CN115007172B - Preparation method and application of dimethyl oxalate selective hydrogenation catalyst - Google Patents
Preparation method and application of dimethyl oxalate selective hydrogenation catalyst Download PDFInfo
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- CN115007172B CN115007172B CN202210875788.5A CN202210875788A CN115007172B CN 115007172 B CN115007172 B CN 115007172B CN 202210875788 A CN202210875788 A CN 202210875788A CN 115007172 B CN115007172 B CN 115007172B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000010949 copper Substances 0.000 claims abstract description 56
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims description 31
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims description 29
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001879 copper Chemical class 0.000 claims description 11
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 238000004817 gas chromatography Methods 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 7
- 208000012839 conversion disease Diseases 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000003378 silver Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 229940071575 silver citrate Drugs 0.000 claims description 5
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 5
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 3
- HXXRDHUDBAILGK-UHFFFAOYSA-L copper;2-hydroxyacetate Chemical compound [Cu+2].OCC([O-])=O.OCC([O-])=O HXXRDHUDBAILGK-UHFFFAOYSA-L 0.000 claims description 3
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- HCRZXNOSPPHATK-UHFFFAOYSA-L copper;3-oxobutanoate Chemical compound [Cu+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HCRZXNOSPPHATK-UHFFFAOYSA-L 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims 2
- 230000001133 acceleration Effects 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 129
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000011258 core-shell material Substances 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000004581 coalescence Methods 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 239000006004 Quartz sand Substances 0.000 description 12
- 239000002114 nanocomposite Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- -1 nitrous acid ester Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- YAGHEUQOAPDHKS-UHFFFAOYSA-N dimethyl oxalate;methanol Chemical compound OC.COC(=O)C(=O)OC YAGHEUQOAPDHKS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 1
- YUUKIOKWOBAUSK-UHFFFAOYSA-L [OH-].[OH-].[Cu+2].NCCN Chemical compound [OH-].[OH-].[Cu+2].NCCN YUUKIOKWOBAUSK-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 description 1
- FGUOYHAMMRMUQO-UHFFFAOYSA-L copper;4-cyclohexylbutanoate Chemical compound [Cu+2].[O-]C(=O)CCCC1CCCCC1.[O-]C(=O)CCCC1CCCCC1 FGUOYHAMMRMUQO-UHFFFAOYSA-L 0.000 description 1
- WFIPUECTLSDQKU-UHFFFAOYSA-N copper;ethyl 3-oxobutanoate Chemical compound [Cu].CCOC(=O)CC(C)=O WFIPUECTLSDQKU-UHFFFAOYSA-N 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BXLNWOAYQXBHCY-UHFFFAOYSA-N diphenylsilylidene(diphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)=[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BXLNWOAYQXBHCY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical class COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- RUJQWQMCBPWFDO-UHFFFAOYSA-M silver;2-hydroxyacetate Chemical compound [Ag+].OCC([O-])=O RUJQWQMCBPWFDO-UHFFFAOYSA-M 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- JIKVETCBELSHNU-UHFFFAOYSA-M silver;3-oxobutanoate Chemical compound [Ag+].CC(=O)CC([O-])=O JIKVETCBELSHNU-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/8926—Copper and noble 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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 discloses a preparation method and application of a dimethyl oxalate selective hydrogenation catalyst. The preparation process of the catalyst is simple, the active nano copper is uniformly dispersed, ag clusters are deposited on the surface of the catalyst to improve stability, migration and coalescence of copper in the use process of the catalyst are effectively prevented, and a synergistic coupling pore canal effect is generated between the silicon dioxide core-shell structures, so that the activity and the thermal stability of the Ag-CuNPS are further improved. The catalyst prepared by the invention can be used for selectively hydrogenating dimethyl oxalate, the reaction conditions are changed according to production requirements, and the co-production of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) is realized by only one catalyst in the same device, so that the catalyst has important significance and value and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method and application of a dimethyl oxalate selective hydrogenation catalyst.
