CN112830877A - Application of a supported single-atom noble metal catalyst in the carboxymethyl esterification of unsaturated hydrocarbons - Google Patents
Application of a supported single-atom noble metal catalyst in the carboxymethyl esterification of unsaturated hydrocarbons Download PDFInfo
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- CN112830877A CN112830877A CN201911154324.XA CN201911154324A CN112830877A CN 112830877 A CN112830877 A CN 112830877A CN 201911154324 A CN201911154324 A CN 201911154324A CN 112830877 A CN112830877 A CN 112830877A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 title claims description 27
- 238000005886 esterification reaction Methods 0.000 title abstract description 6
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title abstract description 4
- 230000032050 esterification Effects 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 5
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 claims abstract description 5
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims abstract description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000004696 coordination complex Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229960003067 cystine Drugs 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012685 metal catalyst precursor Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 9
- -1 methyl ester compounds Chemical class 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 230000004075 alteration Effects 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 10
- 239000012018 catalyst precursor Substances 0.000 description 10
- 238000001493 electron microscopy Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910021012 Co2(CO)8 Inorganic materials 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明公开了负载型单原子贵金属催化剂在不饱和烃羧甲酯化反应中的应用，活性组分为Ru，Rh，Ir，Pt，Pd，Ag，Au中的任意一种或几种，活性金属的负载量为0.05％‑1.5％，载体为硫化铬、硫化锰、硫化铁、硫化钴、硫化镍、硫化铜、硫化锌、硫化钼、硫化钨、硫化钛中的任意一种，催化剂的制备：将载体和活性金属混合后，在一定温度下焙烧。该催化剂用于不饱和烃羧甲酯化制备甲酯化合物，具有良好的活性和选择性。相比于均相羰基镍或钯‑膦配合物为催化剂、并添加强腐蚀性的硫酸或磺酸为助剂的体系，该发明所提供的多相反应过程具有环境友好、操作简单、可循环利用等优点。
The invention discloses the application of a supported single-atom precious metal catalyst in the carboxymethylation reaction of unsaturated hydrocarbons. The active components are any one or more of Ru, Rh, Ir, Pt, Pd, Ag and Au. The loading amount of the metal is 0.05%-1.5%, the carrier is any one of chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide, and titanium sulfide, and the catalyst is Preparation: After mixing the carrier and the active metal, it is calcined at a certain temperature. The catalyst is used for carboxymethyl esterification of unsaturated hydrocarbons to prepare methyl ester compounds, and has good activity and selectivity. Compared with the system in which homogeneous nickel carbonyl or palladium-phosphine complex is used as catalyst, and highly corrosive sulfuric acid or sulfonic acid is added as auxiliary agent, the heterogeneous reaction process provided by the invention has the advantages of environmental friendliness, simple operation and recyclability. Take advantage of other advantages.
Description
Technical Field
The invention relates to an application of a load type single-atom noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction
Background
The unsaturated hydrocarbon carboxymethylation reaction is a green, simple and high atom economy method for preparing methyl ester compounds, such as methyl methacrylate (i.e. organic glass). However, the industry is still using homogeneous nickel carbonyl or palladium-phosphine complexes as catalysts on a large scale and requires strongly corrosive sulfuric or sulfonic acids as auxiliaries. E.g. using Ni (CO)4,Co2(CO)8Or Pd (PPh)3Etc. as main catalyst, and trifluoromethanesulfonic acid and phenylmethanesulfonic acid as auxiliaries. Such catalysts are difficult to recover and separate and corrode equipment. Researchers find that the conversion rate of the reaction can be improved by adding pyridine into the catalytic system respectively, but the catalytic system is not economical and environment-friendly, and the defects of a homogeneous catalyst cannot be overcome. Therefore, there is a strong need for a heterogeneous catalyst with high activity and environmental friendliness for such reactions.
Many patents and literature describe metal sulfide catalysts.
Document 1(Nature nanotechnology 2018,411:417) prepared Pt/MoS by injection substitution theory2The monatomic catalyst is applied to the carbon dioxide reaction, and is found to have ultrahigh activity and selectivity and good industrial value. Meanwhile, the authors found that when the Pt loading is increased, the adjacent Pt atoms have a synergistic catalytic effect, and the effect changes CO2The energy barrier to hydrogenation, thereby altering the reaction path and altering its selectivity.
