CN117380185A - Dimethyl maleate hydrogenation catalyst and preparation method and application thereof - Google Patents
Dimethyl maleate hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN117380185A CN117380185A CN202210784556.9A CN202210784556A CN117380185A CN 117380185 A CN117380185 A CN 117380185A CN 202210784556 A CN202210784556 A CN 202210784556A CN 117380185 A CN117380185 A CN 117380185A
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- dimethyl maleate
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- carrier
- catalyst
- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 155
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 title claims abstract description 131
- 238000002360 preparation method Methods 0.000 title abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 71
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 21
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 18
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 15
- 244000060011 Cocos nucifera Species 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims 3
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 104
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000003993 interaction Effects 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000002035 prolonged effect Effects 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with 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
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a dimethyl maleate hydrogenation catalyst, which comprises an active component, a first auxiliary agent, a second auxiliary agent, a first component and a carrier; the active component comprises palladium, the carrier is an alumina carrier or an active carbon carrier, and the first component comprises one or two of alkali metal and alkaline earth metal; the catalyst comprises, by weight, 0.3-1.0% of active components, 1.0-3.0% of first auxiliary agents, 0.5-2.0% of second auxiliary agents, 0.5-3.0% of first components and the balance of carriers. The dimethyl maleate hydrogenation catalyst provided by the invention has excellent hydrogenation activity, selectivity and stability. The invention also provides a preparation method of the dimethyl maleate hydrogenation catalyst and application of the dimethyl maleate hydrogenation catalyst.
Description
Technical Field
The invention relates to the technical field of dimethyl maleate hydrogenation catalysts, in particular to a dimethyl maleate hydrogenation catalyst, a preparation method and application thereof.
Background
Dimethyl succinate, abbreviated as DMS, also known as dimethyl succinate, is an important synthetic flavor and food additive, and is also an important chemical intermediate in addition to being an edible preservative. The existing preparation process of the dimethyl succinate mainly uses succinic acid and methanol as raw materials and uses concentrated sulfuric acid as a catalyst to prepare the dimethyl succinate through an esterification reaction, but the preparation process which uses the concentrated sulfuric acid as the catalyst to perform the esterification reaction has the defects of multiple side reactions, low yield, complex post-treatment, serious equipment corrosion, and severe environmental pollution and is capable of producing the dimethyl sulfate with extremely toxic byproducts. The latest technology of dimethyl succinate is to prepare the dimethyl maleate (DMM) and hydrogen by hydrogenation reaction with palladium-carbon catalyst.
The Chinese patent with publication number of CN103657693A discloses a dimethyl maleate hydrogenation catalyst, which is prepared by taking hydrotalcite of nickel type as a carrier and loading other microelements after taking charge of palladium nitrate, and has relatively high cost; the Chinese patent publication No. CN103464153A discloses a hydrogenation catalyst for producing dimethyl succinate and a preparation method thereof, wherein the catalyst takes resin-based spherical active carbon with a micropore structure as a carrier, and adopts a liquid phase precipitation method to load palladium nitrate firstly and then load WO 3 Is prepared by washing, drying and roasting; the Chinese patent publication No. CN102070448A discloses a process for preparing dimethyl succinate, the active component of the catalyst is one or more of VIII group metals, the total content of the active components in the catalyst is 0.2-10wt%, and the carrier is Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 One or more of activated carbon; chinese patent publication No. CN101905160a discloses a catalyst for synthesizing dimethyl succinate and its application, the catalyst is composed of copper, zinc oxide and alumina, the catalyst is prepared by coprecipitation method, the catalyst is powder, the hydrogenated material is dimethyl maleate and solvent methanol with a molar ratio of 1:4, but the performance evaluation of the catalyst is only carried out in micro reaction tube.
The catalyst in the prior art has the technical problems of short service life, poor selectivity and high energy consumption. The catalyst surface carbon can cause the catalyst to be deactivated rapidly, the production efficiency can be influenced by frequent replacement of the catalyst, and the production cost is increased, so that the balance of the hydrogenation activity, the selectivity and the long-period stability of the catalyst becomes a key technical problem to be solved.
Therefore, there is a need to develop a catalyst for hydrogenation of dimethyl maleate, a preparation method and application thereof to solve the above problems in the prior art.
Disclosure of Invention
The invention aims to provide a dimethyl maleate hydrogenation catalyst, a preparation method and application thereof, wherein the dimethyl maleate hydrogenation catalyst obtained by modifying a carrier and optimizing the addition amount of an auxiliary agent has excellent hydrogenation activity, selectivity and stability, the dimethyl maleate hydrogenation catalyst can have better hydrogenation stability in the reaction of preparing dimethyl succinate by hydrogenating the dimethyl maleate under mild use conditions, the hydrogenation reaction is simple and has better industrial application value, and the preparation method of the dimethyl maleate hydrogenation catalyst has the advantages of simple process, convenient operation and easy control.
In order to achieve the aim, the dimethyl maleate hydrogenation catalyst comprises an active component, a first auxiliary agent, a second auxiliary agent, a first component and a carrier;
the active component comprises palladium, the carrier is an alumina carrier or an active carbon carrier, and the first component comprises one or two of alkali metal and alkaline earth metal;
the catalyst comprises, by weight, 0.3-1.0% of active components, 1.0-3.0% of first auxiliary agents, 0.5-2.0% of second auxiliary agents, 0.5-3.0% of first components and the balance of carriers.