Background
With the increasing prominence of energy crisis and environmental concerns, there is an urgent need to find catalytic methods for clean utilization of coal, plant resources and further synthesis of high value-added chemicals to meet the needs of havingChallenging environmental requirements and industrialization requirements; the energy structure of 'rich coal and less oil' in China determines the important development direction of developing a coal high-efficiency utilization technology to replace a petroleum route. Meanwhile, china is a large agricultural country, and huge amounts of plant straws, coal and straws are produced into synthesis gas (H) 2 +CO), and then the synthesis gas with wide sources is coupled with nitrous acid ester to obtain dimethyl oxalate, and Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) are prepared by catalytic selective hydrogenation of the dimethyl oxalate (DMO), so that the method is a more economical and environment-friendly non-petroleum-based route, and has great economic benefit and broad market prospect.
Methyl Glycolate (MG) contains two functional groups of hydroxyl and ester, so that the methyl glycolate has the chemical properties of alcohol and ester, has good biocompatibility and degradability, and is widely applied to the fields of chemical industry, medicines, fragrances and high polymer materials (such as PGA). The preparation method comprises a formaldehyde carbonyl method, a methyl formate coupling method, chloroacetate hydrolysis and the like, and compared with the process for preparing methyl glycolate by semi-hydrogenation of dimethyl oxalate (DMO), the preparation method has the advantages of low cost and environmental protection, and has the most development prospect.
Ethylene Glycol (EG) is an important chemical raw material (such as antifreeze, lubricant, plasticizer, surfactant, polyester and the like) used in many industrial processes, and has various commercial applications, wherein the coupling of synthesis gas and nitrous acid ester to generate dimethyl oxalate (DMO), and then the total hydrogenation of dimethyl oxalate (DMO) to generate Ethylene Glycol (EG) are important schemes for the high-value utilization of coal and plant straws.
Ethanol (EtOH) has been used in ethanol gasoline, and industrial ethanol is deeply hydrogenated from dimethyl oxalate (DMO) to ethanol (EtOH), effectively relieving the pressure of ethanol production by fermentation.
Semi-hydrogenating dimethyl oxalate (DMO) to generate Methyl Glycolate (MG); fully hydrogenating to obtain Ethylene Glycol (EG); deep processing to produce ethanol. Therefore, the importance of dimethyl oxalate (DMO) to the performance of hydrogenation catalysts and the selective acquisition of the target products is highlighted.
Production of ethylene glycolAlcohol catalysts, copper is a well-known active ingredient, copper-based catalysts for Ethylene Glycol (EG) from the series ARCO, U.S. Pat. No. 54112245,NL 7704734 and UCC, U.S. Pat. No. 4677234, 4628128, U.S. Pat. No. 4649226, 4628129, and domestic CN101474561B, CN101455976A and CN1014111990B disclose different types of supports, including MCM-14, ZSM-5, siO 2 SAB-15, etc., the reaction temperature for synthesizing Ethylene Glycol (EG) by hydrogenating dimethyl oxalate (DMO) is usually about 200 ℃, the pressure is about 2.5MPa, and the selectivity of ethylene glycol is more than 90%.
Methyl Glycolate (MG) synthesized from dimethyl oxalate (DMO) is a semi-hydrogenated product, and a silver-based catalyst is generally used because of the need for mild reaction conditions and a catalyst with weak hydrogenolysis. Silver nitrate is used as a silver source, but the silver nitrate is easy to decompose by visible light, and nano silver with uniform micro-scale cannot be formed. The smaller the Ag crystallite size, the better the conversion of the selective semi-hydrogenated Methyl Glycolate (MG), but the silver-based catalyst is very sensitive to the Liquid Hourly Space Velocity (LHSV), i.e. the feed rate, and only the LHSV is below 0.6h -1 The catalyst has activity only when the catalyst is in use, the conversion rate can be drastically reduced when the catalyst is in use, the service life of the catalyst is not long, and the industrial operation cost is increased.
According to the production requirements or reaction conditions, the co-production of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) is realized by only one catalyst in the same device, so that the method has important significance and value and wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects and provide a preparation method and application of a dimethyl oxalate selective hydrogenation catalyst.
The invention has high yield and purity of target products, the preparation process is simple and easy to implement, and the prepared catalyst can realize the production of three products of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) by changing the operation conditions in the same device, and the selectivity of each product reaches more than 90.0 percent.
The present invention has been achieved in order to achieve the above object.
