CN116099532A - Supported platinum ruthenium-based catalyst, preparation method thereof and preparation method of alcohol ether carboxylic acid - Google Patents
Supported platinum ruthenium-based catalyst, preparation method thereof and preparation method of alcohol ether carboxylic acid Download PDFInfo
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- CN116099532A CN116099532A CN202111327257.4A CN202111327257A CN116099532A CN 116099532 A CN116099532 A CN 116099532A CN 202111327257 A CN202111327257 A CN 202111327257A CN 116099532 A CN116099532 A CN 116099532A
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- ruthenium
- platinum
- alcohol ether
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 93
- -1 alcohol ether carboxylic acid Chemical class 0.000 title claims abstract description 54
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 47
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021603 Ruthenium iodide Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- QALZILIGOXJDCX-UHFFFAOYSA-N carbonyl dichloride;ruthenium Chemical compound [Ru].ClC(Cl)=O QALZILIGOXJDCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 230000003197 catalytic effect Effects 0.000 abstract description 34
- 238000007254 oxidation reaction Methods 0.000 abstract description 20
- 230000003647 oxidation Effects 0.000 abstract description 15
- 231100000331 toxic Toxicity 0.000 abstract description 8
- 230000002588 toxic effect Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/38—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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a supported platinum ruthenium-based catalyst and a preparation method thereof, and a preparation method of alcohol ether carboxylic acid. According to the invention, the first mixed liquid containing platinum element and ruthenium element in a certain proportion is dripped into carriers such as cerium oxide, silicon dioxide, carbon simple substance, aluminum oxide and the like to prepare a catalyst precursor, and then the catalyst precursor is dried at 40-100 ℃ and baked at 250-500 ℃, so that the prepared supported platinum-ruthenium-based catalyst has good stability, can be recycled, has high catalytic activity, is simple in preparation process, is more beneficial to industrial production, does not need to introduce toxic and harmful substances in the preparation process, does not generate industrial waste residues, waste water and the like which are difficult to treat, and is more environment-friendly; the catalyst is particularly suitable for preparing alcohol ether carboxylic acid by catalytic oxidation, and has higher selectivity and conversion rate compared with the traditional method for preparing alcohol ether carboxylic acid by catalytic oxidation.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a supported platinum ruthenium-based catalyst and a preparation method thereof, and a preparation method of alcohol ether carboxylic acid.
Background
Sodium alkoxide carboxylic acidThe salt is a novel multifunctional anionic surfactant which is safe and nontoxic, and has good detergency, wettability, emulsifying property, dispersibility and calcium soap dispersing power. The general structural formula is as follows: r- (OCH) 2 CH 2 ) n OCH 2 COONa, very similar to soap, but with the built-in EO chain, it combines the characteristics of anionic and nonionic surfactants, can be used under a wide range of pH conditions, and has excellent solubilizing ability, suitable for formulation of functional transparent products.
At present, the method for industrially producing alcohol ether carboxylate is mainly a chloroacetic acid method, but because the viscosity of the alcohol ether carboxylic acid is higher, the chloroacetic acid in the alcohol ether carboxylic acid is difficult to clean, and the produced alcohol ether carboxylic acid has irritation to skin and is difficult to obtain wider application, so that the product quality is improved and the alcohol ether carboxylic acid is more widely applied if the catalytic oxidation method can be realized. Early, the preparation of alcohol ether carboxylic acid by catalytic oxidation requires reaction at high temperature (150-270 ℃), the reaction conditions are harsh, and a noble metal catalyst is needed; with the development of the field, the reaction temperature for preparing alcohol ether carboxylic acid is reduced, noble metal is still needed to be used as a catalyst, the catalyst dosage is high, and the cost is high; therefore, a series of supported catalysts are developed for preparing the alcohol ether carboxylic acid, but the supported catalysts have low catalytic efficiency, or the treatment process is not environment-friendly, or the reusability is poor, so that the preparation cost of the alcohol ether carboxylic acid is difficult to be really and effectively reduced, and the large-scale industrialized production is realized.
Disclosure of Invention
Based on the above, it is necessary to provide a supported platinum ruthenium-based catalyst with green treatment process, low cost and high catalytic activity and a preparation method thereof, and the catalyst is easy to separate and has good stability, so that the catalyst has good reusability, is beneficial to large-scale industrial production, and can effectively reduce cost when being used for preparing alcohol ether carboxylic acid by catalytic oxidation.