The dimethyl maleate hydrogenation catalyst has the beneficial effects that: the dimethyl maleate hydrogenation catalyst comprises an active component, a first auxiliary agent, a second auxiliary agent, a first component and a carrier; the active component comprises palladium, the carrier is an alumina carrier or an active carbon carrier, and the first component comprises one or two of alkali metal and alkaline earth metal; the catalyst comprises, by weight, 0.3-1.0% of active components, 1.0-3.0% of first auxiliary agents, 0.5-2.0% of second auxiliary agents, and 0.5-3.0% of first components, wherein the balance is the carrier, namely, by adding the first components, the acid-base property of the surface of the carrier is improved, the deposition of carbon and colloid in the hydrogenation process is reduced, and the service life of the catalyst for the hydrogenation of the dimethyl maleate is prolonged. By adding the first auxiliary agent, the thermal stability and the chemical stability of the dimethyl maleate hydrogenation catalyst are improved, and the dispersion condition of the active components and the auxiliary agent is improved. Through adding the second auxiliary agent, interaction is generated between the second auxiliary agent and the active component, so that the active component is uniformly distributed on the surface of the carrier, meanwhile, the interaction between the active component and the carrier can be enhanced, and the loss of the active component is reduced, so that the utilization rate of the active component is improved, and the service life of the dimethyl maleate hydrogenation catalyst is prolonged. The content of the active component is 0.3-1.0%, the content of the active component is lower than 0.3% and affects the hydrogenation activity of the dimethyl maleate hydrogenation catalyst in the periodic operation, a higher reaction temperature is required to reach the hydrogenation requirement, and the reaction temperature is too high to affect the selectivity of the dimethyl maleate hydrogenation catalyst, and carbon deposition is easy to occur on the surface of the dimethyl maleate hydrogenation catalyst, so that the hydrogenation stability of the dimethyl maleate hydrogenation catalyst is affected; the content of the active component higher than 1.0% can make the cost of the dimethyl maleate hydrogenation catalyst too high, which is unfavorable for industrial application of the dimethyl maleate hydrogenation catalyst. The dimethyl maleate hydrogenation catalyst provided by the invention has excellent hydrogenation activity, selectivity and stability.
Optionally, the first auxiliary agent comprises one or more than two of boron, phosphorus and silicon.
Optionally, the second auxiliary agent includes one or more of silver, copper, bismuth, nickel and platinum.
Optionally, the first component includes one or more of lithium, potassium, magnesium, and calcium.
Optionally, the content of the first component is 0.5-2.0% based on the weight percentage of the dimethyl maleate hydrogenation catalyst.
Optionally, the crystal form of the alumina in the alumina carrier is any one of a gamma crystal form, a delta crystal form, a gamma and delta mixed crystal form and a delta and theta mixed crystal form.
Optionally, the activated carbon in the activated carbon carrier is any one of wood carbon, shell carbon and coconut shell carbon.
Another object of the present invention is to provide a method for preparing a catalyst for hydrogenation of dimethyl maleate, comprising the steps of:
s0: providing a solution containing an active ingredient, a solution containing a second auxiliary agent, and a solution containing a first ingredient;
s1: mixing a first auxiliary agent and the solution containing the first component with a carrier to obtain a modified carrier;
s2: mixing the solution containing the second auxiliary agent and the solution containing the active component with the modified carrier to obtain the dimethyl maleate hydrogenation catalyst.
The preparation method of the dimethyl maleate hydrogenation catalyst has the beneficial effects that: by adding the first component, the acid-base property of the surface of the carrier is improved, which is favorable for reducing the deposition of carbon and colloid in the hydrogenation process, thereby prolonging the service life of the dimethyl maleate hydrogenation catalyst. By adding the first auxiliary agent, the thermal stability and the chemical stability of the dimethyl maleate hydrogenation catalyst are improved, and the dispersion condition of the active components and the auxiliary agent is improved. By adding a second auxiliary agent, the second auxiliary agent and the active component generate interaction, so that the active component is uniformly distributed on the surface of the carrier; and meanwhile, the interaction between the active component and the carrier can be enhanced, and the loss of the active component is reduced, so that the utilization rate of the active component is improved, and the service life of the dimethyl maleate hydrogenation catalyst is prolonged. The preparation method of the dimethyl maleate hydrogenation catalyst has the advantages of simple process, convenient operation and easy control.
Optionally, the preparation method of the dimethyl maleate hydrogenation catalyst comprises the following steps:
S1: after the first auxiliary agent and pseudo-boehmite are mixed and molded, drying treatment is carried out for 3-8 hours at 110-130 ℃, then roasting treatment is carried out for 3-6 hours at 400-600 ℃ to obtain a mixed carrier, the solution containing the first component is immersed on the mixed carrier, drying treatment is carried out for 3-8 hours at 110-130 ℃, and then roasting treatment is carried out for 3-6 hours at 600-1000 ℃ to obtain the modified carrier;
s2: and immersing the solution containing the second auxiliary agent and the solution containing the active component into the modified carrier, aging for 2-6 hours at room temperature, drying for 3-8 hours at 110-130 ℃, and roasting for 2-6 hours at 300-600 ℃ to obtain the dimethyl maleate hydrogenation catalyst.
Optionally, the preparation method of the dimethyl maleate hydrogenation catalyst comprises the following steps:
s1: providing a solution containing a first auxiliary agent, dipping the solution containing the first auxiliary agent and the solution containing the first component on an active carbon carrier, and drying at 110-130 ℃ for 8-24 hours to obtain the modified carrier;
s2: the solution containing the second auxiliary agent and the solution containing the active component are immersed into the modified carrier and then reduced by a reducing agent for 2-4 hours, firstly, the drying treatment is carried out for 8-24 hours at 110-130 ℃, and then the roasting treatment is carried out for 2-6 hours at 300-600 ℃ in nitrogen atmosphere, so as to obtain the dimethyl maleate hydrogenation catalyst, wherein the immersing time is 20-40 hours.