A preparation method and application of a dimethyl oxalate selective hydrogenation catalyst comprise the following four steps:
(1) And (3) fully and homogeneously mixing the organic copper salt capable of being dissolved in the oleylamine with a certain amount of oleylamine under the protection of nitrogen, then programming the temperature of the mixed solution, preserving heat for reduction, and then cooling to obtain copper nanoparticle (CuNPS) suspension.
(2) Adding soluble silver salt which can be dissolved in oleylamine such as silver citrate and the like into copper nanoparticle (CuNPS) suspension, homogenizing and stirring, carrying out ultrasonic vibration, carrying out electric displacement through Ag (I) copper nanoparticles (CuNPS), carrying out constant temperature, growing silver on the surface of nano copper (CuNPS) at a certain speed, and controlling the growth time to form silver cluster stable copper nano microspheres (Ag-CuNPs). After centrifugation, the silver-copper nanospheres (Ag-CuNPs) were obtained by washing with hexane and ethanol (V/v=1:1).
(3) Stirring the obtained silver-copper nano particles in an alcohol/water solution, and slowly dropwise adding orthosilicate after ultrasonic oscillation; then stirring and crystallizing, and continuously evaporating slowly to obtain a precursor;
(4) And burning the obtained precursor to obtain the dimethyl oxalate selective hydrogenation catalyst.
Further, the soluble copper salt in the step (1) is one or more of copper acetoacetate, copper lactate, copper glycolate, copper isooctanoate, copper cyclohexanebutyrate, copper methacrylate, copper ethylenediamine bishydroxide and copper bis (hexafluoroacetylacetonate).
Further, the soluble silver salt in the step (2) is one or a mixture of more than two of silver lactate, silver acetoacetate, silver citrate and silver ammonia complex.
Further, the alcohol in the alcohol/water solution in the step (3) is one or more of methanol, ethanol, isopropanol or glycol and glycerol, and the volume ratio of the alcohol to the water is 1:0.1-10.
Further, the organic copper salt soluble in the oleylamine in the step (1) and the oleylamine have a dissolved molar concentration of 0.01-1mol/L; the mass percentage concentration of the soluble organic copper salt and the oleylamine is 0.2% -15%.
Further, the temperature is raised at the temperature raising rate of 2-10 ℃/h in the procedure of the step (1); the thermal insulation reduction means that the final temperature of programmed heating is kept for 1-12 hours at 200-230 ℃.
Further, the cooling in the step (1) can be natural cooling, and the medium cooling temperature is 60-0 ℃ and the cooling time is 6-48h.
Further, when the nano copper particles (CuNPs) in the step (2) are subjected to electric displacement, the growth time of silver atoms is constant, the quality of the silver-copper nano particles (Ag-CuNPs) is important, the constant temperature range is 60-20 ℃, and the growth time is 24-48 hours.
The electric displacement in the invention is electric deposition generated by electric coupling action between two nanoscale metal atoms under microscale. For example: potential difference of electrode between copper Cu 2+ /Cu 0 Is 0.34V; ag (silver) + /Ag 0 (0.8V), adding promoter (such as oleylamine), cu 2+ /Cu/Ag + The Ag will produce an electrodynamic displacement, also equivalent to galvanic co-deposition.
Further, the silicate in the step (3) is one or a mixture of more than two of methyl orthosilicate (TMDS), tetraethyl orthosilicate (TEOS) or Tetrapropoxysilane (TPDS).
Further, the orthosilicate dropping speed in the step (3) is 10-60 drops/min; the weight/mole ratio of copper-silver nanoparticles to silicate is: 1:0.5-5.
Further, in the step (3), the re-stirring time is 3-24 hours, and the re-stirring speed is 300-800 revolutions per minute; the evaporation temperature is 80-120 ℃.
Further, the combustion temperature in the step (4) is 300-600 ℃ and the time is 2-8 hours.
As a second aspect of the present invention, there is provided a dimethyl oxalate selective hydrogenation catalyst prepared according to the foregoing method.
As a third aspect of the present invention, the present invention provides the use of the dimethyl oxalate selective hydrogenation catalyst, which may be applied to the catalytic hydrogenation of dimethyl oxalate to produce Methyl Glycolate (MG), ethylene Glycol (EG), and/or ethanol (EtOH).