In one aspect of the present invention, there is provided a method for preparing a supported platinum ruthenium-based catalyst, comprising the steps of:
mixing a platinum source and a ruthenium source with a first solvent to prepare a first mixed solution; dropping the first mixed liquid on a carrier to prepare a catalyst precursor; placing the catalyst precursor in a normal pressure or vacuum environment, and drying at 40-100 ℃; placing the dried catalyst precursor in hydrogen or inert gas, and roasting at the temperature of 250-500 ℃ to prepare the supported platinum ruthenium-based catalyst;
wherein the platinum source is platinum acid and/or platinum salt, and the ruthenium source is ruthenium salt; in the first mixed solution, the mass ratio of the platinum element to the ruthenium element is 1 (0.1-10); the carrier is one or more of cerium oxide, silicon dioxide, carbon simple substance and aluminum oxide.
In some embodiments, the step of preparing the first mixed liquor further comprises: and sequentially adding a surfactant and a reducing agent into the mixed product.
In some embodiments, the surfactant is one or more of polyvinylpyrrolidone, tetrabutylammonium bromide, tetraoctylammonium bromide, and tetraethylammonium bromide; and/or
The reducing agent is one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride and elemental iodine; and/or
In the first mixed solution, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substances of the surfactant is 1 (0.01-1.2); and/or
In the first mixed solution, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substances of the reducing agent is 1 (1.6-2.5).
In some embodiments, the platinum source is one or more of chloroplatinic acid, platinum acetylacetonate, and platinum chloride; and/or
The ruthenium source is one or more of ruthenium chloride, ruthenium iodide, potassium chlororuthenate, sodium chlororuthenate and ruthenium carbonyl chloride; and/or
The first solvent is one or more of acetone, ethyl acetate and dimethyl sulfoxide; and/or
In the first mixed solution, the concentration of the platinum element is 0.01mol/L to 0.05mol/L, and the concentration of the ruthenium element is 0.1mol/L to 0.5mol/L.
In another aspect of the invention, a supported platinum ruthenium-based catalyst is provided, which is prepared by the aforementioned preparation method.
In some embodiments, the total loading of the platinum element and the ruthenium element in the supported platinum ruthenium-based catalyst is 0.5wt% to 10wt%.
In yet another aspect of the present invention, there is provided a method for preparing an alcohol ether carboxylic acid, comprising the steps of:
alcohol ether, the supported platinum ruthenium-based catalyst and a second solvent are mixed to prepare a second mixed solution; and (3) introducing oxidizing gas into the second mixed solution, and reacting at 50-130 ℃ to prepare the alcohol ether carboxylic acid.
In some embodiments, the volume percentage of oxygen in the oxidizing gas is 5% -100%, and the rest is filling gas, wherein the filling gas is nitrogen and/or inert gas; and/or
Before the oxidizing gas is introduced into the second mixed solution, the method further comprises the step of heating the second mixed solution to 50-130 ℃; and/or
The second solvent is one or more of 1, 4-dioxane, tetrahydrofuran, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, toluene and xylene.
In some embodiments, the alcohol ether has the following structure:
wherein R is a linear or branched alkyl group containing 4 to 18 carbon atoms, and n is an integer ranging from 0 to 7; and/or
The mass ratio of the supported platinum ruthenium-based catalyst to the alcohol ether is 1 (100-400); and/or
The mass ratio of the alcohol ether to the second solvent is 1 (1-2); and/or
The reaction time is 12-36 h.
The invention also provides an alcohol ether carboxylic acid, which is prepared by the preparation method.
The first mixed liquid containing platinum element and ruthenium element in a certain proportion is dripped into carriers such as cerium oxide, silicon dioxide, carbon single, aluminum oxide and the like to prepare a catalyst precursor, then the catalyst precursor is dried at 40-100 ℃ and baked at 250-500 ℃, and the prepared supported platinum ruthenium-based catalyst has good stability, can be recycled, has high catalytic activity, is simple in preparation process, is more beneficial to industrial production, does not need to introduce toxic and harmful substances in the preparation process, does not generate industrial waste residues, waste water and the like which are difficult to treat, and is more environment-friendly; the catalyst is particularly suitable for preparing alcohol ether carboxylic acid by catalytic oxidation, and has higher selectivity and conversion rate compared with the traditional method for preparing alcohol ether carboxylic acid by catalytic oxidation.