Yet another object of the invention is toThe application of the dimethyl maleate hydrogenation catalyst is provided, the activated dimethyl maleate hydrogenation catalyst is filled in a fixed bed reactor, hydrogen and a dimethyl maleate solution are introduced into the fixed bed reactor for hydrogenation reaction to obtain dimethyl succinate, the temperature of the hydrogenation reaction is 30-80 ℃, the pressure of the hydrogenation reaction is 1.0-3.0 megapascal, the molar ratio of the hydrogen to the dimethyl maleate is (50-120): 1, and the volume airspeed of the dimethyl maleate solution is 0.5-4.0 hours -1 。
The application of the dimethyl maleate hydrogenation catalyst has the beneficial effects that: under mild use conditions, the reaction for preparing the dimethyl succinate by hydrogenating the dimethyl maleate has better hydrogenation stability, and the hydrogenation reaction is simple and has better industrial application value.
Compared with the prior art, the dimethyl maleate hydrogenation catalyst has the following beneficial effects:
1. the reaction temperature of the dimethyl maleate hydrogenation catalyst in the hydrogenation reaction is low, so that the polymerization of unsaturated matters in raw materials in the hydrogenation reaction can be inhibited; the dimethyl maleate hydrogenation catalyst has the advantages of high hydrogenation activity, good chemical stability and thermal stability, low carbon deposit amount and long service life.
2. According to the dimethyl maleate hydrogenation catalyst, the surface of the carrier is modified by the first component, so that the pH value of the surface of the carrier is improved, and the deposition of carbon and colloid in hydrogenation reaction is reduced, so that the service life of the dimethyl maleate hydrogenation catalyst is prolonged.
3. The dimethyl maleate hydrogenation catalyst is a bimetallic or multi-metal catalyst, and the strong interaction between metals can inhibit the adsorption between unsaturated bonds and active components, so that the loss of the active components is effectively reduced, and the service life of the dimethyl maleate hydrogenation catalyst is prolonged.
4. The preparation process of the dimethyl maleate hydrogenation catalyst is simple and the cost is low. When the catalyst is used for the hydrogenation of the dimethyl maleate, a fixed bed hydrogenation process is adopted, the reaction condition is mild, the operation process is simple, and the catalyst is beneficial to industrial application.
Drawings
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. As used herein, the word "comprising" and the like means that elements or items preceding the word are included in the element or item listed after the word and equivalents thereof without precluding other elements or items.
When the catalyst is used for the hydrogenation reaction of dimethyl maleate, the polymerization reaction of unsaturated substances on the surface of the catalyst is one of the main reasons for causing the deactivation of the catalyst. On one hand, double bonds in the dimethyl maleate are easy to polymerize to form colloid, and the colloid covers the hydrogenation active center of the catalyst, so that the number of active centers on the surface of the catalyst is reduced; on the other hand, the resulting polymer plugs the catalyst channels, affecting the diffusion of the reactants and resultant molecules. Therefore, the hydrogenation activity and the hydrogenation stability of the catalyst can be improved by adjusting the acidity and alkalinity of the catalyst surface, and the acidity and alkalinity of the catalyst carrier surface can be improved by adding alkali metal and/or alkaline earth metal, which is beneficial to reducing the deposition of carbon and colloid in the hydrogenation process, thereby prolonging the service life of the catalyst.
Since palladium as an active component is easy to carry out complexation reaction with unsaturated bonds, the palladium as the active component is gradually lost, and the catalyst is deactivated. The second auxiliary agent added in the invention can generate interaction with the active component palladium, is beneficial to the uniform distribution of the active component palladium particles on the surface of the carrier, can enhance the interaction between the active component palladium and the carrier, and reduces the loss of the active component palladium, thereby improving the utilization rate of the active component palladium and prolonging the service life of the catalyst.
Aiming at the problems existing in the prior art, the embodiment of the invention provides a dimethyl maleate hydrogenation catalyst which comprises an active component, a first auxiliary agent, a second auxiliary agent, a first component and a carrier;
the active component comprises palladium, the carrier is an alumina carrier or an active carbon carrier, and the first component comprises one or two of alkali metal and alkaline earth metal;
the catalyst comprises, by weight, 0.3-1.0% of active components, 1.0-3.0% of first auxiliary agents, 0.5-2.0% of second auxiliary agents, 0.5-3.0% of first components and the balance of carriers. By adding the first component, the acid-base property of the surface of the carrier is improved, which is favorable for reducing the deposition of carbon and colloid in the hydrogenation process, thereby prolonging the service life of the dimethyl maleate hydrogenation catalyst. By adding the first auxiliary agent, the thermal stability and the chemical stability of the dimethyl maleate hydrogenation catalyst are improved, and the dispersion condition of the active components and the auxiliary agent is improved. By adding a second auxiliary agent, the second auxiliary agent and the active component generate interaction, so that the active component is uniformly distributed on the surface of the carrier; and meanwhile, the interaction between the active component and the carrier can be enhanced, and the loss of the active component is reduced, so that the utilization rate of the active component is improved, and the service life of the dimethyl maleate hydrogenation catalyst is prolonged. The content of the active component is 0.3-1.0%, the content of the active component is lower than 0.3% and affects the hydrogenation activity of the dimethyl maleate hydrogenation catalyst in the periodic operation, a higher reaction temperature is required to reach the hydrogenation requirement, and the reaction temperature is too high to affect the selectivity of the dimethyl maleate hydrogenation catalyst, and carbon deposition is easy to occur on the surface of the dimethyl maleate hydrogenation catalyst, so that the hydrogenation stability of the dimethyl maleate hydrogenation catalyst is affected; the content of the active component higher than 1.0% can make the cost of the dimethyl maleate hydrogenation catalyst too high, which is unfavorable for industrial application of the dimethyl maleate hydrogenation catalyst. The dimethyl maleate hydrogenation catalyst provided by the invention has excellent hydrogenation activity, selectivity and stability.