Document 2(Nature chemistry,2017,810:816) produced Co-MoS by an electrostatic adsorption method2A single-atom catalyst used in the reaction of preparing toluene by hydrodeoxygenation of 4-cresolThe excellent activity and stability are shown, and in contrast to the catalyst without Co doping, the authors increase the Co interaction with the support to make the Co center have excellent activity in the reaction.
Reference 3(Nature Communications,2014, sep,17) prepared Pd-MoS2A catalyst exhibiting catalytic activity and stability comparable to Pt electrodes in electrocatalytic HER reactions
Document 4(Adv Funct Mater,2014,24,2155-2162) synthesizes a series of metal sulfides (FeS)2,CoS2,NiS2Etc.), the results show that the transition metal sulfides have good electrocatalytic activity in the electrocatalytic reaction.
Document 5(Energy Environ Sci,2015,8:1594-2The catalyst shows catalytic activity equivalent to that of Pt in HER reaction, and the methanol poisoning resistance of the catalyst is obviously improved.
Disclosure of Invention
The catalyst shows high activity and selectivity in unsaturated hydrocarbon carboxy methyl esterification reaction, and has mild reaction condition, low cost and industrial application prospect.
The invention also aims to provide a method for preparing the supported monatomic metal catalyst, which has simple process flow and easy process control.
In order to achieve the purpose, the invention adopts the technical scheme that:
the active component of the supported monatomic noble metal catalyst is any one or mixture of two of common noble metals of Ru, Rh, Ir, Pt, Pd, Ag and Au, and the carrier is any one or more than two of chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide and titanium sulfide. Wherein the loading amount of the active metal is 0.05-1.5%.
The preparation process of the loaded monatomic noble metal catalyst is as follows:
1) dissolving a soluble precursor of the noble metal in deionized water, and adding an inorganic or organic complexing reagent to obtain a noble metal complex solution;
wherein the concentration of the noble metal in the noble metal precursor solution is 0.1-100mg/ml, and the preferred concentration is 0.5-5 mg/ml; the ratio of the amounts of substance of active metal to complexing agent is 0.02 to 10, preferably 0.1 to 4.
The soluble precursor of the noble metal is one or more than two of chloride, nitrate and organic complex of the precursor; the inorganic complexing reagent is as follows: one or a mixture of more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, wherein the organic complexing reagent is one or a mixture of more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents in any ratio;
2) mixing noble metal complex solution with carrier, stirring at 10-100 deg.C for 10-600 min, filtering, drying at 60-120 deg.C for 8-12 hr to obtain noble metal catalyst precursor, and adding He, Ar and N2、H2、O2Or in any one or more than two of air atmosphere, and roasting for 5-500min at 200-800 ℃.
The reaction is carried out in a solvent, the solvent is methanol or a mixture of methanol and one or more than two of ethanol, isopropanol, tert-butyl alcohol and toluene in any ratio, and the volume concentration of the methanol in the solvent is 5-100%; methanol is simultaneously used as a reaction substrate. The unsaturated hydrocarbon is any one of C2-C5 alkene, alkyne and dialkene, and the molar ratio of the catalyst active component to the reaction substrate is 1 x 10-4To 1. The preferred reaction temperature is 120-200 ℃, the preferred initial pressure of the unsaturated hydrocarbon and carbon monoxide in the reaction vessel is 0.5-1.5Mp at room temperature, and the preferred reaction time is 1-6 h.
The catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.
The activity test method of the catalyst provided by the invention comprises the following steps:
the reactor is a high-pressure reaction kettle, the reaction substrate, the internal standard and the solvent are prepared into reaction liquid with certain concentration, a certain amount of reaction liquid is taken by a pipette for reaction each time, the initial pressure of the unsaturated hydrocarbon and the carbon monoxide in the reaction kettle at room temperature is 0.5-1.5Mpa, the reaction temperature is 120-200 ℃, and the reaction time is not less than 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and then a sample was taken for gas chromatography.
The invention has the following effects:
1. the product obtained by the esterification reaction of unsaturated hydrocarbon carboxyl methyl is an industrially important organic monomer, such as synthetic organic glass, high-grade optical lens, water-based paint, high-grade mould and the like. The invention provides a supported high-dispersion noble metal catalyst which has high activity and selectivity for the reaction.