The alcohol ether carboxylic acid prepared by catalytic oxidation of the supported platinum ruthenium-based catalyst can use oxidizing gas as an oxidant, so that the use of low-selectivity, toxic and harmful oxidants such as hexavalent inorganic chromium reagents and the like is avoided, and the catalyst is more environment-friendly; the residue of toxic reagents in the alcohol ether carboxylic acid which has high viscosity and is easy to wrap the reaction raw materials is avoided, so that the prepared alcohol ether carboxylic acid is safer and milder, and the application scene of the alcohol ether carboxylic acid is effectively expanded; in addition, the oxidation reaction can be carried out at 50-130 ℃, compared with the traditional reaction temperature of 150-270 ℃, the reaction condition is milder, the purity of the alcohol ether carboxylic acid product is improved, the occurrence of side reaction is avoided, the energy consumption is lower, and the production cost is effectively reduced.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. In the description of the present invention, the meaning of "several" means at least one, such as one, two, etc., unless specifically defined otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The "inert gas" in the present invention refers to a rare gas such as helium (He), neon (Ne), argon (Ar), krypton (Kr) or xenon (Xe).
In the present invention, "total loading" means the percentage of the total mass of platinum element and ruthenium element to the total mass of the catalyst, and correspondingly, "wt%" represents the mass percentage.
In one aspect of the present invention, there is provided a method for preparing a supported platinum ruthenium-based catalyst, comprising the steps of:
mixing a platinum source and a ruthenium source with a first solvent to prepare a first mixed solution; dropping the first mixed liquid on a carrier to prepare a catalyst precursor; placing the catalyst precursor in a normal pressure or vacuum environment, and drying at 40-100 ℃; placing the dried catalyst precursor in hydrogen or inert gas, and roasting at 250-500 ℃ to prepare a supported platinum ruthenium-based catalyst;
wherein the platinum source is platinum acid and/or platinum salt, and the ruthenium source is ruthenium salt; in the first mixed solution, the mass ratio of the platinum element to the ruthenium element is 1 (0.1-10); the carrier is one or more of cerium oxide, silicon dioxide, carbon simple substance and aluminum oxide.
The first mixed liquid containing platinum element and ruthenium element in a certain proportion is dripped into carriers such as cerium oxide, silicon dioxide, carbon simple substance, aluminum oxide and the like to prepare a catalyst precursor, then the catalyst precursor is dried at 40-100 ℃ and baked at 250-500 ℃, and the prepared supported platinum ruthenium-based catalyst has good stability, can be recycled, has high catalytic activity, is simple in preparation process, is more beneficial to industrial production, does not need to introduce toxic and harmful substances in the preparation process, does not generate industrial waste residues, waste water and the like which are difficult to treat, and is more environment-friendly; the catalyst is particularly suitable for preparing alcohol ether carboxylic acid by catalytic oxidation, and has higher selectivity and conversion rate compared with the traditional method for preparing alcohol ether carboxylic acid by catalytic oxidation.
In some embodiments, the vacuum environment has a vacuum level of-0.05 MPa to-0.1 MPa.
In some embodiments, the hydrogen or inert gas is at a pressure of 0.1MPa to 1MPa. Alternatively, the gas pressure of the hydrogen gas or the inert gas may be, for example, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa.
Preferably, the support is ceria. The cerium dioxide is used as a catalyst carrier, and the prepared catalyst has higher catalytic efficiency and better stability, is easy to separate from a reaction system after use, and still maintains high catalytic efficiency and selectivity after separation, so that the catalyst has better reusability, can greatly reduce cost in the actual production process, and is more environment-friendly. Meanwhile, when the catalyst is used for preparing alcohol ether carboxylic acid by catalytic oxidation of alcohol ether, the cerium dioxide has a certain protection effect on ether bond, and the oxidant can oxidize terminal hydroxyl groups with high selectivity without breaking ether bond, so that the catalytic oxidation reaction has higher selectivity.
Alternatively, the drying temperature may be, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃. The proper drying temperature can effectively remove the water vapor in the catalyst precursor, and meanwhile, the water vapor is not volatilized too quickly, so that the structure of the catalyst precursor is influenced, and the catalytic efficiency of the catalyst is reduced.
Alternatively, the firing temperature may be, for example, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃. The proper roasting temperature can enable the catalyst to have better stability, so that the catalyst has higher catalytic efficiency, selectivity and recovery rate. Particularly, when the surfactant is introduced in the preparation process, the surfactant can volatilize in the roasting process, and the proper roasting temperature ensures that the surfactant is removed, and meanwhile, pores are not formed at an excessively high volatilization speed, so that the performance of the catalyst is not affected.
Alternatively, the ratio of the amounts of the substances of the platinum element and the ruthenium element in the first mixed liquid may be, for example, 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5. The ratio of the amounts of the substances of the platinum element and the ruthenium element directly influences the performance of the catalyst, and the platinum element and the ruthenium element are compounded in a certain proportion, so that the synergistic effect can be exerted to the greatest extent, and the catalytic efficiency of the catalyst is effectively improved.