In some embodiments of the invention, the active ingredient is a soluble salt.
In some embodiments of the invention, the active component is palladium chloride, palladium nitrate or palladium acetate.
In some embodiments of the invention, the first auxiliary agent includes one or more of boron, phosphorus and silicon.
In some embodiments of the invention, the first auxiliary agent is a mineral acid or a soluble salt.
In some embodiments of the present invention, the first auxiliary agent is phosphoric acid, silica sol, or boric acid.
In some embodiments of the invention, the second promoter comprises one or more of silver, copper, bismuth, nickel, and platinum.
In some embodiments of the invention, the second aid is a soluble salt.
In some embodiments of the present invention, the second auxiliary agent is nitrate or acetate.
In some embodiments of the invention, the first component comprises one or more of lithium, potassium, magnesium, and calcium.
In some embodiments of the invention, the first component is a soluble salt.
In some embodiments of the invention, the first component is nitrate or acetate.
In some embodiments of the present invention, the first component is present in an amount of 0.5 to 2.0% by weight of the dimethyl maleate hydrogenation catalyst.
In some embodiments of the present invention, the crystal form of the alumina in the alumina carrier is any one of a gamma crystal form, a delta crystal form, a gamma and delta mixed crystal form, and a delta and theta mixed crystal form.
In some embodiments of the invention, the alumina support has a specific surface area of 100 to 300 square meters per gram.
In some embodiments of the invention, the alumina support is in the shape of a sphere or clover strip, the diameter of the sphere is 2-3 mm, and the size of the clover strip is phi 2 x 3-8 mm.
In some embodiments of the present invention, the activated carbon in the activated carbon carrier is any one of wood carbon, shell carbon, and coconut shell carbon.
In some embodiments of the invention, the activated carbon support has a specific surface area of 600 to 1000 square meters per gram.
In some embodiments of the invention, the activated carbon support is irregularly shaped.
The embodiment of the invention provides a preparation method of a dimethyl maleate hydrogenation catalyst, which comprises the following steps:
s0: providing a solution containing an active ingredient, a solution containing a second auxiliary agent, and a solution containing a first ingredient;
s1: mixing a first auxiliary agent and the solution containing the first component with a carrier to obtain a modified carrier;
S2: mixing the solution containing the second auxiliary agent and the solution containing the active component with the modified carrier to obtain the dimethyl maleate hydrogenation catalyst. By adding the first component, the acid-base property of the surface of the carrier is improved, which is favorable for reducing the deposition of carbon and colloid in the hydrogenation process, thereby prolonging the service life of the dimethyl maleate hydrogenation catalyst. By adding the first auxiliary agent, the thermal stability and the chemical stability of the dimethyl maleate hydrogenation catalyst are improved, and the dispersion condition of the active components and the auxiliary agent is improved. By adding a second auxiliary agent, the second auxiliary agent and the active component generate interaction, so that the active component is uniformly distributed on the surface of the carrier; and meanwhile, the interaction between the active component and the carrier can be enhanced, and the loss of the active component is reduced, so that the utilization rate of the active component is improved, and the service life of the dimethyl maleate hydrogenation catalyst is prolonged. The preparation method of the dimethyl maleate hydrogenation catalyst has the advantages of simple process, convenient operation and easy control.
In some embodiments of the invention, the method for preparing the dimethyl maleate hydrogenation catalyst comprises the following steps:
s1: after the first auxiliary agent and pseudo-boehmite are mixed and molded, drying treatment is carried out for 3-8 hours at 110-130 ℃, then roasting treatment is carried out for 3-6 hours at 400-600 ℃ to obtain a mixed carrier, the solution containing the first component is immersed on the mixed carrier, drying treatment is carried out for 3-8 hours at 110-130 ℃, and then roasting treatment is carried out for 3-6 hours at 600-1000 ℃ to obtain the modified carrier;
s2: and immersing the solution containing the second auxiliary agent and the solution containing the active component into the modified carrier, aging for 2-6 hours at room temperature, drying for 3-8 hours at 110-130 ℃, and roasting for 2-6 hours at 300-600 ℃ to obtain the dimethyl maleate hydrogenation catalyst.
In some embodiments of the present invention, the impregnation is performed by a conventional impregnation method, and the solution containing the second auxiliary agent and the solution containing the active ingredient may be impregnated into the modified carrier by a co-impregnation method or may be impregnated into the modified carrier by a distributed impregnation method.
In some embodiments of the present invention, the preparation method of the dimethyl maleate hydrogenation catalyst includes the following steps:
s1: providing a solution containing a first auxiliary agent, dipping the solution containing the first auxiliary agent and the solution containing the first component on an active carbon carrier, and drying at 110-130 ℃ for 8-24 hours to obtain the modified carrier;
s2: the solution containing the second auxiliary agent and the solution containing the active component are immersed into the modified carrier and then reduced by a reducing agent for 2-4 hours, firstly, the drying treatment is carried out for 8-24 hours at 110-130 ℃, and then the roasting treatment is carried out for 2-6 hours at 300-600 ℃ in nitrogen atmosphere, so as to obtain the dimethyl maleate hydrogenation catalyst, wherein the immersing time is 20-40 hours.