2. The invention provides a load type single atom noble metal catalyst which can be recycled for a plurality of times in the unsaturated hydrocarbon carboxymethyl esterification reaction without obviously reducing the activity.
3. The invention provides a load type single atom noble metal catalyst which is easy to separate from a reaction solution after reaction and is simple and convenient to operate.
In a word, the invention realizes the high-efficiency and high-selectivity conversion of unsaturated hydrocarbon, carbon monoxide and methanol to prepare ester compounds, compared with an industrial homogeneous catalyst system, the catalyst provided by the invention is green and friendly in the reaction process, saves the cost, and is expected to be applied in industry.
Drawings
FIG. 1 is a Pt-MoS of a supported monatomic noble metal prepared in example 12Spherical aberration electron microscope pictures of the catalyst.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and detailed description, but the invention is not limited thereto.
Example 1: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of molybdenum sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the mixture is placed in a drying oven at 120 ℃, a supported high-dispersion platinum-based catalyst precursor is obtained after drying for 12 hours, the precursor is placed in a quartz tube, and the precursor is treated for 120 minutes at 500 ℃ under Ar condition to obtain 1% Pt/MoS2 catalyst which is used in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 2: dissolving 0.015g of ruthenium chloride in 20g of deionized water, adding 0.5g of 25% ammonia water, stirring for 3h, adding 1g of molybdenum disulfide, stirring for 5h, filtering, washing, placing in a 60 ℃ oven, drying for 8h to obtain a supported high-dispersion ruthenium-based catalyst precursor, placing the precursor in a quartz tube, treating at 600 ℃ for 100min under the He condition to obtain a 1% Ru/MoS2 catalyst, and placing in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 3: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of iron sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in a drying oven at 120 ℃, a supported high-dispersion platinum-based catalyst precursor is obtained after drying for 12 hours, the precursor is placed in a quartz tube, and the precursor is treated for 120 minutes at 500 ℃ under Ar condition to obtain a 1% Pt/FeS catalyst which is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 4: dissolving 0.015g of chloroplatinic acid in 20g of deionized water, adding 1.5g of ammonium nitrate, stirring for 2 hours, adding 1g of cobalt sulfide, stirring for 1 hour, filtering, washing, placing in a drying oven at 100 ℃, drying for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and adding N2After 240 seconds of treatment at 300 ℃ under the conditions, 1% Pt/CoS2 monatomic catalyst was obtained and was ready for use in the desiccator. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 5: dissolving 0.017g palladium chloride in 20g deionized water, adding 0.2g ethanolamine organic reagent, stirring for 3h, adding 1g zinc sulfide, stirring for 4h, filtering, washingPlacing the precursor in an oven at 90 ℃, drying for 10H to obtain a supported high-dispersion palladium-based catalyst precursor, and placing the precursor in a quartz tube, wherein H is2Treating at 350 deg.c for 150min to obtain 1% Pd/ZnS catalyst in a drier for further use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 6: 0.021g of chloroauric acid is dissolved in 20g of deionized water, 0.8g of triethyl phosphate organic reagent is added, the mixture is stirred for 1 hour, 1g of tungsten sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 70 ℃ and dried for 7 hours to obtain a supported high-dispersion gold-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated for 300 minutes at 550 ℃ under the air condition to obtain 1% Au/WS2And (5) putting the catalyst in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 7: 0.027g of chloroplatinic acid is dissolved in 10g of deionized water, 2g of cysteine organic reagent is added, the mixture is stirred for 2 hours, 1g of titanium sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 80 ℃, the obtained product is dried for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, the obtained product is treated for 80 minutes at 400 ℃ under the He condition to obtain a 1% Pt/TiS2 catalyst, and the obtained product is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 8: dissolving 0.027g of chloroplatinic acid in 10g of deionized water, adding 2g of thiourea organic reagent, stirring for 2h, adding 1g of chromium sulfide, stirring for 2h, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and treating at 500 ℃ for 90min under the He condition to obtain 1% Pt/Cr2S3And (5) putting the catalyst in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 9: dissolving 0.017g of palladium chloride in 10g of deionized water, adding 2g of ethylenediamine organic reagent, stirring for 2h, adding 1g of copper sulfide, stirring for 2h, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion palladium-based catalyst precursor, placing the precursor in a quartz tube, treating at 400 ℃ for 120min under the He condition to obtain a 1% Pd/CuS catalyst, and placing in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Example 10: 0.015g of rhodium chloride is dissolved in 20g of deionized water, 0.5g of 25% ammonia water is added, stirring is carried out for 3h, 1g of iron sulfide is added, stirring is carried out for 2h, filtering and washing are carried out, the mixture is placed in an oven at 80 ℃, drying is carried out for 8h to obtain a supported high-dispersion rhodium-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated at 550 ℃ for 120min under the He condition to obtain a 1% Rh/FeS catalyst which is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.