In some embodiments, the drying time is from 12 hours to 48 hours. Alternatively, the drying time may be, for example, 24 hours, 36 hours.
In some embodiments, the firing time is 2 to 5 hours. Alternatively, the roasting time can be, for example, 2.5h, 3h, 3.5h, 4h, 4.5h.
In some embodiments, the step of preparing the first mixed liquor further comprises: to the mixture of the platinum source, the ruthenium source and the first solvent, a surfactant and a reducing agent were added in this order. The surfactant and the reducer are added into the system, so that the stability of the catalyst can be improved, and the loss of active metals caused by carrier collapse can be avoided.
In some embodiments, the system is stirred for 10 to 48 hours after the surfactant and the reducing agent are added thereto. Alternatively, the stirring time may be, for example, 15h, 20h, 25h, 30h, 35h, 40h, 45h.
In some embodiments, the platinum source is one or more of chloroplatinic acid, platinum acetylacetonate, and platinum chloride.
In some embodiments, the ruthenium source is one or more of ruthenium chloride, ruthenium iodide, potassium chlororuthenate, sodium chlororuthenate, and ruthenium carbonyl chloride.
In some embodiments, the first solvent is one or more of acetone, ethyl acetate, and dimethyl sulfoxide.
In some embodiments, the concentration of elemental platinum is from 0.01mol/L to 0.05mol/L and the concentration of elemental ruthenium is from 0.1mol/L to 0.5mol/L. The proper concentration can lead the metal distribution in the prepared catalyst to be more uniform, thereby having higher catalytic activity. Optionally, the concentration of the platinum element in the first mixed solution may be, for example, 0.0125mol/L to 0.03mol/L, and may also be, for example, 0.015mol/L, 0.02mol/L, and 0.025mol/L; the concentration of the ruthenium element may be, for example, 0.125mol/L to 0.3mol/L, and may be, for example, 0.15mol/L, 0.2mol/L, or 0.25mol/L.
In some embodiments, the surfactant is one or more of polyvinylpyrrolidone, tetrabutylammonium bromide, tetraoctylammonium bromide, and tetraethylammonium bromide.
In some embodiments, the reducing agent is one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride, and elemental iodine.
In some embodiments, the ratio of the sum of the amounts of the platinum element and the ruthenium element to the amount of the surfactant material in the first mixed solution is 1 (0.01 to 1.2). In some embodiments, the ratio of the sum of the amounts of the platinum element and the ruthenium element to the amount of the surfactant is 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1.
In the first mixed solution, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substance of the reducing agent is 1 (1.6-2.5). In some embodiments, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substance of the reducing agent is 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4.
In another aspect of the invention, a supported platinum ruthenium-based catalyst is provided, which is prepared by the aforementioned preparation method. The supported platinum ruthenium-based catalyst prepared by the preparation method has good stability, can be recycled and has high catalytic activity.
In some embodiments, the total loading of the platinum element and the ruthenium element in the supported platinum ruthenium-based catalyst is from 0.5wt% to 10wt%. When the total loading of the platinum element and the ruthenium element is limited in a proper range, the obtained catalyst is more suitable for preparing alcohol ether carboxylic acid by catalytic oxidation of alcohol ether, can realize better conversion rate and selectivity, and has lower production cost.
Alternatively, the total loading of the platinum element and the ruthenium element may be, for example, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%.
In yet another aspect of the present invention, there is provided a method for preparing an alcohol ether carboxylic acid, comprising the steps of:
alcohol ether, the supported platinum ruthenium-based catalyst and a second solvent are mixed to prepare a second mixed solution; and (3) introducing oxidizing gas into the second mixed solution to react at 50-130 ℃ to prepare the alcohol ether carboxylic acid.
The alcohol ether carboxylic acid prepared by catalytic oxidation of the supported platinum ruthenium-based catalyst can use oxidizing gas as an oxidant, so that the use of low-selectivity, toxic and harmful oxidants such as hexavalent inorganic chromium reagents and the like is avoided, and the catalyst is more environment-friendly; the residue of toxic reagents in the alcohol ether carboxylic acid which has high viscosity and is easy to wrap the reaction raw materials is avoided, so that the prepared alcohol ether carboxylic acid is safer and milder, and the application scene of the alcohol ether carboxylic acid is effectively expanded; in addition, the oxidation reaction can be carried out at 50-130 ℃, compared with the traditional reaction temperature of 150-270 ℃, the reaction condition is milder, the purity of the alcohol ether carboxylic acid product is improved, the occurrence of side reaction is avoided, the energy consumption is lower, and the production cost is effectively reduced.