In some embodiments of the present invention, the impregnation adopts a conventional impregnation method, and the solution containing the first auxiliary agent and the solution containing the first component may be impregnated onto the activated carbon carrier by a co-impregnation method, or may be impregnated onto the activated carbon carrier by a distributed impregnation method; the solution containing the second auxiliary agent and the solution containing the active component can be impregnated on the modified carrier by adopting a co-impregnation method, and can also be impregnated on the modified carrier by adopting a distribution impregnation method.
In some embodiments of the invention, the reducing agent is any one of sodium formate and hydrazine hydrate.
The embodiment of the invention provides an application of the dimethyl maleate hydrogenation catalyst, wherein the activated dimethyl maleate hydrogenation catalyst is filled in a fixed bed reactor, hydrogen and a dimethyl maleate solution are introduced into the fixed bed reactor for hydrogenation reaction to obtain dimethyl succinate, the temperature of the hydrogenation reaction is 30-80 ℃, the pressure of the hydrogenation reaction is 1.0-3.0 megapascal, the molar ratio of the hydrogen to the dimethyl maleate is (50-120): 1, and the volume airspeed of the dimethyl maleate solution is 0.5-4.0 hours -1 . Under mild use conditions, the reaction for preparing the dimethyl succinate by hydrogenating the dimethyl maleate has better hydrogenation stability, and the hydrogenation reaction is simple and has better industrial application value.
Example 1
Preparation of catalyst C1:
preparing a magnesium nitrate solution, a palladium chloride solution and a silver nitrate solution;
mixing and kneading pseudo-boehmite, sesbania powder, phosphoric acid, acetic acid and water, extruding strips, forming, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 4 hours to obtain a mixed carrier, soaking the magnesium nitrate solution on the mixed carrier in an equal volume, drying at 120 ℃ for 3 hours, and roasting at 850 ℃ for 3 hours to obtain a modified carrier, wherein the modified carrier is an alumina carrier containing phosphorus and magnesium, and the crystal forms of alumina in the alumina carrier are gamma and delta mixed crystal forms;
Immersing 100 g of the modified carrier into the palladium chloride solution, boiling for 20 minutes, removing residual liquid, washing with distilled water, aging at room temperature for 2 hours, drying at 120 ℃ for 4 hours, and roasting at 400 ℃ for 4 hours; the silver nitrate solution is immersed on the modified carrier containing palladium, and is dried for 4 hours at 120 ℃, and then is roasted for 4 hours at 450 ℃ to obtain a catalyst C1, wherein the content of Pd is 0.45%, the content of P is 2.0%, the content of Mg is 1.0% and the content of Ag is 0.8% based on the weight percentage of the catalyst C1. The specific surface area of the catalyst C1 is 174 square meters per gram, and the pore volume is 0.62 milliliter per gram.
Preparation of catalyst C2:
preparing a lithium nitrate solution, a palladium nitrate solution and a nickel nitrate solution;
mixing and kneading pseudo-boehmite, sesbania powder, silica sol, acetic acid and water, extruding strips, forming, drying at 120 ℃ for 4 hours, roasting at 450 ℃ for 4 hours to obtain a mixed carrier, soaking the lithium nitrate solution on the mixed carrier in an equal volume, drying at 120 ℃ for 3 hours, and roasting at 650 ℃ for 4 hours to obtain a modified carrier, wherein the modified carrier is an alumina carrier containing silicon and lithium, and the crystal form of alumina in the alumina carrier is gamma crystal form;
Immersing 100 g of the modified carrier into the palladium nitrate solution, immersing in an equal volume, washing with water, aging for 3 hours at room temperature, drying for 5 hours at 120 ℃, and roasting for 4 hours at 450 ℃; the nickel nitrate solution is immersed on the modified carrier containing palladium in an equal volume, is dried at 120 ℃ for 4 hours, and is baked at 500 ℃ for 3 hours to obtain a catalyst C2, wherein the content of Pd is 0.5%, the content of Si is 1.5%, the content of Li is 0.5% and the content of Ni is 1.5% based on the weight percentage of the catalyst C2. The specific surface area of the catalyst C2 is 262 square meters per gram, and the pore volume is 0.56 milliliter per gram.
Preparation of catalyst C3:
preparing a monopotassium phosphate solution and a mixed solution, wherein the mixed solution comprises a palladium chloride solution and a platinum chloride solution;
mixing and kneading pseudo-boehmite, sesbania powder, acetic acid and water, extruding strips, forming, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 4 hours to obtain a mixed carrier, soaking the mixed carrier with the monopotassium phosphate solution in an equal volume, drying at 120 ℃ for 3 hours, and roasting at 950 ℃ for 4 hours to obtain a modified carrier, wherein the modified carrier is an alumina carrier containing phosphorus and potassium, and the alumina in the alumina carrier is in a delta and theta mixed crystal form;
Immersing 100 g of the modified carrier into the mixed solution, boiling for 20 minutes, removing residual liquid, washing with distilled water, ageing at room temperature for 5 hours, drying at 120 ℃ for 5 hours, and roasting at 450 ℃ for 4 hours to obtain a catalyst C3, wherein the content of Pd is 0.3%, the content of P is 1.0%, the content of K is 1.5% and the content of Pt is 0.7% based on the weight percentage of the catalyst C3. The specific surface area of the catalyst C3 is 115 square meters per gram, and the pore volume is 0.57 milliliter per gram.