According to the application of the invention, the specific steps of the application are as follows:
taking the dimethyl oxalate selective hydrogenation catalyst, filling a constant temperature interval of a fixed bed reactor, and activating, wherein the material feeding amount is 0.15mL/min, and the material is a methanol solution of 15% dimethyl oxalate;
reaction conditions (1): the gasification temperature is 180 ℃, the reaction temperature is 200 ℃, the hydrogen flow is 300mL/min, the reaction liquid is obtained under the condition of 2.5MPa, after cooling, the reaction conversion rate reaches 100% through gas chromatography analysis, and the selectivity of methyl glycolate is higher than 90%;
reaction conditions (2): the gasification temperature is 190 ℃, the reaction temperature is 230 ℃, the hydrogen flow is 600mL/min, the reaction liquid is obtained under the pressure of 2.5MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of Ethylene Glycol (EG) is higher than 90%;
reaction conditions (3): the gasification temperature is 210 ℃, the reaction temperature is 260 ℃, the hydrogen flow is 700mL/min, the reaction liquid is obtained under the pressure of 4.0MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of ethanol (EtOH) is higher than 90%.
The reaction formula can be expressed as follows:
。
compared with the prior art, the invention has the following characteristics:
(1) The invention develops a preparation method and an application new process route of a dimethyl oxalate selective hydrogenation catalyst, wherein the preparation process of the catalyst in the process is simple, active nano copper is uniformly dispersed, and the problems of migration and agglomeration of copper particles and sintering deactivation of most of traditional copper catalysts are serious. According to the invention, ag clusters are deposited on the surfaces of nano copper particles (CuNPs) to improve stability, and the activity and thermal stability of the Ag-CuNPs are further improved through the synergistic coupling pore canal effect generated between the silicon load and Cu, ag, copper ions and silver ions.
(2) The target products methyl glycolate, ethylene glycol and ethanol are all realized by the action of dimethyl oxalate on a selective hydrogenation catalyst and by changing operation parameters, the conversion rate is 100 percent, the selectivity of the target products is more than 90 percent, and the requirements of the industrial application field on the selective hydrogenation catalyst of the dimethyl oxalate can be met.
(3) The dimethyl oxalate selective hydrogenation catalyst prepared by the invention can realize flexible switching production of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) by the same equipment, so that the application range of the catalyst is enlarged, the cost performance is high, and the industrial application significance is great.
Drawings
FIGS. 1 to 3 are SEM images of the catalyst for selective hydrogenation of dimethyl oxalate prepared in example 1.
FIG. 4 is an X-ray diffraction pattern of the dimethyl oxalate selective hydrogenation catalyst prepared in example 1.
FIG. 5 is a TEM image of the dimethyl oxalate selective hydrogenation catalyst prepared in example 1.
FIG. 6 is a schematic diagram showing the selective hydrogenation catalyst Ag-CuNPs@SiO of dimethyl oxalate prepared in example 1 2 SEM image of core-shell structure; "@" means coated, meaning: silver-copper nano-microspheres are core, centered; silica is the shell, the outer layer.
Detailed Description
The invention will be further described with reference to the following embodiments, but the scope of the invention is not limited to the following descriptions.
The invention designs a catalyst material with a core-shell structure, which is formed by electrically shifting copper nano particles (CuNPs) in an oleylamine solution through a new chemical preparation method to form copper in-situ growth silver clusters and then coating a layer of silicon dioxide nano material.
The roasted catalyst material is subjected to grinding, tabletting, crushing and screening with hydrogen gas with the flow rate of 100-300mL/min, reduced for 6-12 hours at the temperature of 100-300 ℃, cooled and subjected to different reaction pressures, temperatures and hydrogen-ester ratios. And (3) under the condition of liquid time control speed (LHSV), pumping a methanol solution of dimethyl oxalate with the mass concentration of 15% into a reactor at different speeds by a high-pressure constant-flow pump to react, and quantitatively analyzing and detecting the obtained reaction liquid by using corrected gas chromatography and evaluating the performance of the corresponding catalyst.