In some embodiments, the volume percentage of oxygen in the oxidizing gas is 5% -100%, and the balance is a filling gas, wherein the filling gas is nitrogen and/or inert gas.
The oxidability of the zinc oxide gas can be regulated and controlled by controlling the content of oxygen in the oxidability gas, so that the zinc oxide gas can be better used for the oxidation of alcohol ethers with different structures. Alternatively, the volume percentage of oxygen may be, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%.
Alternatively, the reaction temperature may be, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃.
In some embodiments, the oxidizing gas has a gas pressure of 0.1MPa to 1MPa. Alternatively, the gas pressure of the oxidizing gas may be, for example, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa.
In some embodiments, the method further comprises the step of heating the second mixed liquor to a temperature of 50 ℃ to 130 ℃ before introducing the oxidizing gas into the second mixed liquor. Before the oxidizing gas is introduced, the system is heated to the reaction temperature, so that other reactants can be better oxidized, and the reaction efficiency is improved.
In some embodiments, the alcohol ether has the following structure:
wherein R is a linear or branched alkyl group having 4 to 18 carbon atoms, and n is an integer ranging from 0 to 7.
Alternatively, the number of carbon atoms of R may be, for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18.
Alternatively, n is 0, 1, 2, 3, 4, 5, 6 or 7.
In some embodiments, the second solvent is one or more of 1, 4-dioxane, tetrahydrofuran, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, toluene, and xylene.
In some embodiments, the mass ratio of supported platinum ruthenium-based catalyst to alcohol ether is 1 (100-400). Alternatively, the mass ratio of the supported platinum ruthenium-based catalyst to the alcohol ether may be, for example, 1:150, 1:200, 1:250, 1:300, 1:350.
In some embodiments, the mass ratio of alcohol ether to second solvent is 1 (1-2). Alternatively, the mass ratio of alcohol ether to second solvent may be, for example, 1:1.2, 1:1.4, 1:1.6, 1:1.8.
In some embodiments, the reaction time is from 12 hours to 36 hours. Alternatively, the reaction time may be, for example, 16h, 20h, 24h, 28h, 32h.
In some embodiments, the post-treatment step after the end of the reaction comprises: and (3) after the reaction system is cooled to room temperature, filtering to remove solid matters, extracting and washing filtrate, and then removing organic solvent in the system.
In some embodiments, the solvent employed for extraction is one or more of 1, 4-dioxane, ethyl acetate, diethyl ether, chloroform, dichloroethane, bromopropane.
In some embodiments, the solution employed for washing is one or more of dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, dilute sodium hydroxide solution.
In some embodiments, the organic solvent is removed from the system by distillation at atmospheric or reduced pressure, at a temperature of 20 ℃ to 70 ℃.
The invention also provides an alcohol ether carboxylic acid, which is prepared by the preparation method. Because alcohol ether carboxylic acid has higher viscosity, if chloroacetic acid method is adopted for preparation or hexavalent inorganic chromium is adopted as oxidant, corrosive or toxic and harmful chemical reagents are easy to remain in the product, which can greatly limit the application of alcohol ether carboxylic acid. The preparation method of the invention does not involve heavy metal oxidant, the preparation process is environment-friendly, and the used catalyst is easy to separate from the reaction system and reuse, so the prepared alcohol ether carboxylic acid has higher purity and wider use prospect.
The present invention will be described in further detail with reference to specific examples and comparative examples. The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the application document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer. It will be appreciated that the apparatus and materials used in the examples below are more specific and in other embodiments may not be limited thereto, for example, the use of a three-necked flask as a reaction vessel.
Example 1
0.265g of chloroplatinic acid (0.5 mmol) and 1.030g ruthenium chloride trihydrate (5 mmol) were weighed and mixed with 20.0mL of acetone, respectively, and combined into a first mixed solution; the first mixed solution was directly added dropwise to 59.4g CeO 2 Obtaining a catalyst precursor; drying the catalyst precursor at 40 ℃ and normal pressure for 12 hours, and roasting at 250 ℃ and under 0.1MPa of argon for 2 hours to obtain a supported platinum ruthenium-based catalyst with the load of 1 percent, which is recorded as 1 percent PtRu-0.1/CeO 2 -250；
Into a three-necked flask were charged 10g of an alcohol ether obtained by condensing stearyl alcohol and 6 ethylene oxides, 20g of 1, 4-dioxane, 0.10g of 1% PtRu/CeO 2 250, after the temperature is raised to 100 ℃, continuously introducing air of 0.1MPa, and reacting for 20 hours under the condition of stirring; after the reaction solution cooled to room temperature, the solid was removed by filtrationThe material, the filtrate, was retained, extracted with chloroform, and the organic phase was washed with a dilute sulfuric acid detergent, followed by distillation under reduced pressure at 70 ℃ to remove the organic solvent, to give an alcohol ether carboxylic acid product.