Preparation of catalyst C4:
preparing a calcium nitrate solution and a mixed solution, wherein the mixed solution comprises a palladium nitrate solution and a copper nitrate solution;
mixing and kneading pseudo-boehmite, sesbania powder, boric acid, acetic acid and water, extruding strips, forming, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 4 hours to obtain a mixed carrier, soaking the mixed carrier with the calcium nitrate solution in an equal volume, drying at 120 ℃ for 3 hours, and roasting at 900 ℃ for 4 hours to obtain a modified carrier, wherein the modified carrier is an alumina carrier containing boron and calcium, and the crystal form of alumina in the alumina carrier is delta crystal form;
Immersing 100 g of the modified carrier into the mixed solution, soaking in an equal volume, washing with water, aging for 6 hours at room temperature, drying for 5 hours at 120 ℃, and roasting for 4 hours at 400 ℃ to obtain a catalyst C4, wherein the content of Pd is 0.6%, the content of B is 1.5%, the content of Ca is 2.0% and the content of Cu is 1.0% based on the weight percentage of the catalyst C4. The specific surface area of the catalyst C4 is 135 square meters per gram, and the pore volume is 0.59 milliliter per gram.
Preparation of catalyst C5:
preparing a magnesium nitrate solution, a palladium chloride solution and a nickel nitrate solution;
mixing and kneading pseudo-boehmite, sesbania powder, silica sol, acetic acid and water, extruding strips, forming, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 4 hours to obtain a mixed carrier, soaking the mixed carrier with the magnesium nitrate solution in an equal volume, drying at 120 ℃ for 3 hours, and roasting at 1000 ℃ for 4 hours to obtain a modified carrier, wherein the modified carrier is an alumina carrier containing silicon and magnesium, and the alumina in the alumina carrier is in a delta and theta mixed crystal form;
Immersing 100 g of the modified carrier into the palladium chloride solution, boiling for 20 minutes, removing residual liquid, washing with distilled water, aging at room temperature for 4 hours, drying at 120 ℃ for 4 hours, and roasting at 450 ℃ for 4 hours; the nickel nitrate solution is immersed on the modified carrier containing palladium, and is dried for 4 hours at 120 ℃, and then is roasted for 4 hours at 550 ℃ to obtain a catalyst C5, wherein the content of Pd is 1.0%, the content of Si is 1.0%, the content of Mg is 2.8% and the content of Ni is 0.5% in percentage by weight of the catalyst C5. The specific surface area of the catalyst C5 is 103 square meters per gram, and the pore volume is 0.55 milliliter per gram.
Preparation of catalyst C6:
preparing a phosphoric acid solution, a potassium nitrate solution and a mixed solution, wherein the mixed solution comprises a palladium nitrate solution and a silver nitrate solution;
putting coconut shell carbon into the phosphoric acid solution for treatment for 4 hours, washing the coconut shell carbon to be neutral by deionized water, and drying the coconut shell carbon at 120 ℃ for 12 hours to obtain a modified carrier;
treating the modified carrier with the potassium nitrate solution, and drying at 110 ℃ for 16 hours; immersing 100 g of the modified carrier treated by the potassium nitrate solution into the mixed solution, immersing for 24 hours in an equal volume, reducing by using a sodium formate solution, wherein the reduction time is 3 hours, washing to neutrality by using deionized water, drying at 120 ℃ for 5 hours, roasting at 450 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst C6, wherein the content of Pd is 0.5%, the content of P is 2.0%, the content of K is 1.5% and the content of Ag is 1.0% based on the weight percentage of the catalyst C8. The specific surface area of catalyst C6 was 976 square meters per gram.
Preparation of catalyst C7:
preparing boric acid solution, magnesium nitrate solution and mixed solution, wherein the mixed solution comprises palladium chloride solution and platinum chloride solution;
putting the coconut shell carbon into the boric acid solution for treatment for 5 hours, washing the coconut shell carbon to be neutral by deionized water, and drying the coconut shell carbon at 120 ℃ for 8 hours to obtain a modified carrier;
treating the modified carrier with the magnesium nitrate solution, and drying at 120 ℃ for 10 hours; immersing 100 g of the modified carrier treated by the magnesium nitrate solution into the mixed solution, immersing for 36 hours in an equal volume, reducing by using a sodium formate solution, wherein the reduction time is 4 hours, washing to neutrality by using deionized water, drying at 120 ℃ for 6 hours, roasting at 500 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst C7, wherein the content of Pd is 0.35%, the content of B is 3.0%, the content of Mg is 2.8% and the content of Pt is 0.5% based on the weight percentage of the catalyst C8. The specific surface area of catalyst C7 was 828 square meters per gram.
Preparation of catalyst C8:
preparing a phosphoric acid solution, a lithium nitrate solution and a mixed solution, wherein the mixed solution comprises a palladium nitrate solution and a copper nitrate solution;
Putting coconut shell carbon into the phosphoric acid solution for treatment for 5 hours, washing the coconut shell carbon to be neutral by deionized water, and drying the coconut shell carbon at 120 ℃ for 8 hours to obtain a modified carrier;
treating the modified carrier with the lithium nitrate solution, and drying at 110 ℃ for 10 hours; immersing 100 g of the modified carrier treated by the lithium nitrate solution into the mixed solution, immersing for 32 hours in an equal volume, reducing by using a hydrazine hydrate solution, wherein the reduction time is 3 hours, washing to neutrality by using deionized water, drying at 120 ℃ for 6 hours, roasting at 400 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst C8, wherein the content of Pd is 0.4%, the content of P is 1.6%, the content of Li is 0.5% and the content of Cu is 2.0% based on the weight percentage of the catalyst C8. The specific surface area of catalyst C8 was 876 square meters per gram.