Application example 1:
a certain amount of monatomic catalyst is taken to be put in a reaction kettle, 5ml of methanol reaction solution is added by a pipette, and the reaction conditions are 1Mpa of ethylene and 1Mpa of carbon monoxide (initial pressure) and 160 ℃.
The specific experimental results are as follows:
TABLE-results of the hydroformylation of ethylene with a different supported monatomic catalyst
TABLE results of different noble metal monoatomic catalysts in the hydromethyl esterification of ethylene
Claims (7)
1. The application of the supported monatomic noble metal catalyst in the unsaturated hydrocarbon carboxymethylation reaction is characterized in that: the active component of the supported noble metal catalyst is any one or more than two of Ru, Rh, Ir, Pt, Pd, Ag and Au, and the carrier is any one or more than two of chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide and titanium sulfide. Wherein the loading amount of the active metal is 0.05-1.5%.
2. Use according to claim 1, wherein the active metal is dispersed on the support in monoatomic form.
3. The use of claim 1, wherein: preferably selecting any one or more of active metals of Pt, Pd, Ru and Rh, and preferably selecting the load amount to be 0.1% -1%; preferably, the carrier is any one or more of chromium sulfide, molybdenum sulfide, tungsten sulfide and zinc sulfide.
4. The use according to claim 1, which is prepared by the following process:
1) dissolving a soluble precursor of the noble metal in deionized water, and adding an inorganic or organic complexing reagent to obtain a noble metal complex solution;
wherein the concentration of the noble metal in the noble metal precursor solution is 0.1-100mg/ml, and the preferred concentration is 0.5-5 mg/ml; the ratio of the amounts of substance of active metal to complexing agent is 0.02 to 10, preferably 0.1 to 4.
The soluble precursor of the noble metal is one or more than two of chloride, nitrate and organic complex of the precursor; the inorganic complexing reagent is as follows: one or a mixture of more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, wherein the organic complexing reagent is one or a mixture of more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents in any ratio;
2) mixing noble metal complex solution with carrier, stirring at 10-100 deg.C for 10-600 min, filtering, drying at 60-120 deg.C for 8-12 hr to obtain noble metal catalyst precursor, and adding He, Ar and N2、H2、O2Or in any one or more than two of air atmospheresAnd roasting at 200-800 deg.c for 5-500 min.
5. Use according to claims 1-4, characterized in that:
dispersing the catalyst in a solvent in a closed reaction kettle, and charging carbon monoxide and unsaturated hydrocarbon gas, wherein the initial pressure of the carbon monoxide and unsaturated hydrocarbon gas at room temperature is 0.1-10Mpa, the reaction temperature is 50-300 ℃, and the reaction time is not less than 1 hour.
6. Use according to claim 5, characterized in that:
wherein the solvent is methanol or a mixture of methanol and one or more than two of ethanol, isopropanol, tert-butanol and toluene in any ratio, and the volume concentration of the methanol in the solvent is 5-100%; the unsaturated hydrocarbon is one or more of C2-C5 olefin, alkyne and dialkene, and the molar ratio of the catalyst active component to the reaction substrate is 1 × 10-4To 1.
7. Use according to claims 5 and 6, characterized in that: the preferred reaction temperature is 120-200 ℃, the preferred initial pressure of the unsaturated hydrocarbon and carbon monoxide in the reaction vessel is 0.5-1.5Mp at room temperature, and the preferred reaction time is 1-6 h.
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