Example 2
Substantially the same as in example 1, except that CeO 2 The amount of the catalyst was 5.4g, the catalyst loading was 10%, and the obtained supported platinum ruthenium-based catalyst was designated as 1% PtRu-0.1/CeO 2 -250。
Example 3
Substantially the same as in example 1, except that CeO 2 The amount of the catalyst was 11.4g, the catalyst loading was 5%, and the obtained supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1/CeO 2 -250。
Example 4
Substantially the same as in example 3, except that the calcination temperature was 350℃and the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1/CeO 2 -350。
Example 5
Substantially the same as in example 3, except that the calcination temperature was 450℃and the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1/CeO 2 -450。
Example 6
Substantially the same as in example 5, except that the ratio of the amounts of chloroplatinic acid and ruthenium chloride was 1:5, the amount of the carrier was changed correspondingly to maintain the supported amount at 5%, and the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.2/CeO 2 -450。
Example 7
Substantially the same as in example 5, except that the ratio of the amounts of chloroplatinic acid and ruthenium chloride was 1:0.5, and the amount of the carrier was changed accordingly so as to maintain the supported amount at 5%, the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-2/CeO 2 -450。
Example 8
Substantially the same as in example 5, except that the ratio of the amounts of chloroplatinic acid and ruthenium chloride was 1:0.1, the amount of the carrier was changed accordingly to maintain the supported amount at 5%, and the resulting supported platinum ruthenium-based catalyst was obtainedIs recorded as 5% PtRu-10/CeO 2 -450。
Example 9
Substantially the same as in example 3, except that (1) the platinum source was platinum acetylacetonate, and the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1/CeO 2 -350; (2) the solvent for the catalytic oxidation reaction is dichloroethane.
Example 10
Substantially the same as in example 9, except that 0.62g of polyvinylpyrrolidone (0.08 mmol) having a molecular weight of 8000 and 0.50g of lithium aluminum hydride (13.2 mmol) were further added to the first mixed solution, and after the addition of polyvinylpyrrolidone and lithium aluminum hydride, the mixture was stirred for 12 hours to uniformly disperse the mixture; the obtained supported platinum ruthenium-based catalyst is recorded as 5% PtRu-0.1@8000PVP/CeO 2 -350。
Example 11
Substantially the same as in example 9, except that 4.49g of polyvinylpyrrolidone (0.08 mmol) having a molecular weight of 58000 and 0.50g of potassium borohydride (9.3 mmol) were further added to the first mixed solution, the resulting supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1@58000PVP/CeO 2 -350。
Example 12
Substantially the same as in example 9, except that: (1) The first mixed solution is also added with 2.48g of polyvinylpyrrolidone (0.08 mmol) with the molecular weight of 32000 and 0.50g of lithium aluminum hydride (13.2 mmol), and the obtained supported platinum ruthenium-based catalyst is marked as 5 percent PtRu-0.1@32000PVP/CeO 2 -350; (2) The alcohol ether was obtained by condensing octanol with 7 ethylene oxide in an amount of 15g.
Example 13
Substantially the same as in example 12, except that: 10.07g of polyvinylpyrrolidone (0.08 mmol) with a molecular weight of 130000 and 0.50g of sodium borohydride (13.2 mmol) were used as surfactants, and the obtained supported platinum ruthenium-based catalyst was designated as 5% PtRu-0.1@130000PVP/CeO 2 -350。
Example 14
Substantially the same as in example 12, except that: (1) the platinum source is platinum chloride; (2) 2.06g of tetrabutylammonium bromide (6.4 mmol) was used as the surfactant; (3) RoastingThe temperature is 450 ℃; the obtained supported platinum ruthenium-based catalyst is recorded as 5% PtRu-0.1@TBAB/CeO 2 -450。
Example 15
Substantially the same as in example 14, except that: the amount of alcohol ether used was 40g.
Example 16
Substantially the same as in example 1, except that the carrier was SiO 2 The resulting supported platinum ruthenium-based catalyst was designated 1% PtRu-0.1/SiO 2 -250。
Example 17
Substantially the same as in example 1, except that the carrier was C, the resulting supported platinum ruthenium-based catalyst was designated as 1% PtRu-0.1/C-250.
