size of 0.5-1 mm), and the other conditions are the same as those in example 17.
The conversion rate of the reaction raw material is 99.9%, and the content of unreacted cyclododecanone is 0.1%. Cyclododecane methanol was chosen to be 8.3%, n-undecane selectivity to be 9.5%, cyclododecane selectivity to be 12.1%, cyclododecanol selectivity to be 68.1%. The purity of the product after rectification and separation is 98.5 percent.
Claims (10)
1. A method for inhibiting cyclododecane methanol as a byproduct in a cyclododecane alcohol hydrogenation preparation process is characterized by comprising the following steps: adding one or more components of cyclododecanone, epoxy cyclododecadiene, epoxy cyclododecene and epoxy cyclododecane and a catalyst into a reactor for reaction, and converting into cyclododecanol under certain reaction temperature and pressure.
2. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 1, wherein: the reaction temperature is 200-280 ℃; preferably, the reaction temperature is 220-260 ℃;
the reaction pressure is 0.5-15MPaG; preferably, the reaction pressure is 2.0 to 4.0MPaG.
3. The method for suppressing cyclododecanemethanol produced as a by-product in a process for the hydrogenation production of cyclododecanol according to claim 1, wherein: the reactor comprises one of a fixed bed, a fluidized bed, a slurry bed and a circulating tube reactor, and preferably, the reactor is a slurry bed reactor.
4. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 1, wherein: the catalyst adopts a low-content supported metal catalyst, the carrier of the catalyst is a metal oxide or two mixed metal oxide carriers, and the carrier modification auxiliary agent is IA alkali metal and IIA alkaline earth metal; the metal dispersing auxiliary is lanthanide series metal oxide.
5. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 1, wherein: the metal of the low-content supported metal catalyst is nickel, ruthenium, rhodium, palladium, iridium and platinum; preferably, the metal is nickel;
the metal of the low content supported metal catalyst is 0.05-1.5% of the weight of the metal oxide carrier; preferably, the metal is 0.3% to 0.6% by weight of the metal oxide support.
6. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 4, wherein: the carrier is aluminum oxide, silicon dioxide, mg-Al hydrotalcite, titanium dioxide and zirconium dioxide; preferably, the support is silica and titania; the BET surface area of the support is from 80 to 250m 2 (ii)/g; preferably 100 to 200m 2 /g。
7. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 4, wherein: the carrier modification aid accounts for 0.125-5% of the weight of the metal oxide carrier; preferably, the carrier modification aid is 1-3% by weight of the metal oxide carrier;
preferably, the carrier-modifying adjuvant comprises sodium and potassium.
8. The method for suppressing cyclododecane methanol as a by-product in a process for preparing cyclododecane alcohol by hydrogenation according to claim 4, wherein: the lanthanide metal oxide of the metal dispersing aid is cerium oxide.
9. The method of claim 4 for suppressing cyclododecanemethanol produced as a by-product of cyclododecanol hydrogenation process, wherein: the mass ratio of the metal dispersing auxiliary agent to the catalyst metal is (0.05-1.0): 1; preferably, the mass ratio of the metal dispersing aid to the catalyst metal is (0.1-0.5): 1.
10. the method of claim 4 for suppressing cyclododecanemethanol produced as a by-product of cyclododecanol hydrogenation process, wherein: the preparation process of the catalyst comprises equal-volume impregnation, coprecipitation and spray impregnation; equal volume impregnation is preferred;
the selectivity of the cyclododecane methanol which is a byproduct of the catalytic hydrogenation process is reduced to 0.01-0.05%.
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