Preparation of catalyst C9:
preparing boric acid solution, calcium nitrate solution, palladium chloride solution and bismuth nitrate solution;
putting the coconut shell carbon into the boric acid solution for treatment for 6 hours, washing the coconut shell carbon to be neutral by deionized water, and drying the coconut shell carbon at 120 ℃ for 8 hours to obtain a modified carrier;
treating the modified carrier with the calcium nitrate solution, and drying at 120 ℃ for 8 hours; immersing 100 g of the modified carrier treated by the calcium nitrate solution into the palladium chloride solution, immersing for 30 hours in an equal volume, reducing by using a hydrazine hydrate solution for 2 hours, washing to be neutral by using deionized water, and drying at 120 ℃ for 8 hours; then soaking in bismuth nitrate solution for 20 hours in a medium volume, drying at 120 ℃ for 10 hours, roasting at 350 ℃ for 4 hours in a nitrogen atmosphere to obtain a catalyst C9, wherein the catalyst C9 comprises 0.45% of Pd, 2.2% of B, 1.2% of Ca and 1.5% of Bi by weight percent. The specific surface area of catalyst C9 was 932 square meters per gram.
Comparative example 1
The catalyst D1 was prepared as described in example 2 of the Chinese patent publication No. CN103657693A, the palladium content of the catalyst D1 was 0.5%, moO 3 The content of (2) was 5.0%.
Preparation of catalyst D2:
the catalyst D2 was prepared as described in example 2 of the Chinese patent publication No. CN103464153A, the palladium content of the catalyst D2 was 0.5%, WO 3 The content of (2) was 3.0%.
Preparation of catalyst D3:
the catalyst D3 is prepared by a conventional impregnation method in China patent with the publication number of CN102070448A, and the composition of the catalyst D3 is 0.4% Pd/C.
Example 2 evaluation of catalyst
Activation of the catalyst: the catalyst C1-C9, the catalyst D1-D3 and the industrial catalyst are reduced by hydrogen for 6-10 hours at 120-150 ℃ and then are applied to the hydrogenation reaction of the dimethyl maleate.
Hydrogenation reaction: the activated catalysts C1-C9, the activated catalysts D1-D3 and the activated industrial catalyst are respectively filled in a fixed bed reactor, hydrogen and a dimethyl maleate solution are introduced into the fixed bed reactor for hydrogenation reaction to obtain dimethyl succinate, the temperature of the hydrogenation reaction is 50 ℃, the pressure of the hydrogenation reaction is 1.0 megapascal, the molar ratio of the hydrogen to the dimethyl maleate is 50:1, and the volume space velocity of the dimethyl maleate solution is 3.0 hours -1 The loading of the activated catalysts C1 to C9, the activated catalysts D1 to D3 and the activated industrial catalyst is 50 ml. The dimethyl maleate is industrial dimethyl maleate.
The evaluation criteria for the catalyst were: the catalyst deactivation was found to be a conversion of less than 90% of dimethyl maleate (DMM).
The hydrogenation results for catalysts C1 to C9 in the examples and catalysts D1 to D3 in the comparative examples are shown in Table 1.
Table 1 evaluation results of catalysts
Note that: DMM is dimethyl maleate, DMS is dimethyl succinate; average conversion: sampling and analyzing every 4 hours within 200 hours of running time, taking 50 samples for analysis, wherein the average value of the conversion rate of the 50 samples is the average conversion rate; average selectivity: during the operation time of 200 hours, sampling analysis is performed every 4 hours, 50 samples are taken for analysis, and the average value of the selectivity of the 50 samples is the average selectivity.
As can be seen from the data in Table 1, the average conversion of DMM of catalysts C1 to C9 was 99.5% or more, the average selectivity of DMS of catalysts C1 to C9 was 99.6% or more, and the average conversion of DMM of catalysts D1 to D3 and industrial catalyst was 89.2% or less, and the average conversion of DMM of catalysts D1 to D3 and industrial catalyst was 94.5% or less, whereby it was found that the dimethyl maleate hydrogenation catalyst of the present invention was excellent in hydrogenation performance.
Activation of catalyst C2 and commercial catalyst: both the catalyst C2 and the commercial catalyst were reduced with hydrogen at 150 degrees celsius for 5 hours.
Hydrogenation reaction: the activated catalyst C2 and the activated industrial catalyst are respectively filled in a fixed bed reactor, hydrogen and a dimethyl maleate solution are introduced into the fixed bed reactor for hydrogenation reaction to obtain dimethyl succinate, the temperature of the hydrogenation reaction is 60 ℃, the pressure of the hydrogenation reaction is 2.0 megapascals, the molar ratio of the hydrogen to the dimethyl maleate is 70:1, the filling amounts of the catalyst C2 and the industrial catalyst are 50 milliliters, and the volume space velocity of the dimethyl maleate solution is 1.0 hour -1 The catalyst C2 and the industrial catalyst were subjected to 1000h long period comparative evaluation, and the average value of the 1000h hydrogenation results is shown in Table 2.
TABLE 2 evaluation results of catalyst C2 and commercial catalyst
| Catalyst | Run time/hour | Average conversion of DMM/% | Mean selectivity/% |
| C2 | 1000 | 99.7 | 99.6 |
| Industrial catalyst | 1000 | 82.2 | 87.5 |
Note that: DMM is dimethyl maleate and DMS is dimethyl succinate.
Compared with the prior art, the preparation process of the dimethyl maleate hydrogenation catalyst is simple, and the hydrogenation reaction has mild process conditions. The dimethyl maleate hydrogenation catalyst not only has higher hydrogenation activity and selectivity, but also has excellent long-period stability, and is suitable for industrial application. And the dimethyl maleate hydrogenation catalyst is a supported catalyst, and the hydrogenation reaction is carried out by using a fixed bed reactor, so that the fixed bed reactor has strong adaptability to process conditions, is convenient to produce and operate, and is particularly simple in loading and unloading, reduction and startup operation of the catalyst, and easy to industrialize.