Example 18
Substantially the same as in example 1, except that the carrier was Al 2 O 3 The resulting supported platinum ruthenium-based catalyst was designated 1% PtRu-0.1/Al 2 O 3 -250。
Example 19
Substantially identical to example 1, except that: (1) Roasting the catalyst precursor in a hydrogen atmosphere of 0.2 MPa; (2) The oxidation reaction was carried out under a mixture of oxygen and nitrogen (0.2 MPa), wherein the volume ratio of oxygen to nitrogen was 1:1.
Comparative example 1
Substantially the same as in example 1, except that only ruthenium element was contained, the resulting catalyst was designated as 1% Ru-0.1/CeO 2 -250。
Comparative example 2
Substantially the same as in example 1, except that only platinum element was contained, the resulting catalyst was designated 1% Pt-0.1/CeO 2 -250。
Comparative example 3
Substantially the same as in example 1, except that palladium chloride was used in the same amount as in example 1 in place of chloroplatinic acid, the amount of the carrier was changed correspondingly, and the supported amount was maintained at 1%, and the resulting catalyst was designated as 1% PdRu-0.1/CeO 2 -250。
Comparative example 4
Substantially the same as in example 1, except thatThe copper chloride with equal amount is adopted to replace ruthenium chloride, the carrier dosage is correspondingly changed, the load is kept to be 1 percent, and the obtained catalyst is recorded as 1 percent PtCu-0.1/CeO 2 -250。
Comparative example 5
Substantially the same as in example 1, except that the calcination temperature was 600℃and the resulting supported platinum ruthenium-based catalyst was designated as 1% PtRu-0.1/CeO 2 -600。
The conversion of the alcohol ether feedstock in each of the example and comparative reactions was calculated to investigate the catalytic efficiency; the alcohol ether carboxylic acid ratio in the oxidation product was calculated to examine the reaction selectivity, and the results are shown in Table 1:
TABLE 1
The catalyst after the completion of the reaction of example 3 and examples 16 to 18 was recovered from the system, and the catalyst was subjected to a catalytic test again, and the results are shown in Table 2:
TABLE 2
| Group of | Conversion rate | Selectivity of |
| Example 3 | 90％ | 91％ |
| Example 16 | 25％ | 68％ |
| Example 17 | 52％ | 68％ |
| Example 18 | 59％ | 70％ |
From examples 1 to 3, it is known that the higher the catalyst loading, the higher the conversion and the selectivity, respectively, but from the standpoint of comprehensive cost, a loading of 5% is a more suitable choice; from examples 3 to 5, the effect of the firing temperature of 250 degrees celsius is slightly better; from examples 5 to 8, it is understood that the selectivity of the reaction is best when the ratio of the amounts of the platinum element and the ruthenium element is 1:5, the conversion rate of the reaction is highest when the ratio of the amounts of the platinum element and the ruthenium element is 1:0.1, and overall, the combination property is better when the ratio of the amounts of the substances is 1:0.1; comparative examples 9 and 10 show that the addition of the surfactant and the reducing agent can make the catalyst more stable, thereby having higher catalytic efficiency and selectivity; as can be seen from comparative examples 14 and 15, when the amount of alcohol ether used is large, the selectivity of the reaction can be greatly improved, but the conversion rate is also significantly reduced; it is clear from examples 16 to 18 that when other types of carriers are used, the conversion rate and selectivity of the reaction are significantly reduced, and when alumina is used as the carrier, the first-time catalytic efficiency and the reaction selectivity are superior to those of the conventional catalytic method, but the catalytic efficiency and the reaction selectivity after recovery are significantly reduced, and the catalyst recycling property is poor.
The comparative examples 1 and 2 are catalyzed by ruthenium or platinum alone, and the reaction conversion rate and selectivity are obviously reduced compared with example 1; in comparative examples 3 and 4, if common metals similar to ruthenium or platinum are used for replacement, the effect of the obtained composite catalyst is even inferior to that of a single catalyst, and as can be seen, the platinum-ruthenium-based composite catalyst has a synergistic effect, is compounded in a certain proportion and is assisted by a specific carrier, so that the catalytic efficiency and the reaction selectivity of the catalyst can be greatly improved; in comparative example 5, too high a calcination temperature also significantly affected the performance of the catalyst, and it can be seen that a suitable preparation process also has an important effect on the performance of the catalyst.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (10)
1. The preparation method of the supported platinum ruthenium-based catalyst is characterized by comprising the following steps of:
mixing a platinum source and a ruthenium source with a first solvent to prepare a first mixed solution; dropping the first mixed liquid on a carrier to prepare a catalyst precursor; placing the catalyst precursor in a normal pressure or vacuum environment, and drying at 40-100 ℃; placing the dried catalyst precursor in hydrogen or inert gas, and roasting at the temperature of 250-500 ℃ to prepare the supported platinum ruthenium-based catalyst;
wherein the platinum source is platinum acid and/or platinum salt, and the ruthenium source is ruthenium salt; in the first mixed solution, the mass ratio of the platinum element to the ruthenium element is 1 (0.1-10); the carrier is one or more of cerium oxide, silicon dioxide, carbon simple substance and aluminum oxide.