According to the invention, nano silver-copper particles (Ag-CuNPs) are formed by in-situ growth through electric displacement from organic copper and silver salt which are soluble in oleylamine; fully mixing the mixture in alcohol/water solution, slowly dripping silicate for sol-gel reaction, and performing heat treatment to obtain silver-copper nano particles (Ag-CuNPs) @ silicon dioxide (SiO) 2 ) And roasting the precursor with the core-shell structure to obtain the target product.
The specific preparation steps of the catalyst are as follows:
(1) Preparation of copper nanoparticles (Cu-NPS)
Dissolving soluble metallic copper organic salt in oleylamine under the protection of nitrogen, wherein the molar concentration is 0.01-1mol/L; the mass percentage concentration of the soluble organic metal copper salt and the oleylamine is as follows: 0.2-15.0%. And (3) carrying out programmed heating at a heating rate of 2-10 ℃/h, keeping the final temperature at 200-230 ℃ for 1-12 hours, and cooling to obtain the copper nanoparticle (Cu-NPS) suspension.
(2) Preparation of copper-silver nanocomposite microspheres (Ag-CuNPs)
Dissolving soluble silver salt capable of being dissolved in oleylamine into oleylamine under the protection of nitrogen, dropwise adding the soluble silver salt with the mass percentage concentration of 5.0-15.0% into the copper nanoparticle (Cu-NPS) suspension, uniformly stirring and oscillating by ultrasonic waves during the dropwise adding process, and passing Ag at 30 DEG C + And (I) carrying out electric displacement on the silver-copper nano composite microsphere and nano copper (Cu-NPS) so that Ag grows on the surface of the Cu-NPS, controlling the growth time at constant temperature to form the silver-copper nano composite microsphere with stable silver clusters, centrifuging, and washing with ethanol (V/V=1:1) after hexane to obtain the silver-copper nano (Ag-CuNPs) composite microsphere.
(3) Preparation of silver-copper nanoparticle @ silicon dioxide sphere core-shell structure precursor
Stirring the silver-copper nanoparticle microspheres in an alcohol/water solution for 3-4 hours at a stirring speed of 300-800 rpm, ultrasonically oscillating for 3-6 hours, and slowly dripping silicate at a speed of 10-60 drops/min. The mass mol ratio of Ag-CuNPs to silicate is as follows: 1:0.5-5, then stirring for 3-24 hours at a speed of 300-800 rpm. And continuously evaporating slowly at 80-120 ℃ to obtain a precursor.
(4) Preparation of the catalyst
The precursor is put into a muffle furnace for heat treatment, the roasting temperature is 300-600 ℃ and the time is 3-6 hours, and the silver-copper nano particle@silicon dioxide core-shell structure catalyst (Ag-CuNPs@SiO) is obtained 2 ）。
As shown in fig. 1-6, the catalyst performance characterization for the selective hydrogenation of dimethyl oxalate according to example 1 of the present invention. The test results showed that the diameter of the particulate spheres was 1-3 μm and the diameter of the silver-copper nanoparticles was 10-30nm. FIG. 4 is an X-ray diffraction pattern of a catalyst prepared according to the present invention. FIGS. 5 and 6 are TEM images of silver-copper nanoparticle @ silica core-shell structure of the present invention, resulting in a diameter of 10-30nm of the core material silver-copper nanoparticle sphere; the shell material is silicon dioxide (SiO 2 ) The thickness is 5-10nm.
Ag-CuNPs@SiO 2 Grinding, tabletting, crushing and sieving to obtain 40-60 mesh small-particle packed catalyst, filling a constant temperature zone of a fixed bed reactor, reducing for 6-12 hours at 100-300 ℃ by using hydrogen with the flow rate of 100-300mL/min, and cooling to obtain the catalyst with different reaction pressures, temperatures and hydrogen-ester ratios. And (3) under the condition of liquid time control speed (LHSV), pumping a methanol solution of dimethyl oxalate with the mass concentration of 15% into a reactor at different speeds by a high-pressure constant-flow pump to react, and quantitatively analyzing and detecting the obtained reaction liquid by using corrected gas chromatography and evaluating the performance of the corresponding catalyst.
According to the production requirements and reaction conditions, the co-production of three products of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) is realized by only one catalyst in the same device, so that the catalyst has important significance and value and wide application prospect.
(1) Feed conditions:
the feeding amount is 0.15mL/min, and the material is 15% dimethyl oxalate methanol solution.