And (3) carrying out analysis test on the palladium content of the catalyst C2 and the industrial catalyst after long period evaluation, wherein an instrument for the analysis test is a plasma photoelectric direct-reading spectrometer (ICP), and the results of the analysis test are shown in Table 3, so that the active component palladium is not basically lost.
TABLE 3 Palladium content of catalyst C2 and commercial catalyst before and after operation
| Palladium content/% | Palladium content/% | Theoretical palladium content/% | |
| Catalyst C2 | 0.495 | 0.492 | 0.50 |
| Industrial catalyst | 0.494 | 0.404 | 0.50 |
Note that: the percentage of the palladium content is weight percentage; the theoretical palladium content is common knowledge in the art and will not be described in detail herein.
The dimethyl maleate hydrogenation catalyst provided by the invention has the advantages that after 1000h long-period evaluation, the palladium content of the active component is not obviously reduced, which indicates that the interaction among the components obviously inhibits the loss of the palladium content of the active component, and the dimethyl maleate hydrogenation catalyst can resist the scouring of long-time reaction materials, and is proved to have better hydrogenation performance again.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (11)
1. The dimethyl maleate hydrogenation catalyst is characterized by comprising an active component, a first auxiliary agent, a second auxiliary agent, a first component and a carrier;
the active component comprises palladium, the carrier is an alumina carrier or an active carbon carrier, and the first component comprises one or two of alkali metal and alkaline earth metal;
the catalyst comprises, by weight, 0.3-1.0% of active components, 1.0-3.0% of first auxiliary agents, 0.5-2.0% of second auxiliary agents, 0.5-3.0% of first components and the balance of carriers.
2. The dimethyl maleate hydrogenation catalyst according to claim 1 wherein the first promoter comprises one or more of boron, phosphorus and silicon.
3. The dimethyl maleate hydrogenation catalyst according to claim 1 wherein the second promoter comprises one or more of silver, copper, bismuth, nickel and platinum.
4. The dimethyl maleate hydrogenation catalyst according to claim 1 wherein the first component comprises one or more of lithium, potassium, magnesium and calcium.
5. The dimethyl maleate hydrogenation catalyst according to claim 1 wherein the first component is present in an amount of from 0.5 to 2.0% by weight of the dimethyl maleate hydrogenation catalyst.
6. The dimethyl maleate hydrogenation catalyst according to claim 1 wherein the alumina of the alumina support is in any of the gamma, delta, gamma and delta mixed and delta and theta mixed forms.
7. The dimethyl maleate hydrogenation catalyst according to claim 1, wherein the activated carbon in the activated carbon support is any of wood charcoal, fruit shell charcoal and coconut shell charcoal.
8. A process for preparing a dimethyl maleate hydrogenation catalyst as claimed in any of claims 1 to 7 comprising the steps of:
s0: providing a solution containing an active ingredient, a solution containing a second auxiliary agent, and a solution containing a first ingredient;
s1: mixing a first auxiliary agent and the solution containing the first component with a carrier to obtain a modified carrier;
s2: mixing the solution containing the second auxiliary agent and the solution containing the active component with the modified carrier to obtain the dimethyl maleate hydrogenation catalyst.
9. The method for preparing the dimethyl maleate hydrogenation catalyst according to claim 8, comprising the steps of:
s1: after the first auxiliary agent and pseudo-boehmite are mixed and molded, drying treatment is carried out for 3-8 hours at 110-130 ℃, then roasting treatment is carried out for 3-6 hours at 400-600 ℃ to obtain a mixed carrier, the solution containing the first component is immersed on the mixed carrier, drying treatment is carried out for 3-8 hours at 110-130 ℃, and then roasting treatment is carried out for 3-6 hours at 600-1000 ℃ to obtain the modified carrier;
s2: and immersing the solution containing the second auxiliary agent and the solution containing the active component into the modified carrier, aging for 2-6 hours at room temperature, drying for 3-8 hours at 110-130 ℃, and roasting for 2-6 hours at 300-600 ℃ to obtain the dimethyl maleate hydrogenation catalyst.
10. The method for preparing the dimethyl maleate hydrogenation catalyst according to claim 8, comprising the steps of:
s1: providing a solution containing a first auxiliary agent, dipping the solution containing the first auxiliary agent and the solution containing the first component on an active carbon carrier, and drying at 110-130 ℃ for 8-24 hours to obtain the modified carrier;
S2: the solution containing the second auxiliary agent and the solution containing the active component are immersed into the modified carrier and then reduced by a reducing agent for 2-4 hours, firstly, the drying treatment is carried out for 8-24 hours at 110-130 ℃, and then the roasting treatment is carried out for 2-6 hours at 300-600 ℃ in nitrogen atmosphere, so as to obtain the dimethyl maleate hydrogenation catalyst, wherein the immersing time is 20-40 hours.
11. The use of the catalyst for the hydrogenation of dimethyl maleate according to any of claims 1 to 7, wherein the activated catalyst for the hydrogenation of dimethyl maleate is filled in a fixed bed reactor, hydrogen and a solution of dimethyl maleate are introduced into the fixed bed reactor for the hydrogenation reaction to obtain dimethyl succinate, the temperature of the hydrogenation reaction is 30 to 80 ℃, the pressure of the hydrogenation reaction is 1.0 to 3.0 megapascals, the molar ratio of the hydrogen to the dimethyl maleate is (50 to 120): 1, and the volume space velocity of the solution of dimethyl maleate is 0.5 to 4.0 hours -1 。
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