2. The method of preparing according to claim 1, wherein the step of preparing the first mixed liquor further comprises: and sequentially adding a surfactant and a reducing agent into the mixed product.
3. The method of preparation according to claim 2, wherein the surfactant is one or more of polyvinylpyrrolidone, tetrabutylammonium bromide, tetraoctylammonium bromide and tetraethylammonium bromide; and/or
The reducing agent is one or more of lithium aluminum hydride, sodium borohydride, potassium borohydride and elemental iodine; and/or
In the first mixed solution, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substances of the surfactant is 1 (0.01-1.2); and/or
In the first mixed solution, the ratio of the sum of the amounts of the substances of the platinum element and the ruthenium element to the amount of the substances of the reducing agent is 1 (1.6-2.5).
4. A method of preparation according to any one of claims 1 to 3 wherein the platinum source is one or more of chloroplatinic acid, platinum acetylacetonate and platinum chloride; and/or
The ruthenium source is one or more of ruthenium chloride, ruthenium iodide, potassium chlororuthenate, sodium chlororuthenate and ruthenium carbonyl chloride; and/or
The first solvent is one or more of acetone, ethyl acetate and dimethyl sulfoxide; and/or
In the first mixed solution, the concentration of the platinum element is 0.01mol/L to 0.05mol/L, and the concentration of the ruthenium element is 0.1mol/L to 0.5mol/L.
5. A supported platinum ruthenium-based catalyst characterized by being prepared by the preparation method according to any one of claims 1 to 4.
6. The supported platinum ruthenium-based catalyst according to claim 5, wherein the total loading of the platinum element and the ruthenium element in the supported platinum ruthenium-based catalyst is 0.5wt% to 10wt%.
7. A process for the preparation of an alcohol ether carboxylic acid comprising the steps of:
mixing alcohol ether, the supported platinum ruthenium-based catalyst of claim 5 or 6 and a second solvent to prepare a second mixed solution; and (3) introducing oxidizing gas into the second mixed solution, and reacting at 50-130 ℃ to prepare the alcohol ether carboxylic acid.
8. The preparation method according to claim 7, wherein the volume percentage of oxygen in the oxidizing gas is 5-100%, and the balance is filling gas, and the filling gas is nitrogen and/or inert gas; and/or
Before the oxidizing gas is introduced into the second mixed solution, the method further comprises the step of heating the second mixed solution to 50-130 ℃; and/or
The second solvent is one or more of 1, 4-dioxane, tetrahydrofuran, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, toluene and xylene.
9. The method of claim 7, wherein the alcohol ether has the structure:
wherein R is a linear or branched alkyl group containing 4 to 18 carbon atoms, and n is an integer ranging from 0 to 7; and/or
The mass ratio of the supported platinum ruthenium-based catalyst to the alcohol ether is 1 (100-400); and/or
The mass ratio of the alcohol ether to the second solvent is 1 (1-2); and/or
The reaction time is 12-36 h.
10. An alcohol ether carboxylic acid, characterized by being produced by the production method according to any one of claims 7 to 9.
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| CN101905158A (en) * | 2010-07-21 | 2010-12-08 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| WO2016026132A1 (en) * | 2014-08-22 | 2016-02-25 | Rhodia Operations | Process for oxidation of alcohols |
| CN106391001A (en) * | 2016-08-25 | 2017-02-15 | 浙江工业大学 | Active carbon loaded ruthenium-platinum bimetallic composite catalyst, and preparation method and applications thereof |
| CN111151243A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Ruthenium-based catalyst, preparation method and application thereof |
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| CN101905158A (en) * | 2010-07-21 | 2010-12-08 | 中国日用化学工业研究院 | Platinum carbon catalyst for preparing alcohol ether carboxylic acid and preparation method and application thereof |
| WO2016026132A1 (en) * | 2014-08-22 | 2016-02-25 | Rhodia Operations | Process for oxidation of alcohols |
| CN106391001A (en) * | 2016-08-25 | 2017-02-15 | 浙江工业大学 | Active carbon loaded ruthenium-platinum bimetallic composite catalyst, and preparation method and applications thereof |
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