Reaction conditions: the gasification temperature is 180 ℃, the reaction temperature is 200 ℃, the hydrogen flow is 300mL/min, the reaction liquid is obtained under the condition of 2.5MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of methyl acetate is higher than 90%.
Therefore, the selective hydrogenation catalyst prepared by the invention is one of the applications of preparing Methyl Glycolate (MG) by hydrogenating dimethyl oxalate.
(2) Feed conditions:
the feeding amount is 0.15mL/min, and the material is 15% dimethyl oxalate methanol solution.
Reaction conditions: the gasification temperature is 190 ℃, the reaction temperature is 230 ℃, the hydrogen flow is 600mL/min, the reaction liquid is obtained under the condition of 2.5MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of Ethylene Glycol (EG) is higher than 90%.
The selective hydrogenation catalyst prepared by the invention is second to the application of dimethyl oxalate hydrogenation to prepare Ethylene Glycol (EG).
(3) Feed conditions:
the feeding amount is 0.15mL/min, and the material is 15% dimethyl oxalate methanol solution.
Reaction conditions: the gasification temperature is 210 ℃, the reaction temperature is 260 ℃, the hydrogen flow is 700mL/min, the reaction liquid is obtained under the pressure of 4.0MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of ethanol (EtOH) is higher than 90%.
The selective hydrogenation catalyst prepared by the invention is three applications of preparing ethanol (EtOH) by hydrogenating dimethyl oxalate.
Example 1
1. Preparation of the catalyst
(1) Preparation of copper nanoparticles (Cu-NPs)
13g of copper ethylacetoacetate (Cu (acac) 2 ) Dissolving in 100g oleylamine (oAm) under nitrogen protection, starting homogenizing mixer and ultrasonic oscillating to thoroughly mix copper salt and oleylamine, heating from 30deg.C to 230deg.C, maintaining at 230deg.C for 5 hr, and cooling to 30deg.C to obtain Cu nanoparticles (Cu-NPs) suspensionAnd (3) liquid.
(2) Preparation of silver-copper nanocomposite microspheres (Ag-CuNPs)
Dissolving 11.6g silver citrate in 100g oleylamine under nitrogen protection, dripping into copper nanoparticle (Cu-NPs) suspension in (1), stirring homogeneously during dripping, ultrasonic oscillating, and passing Ag at room temperature (30deg.C) + And (I) and nano copper (Cu-NPs) are subjected to electric displacement, so that Ag grows on the surface of the Cu-NPs for 12 hours, silver-copper nano composite microspheres with stable silver clusters are formed, and 3.4g of Ag-CuNPs composite microspheres are obtained after centrifugal separation, washing and drying with hexane and ethanol (V/V=1:1).
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
3.4g of the silver-copper nano composite microsphere (Ag-CuNPs) obtained in the step (2) is added into a solution of 60g of ethanol and 700g of water, the solution is stirred at 300 revolutions per minute, ultrasonic vibration is carried out, 27.7g of tetraethyl silicate (TESO) is added dropwise at the speed of 30 drops per minute, and stirring is continued for 3 hours after the dripping is finished. And then the viscous colloid is subjected to rotary evaporation at 80-120 ℃ until the precursor of the catalyst is obtained, and then the precursor is transferred to a muffle furnace to be roasted for 4 hours at 350 ℃, and grinding, tabletting, crushing and obtaining the catalyst after roasting is finished: 11.4g of finished selective hydrogenation catalyst, which contains 18.9 percent of silver and 11.1 percent of copper, namely: 18.9% Ag-11.1% Cu@SiO 2 。
2. Application of selective hydrogenation catalyst
Mixing 5g of catalyst with 10g of quartz sand, filling the mixture into a constant temperature zone of a phi 14 mm and phi 400mm fixed bed reactor, and sealing the bottom of the reactor by 30mL of 10-mesh quartz sand; the upper part is sealed by 30mL of 10-mesh quartz sand, the catalyst is activated for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300mL/min and temperature of 300 ℃, then the feeding amount is 0.15mL/min, and the fed materials are as follows: 15% dimethyl oxalate in methanol. Under the parameters of different reaction temperatures, reaction pressures, hydrogen flow rates and the like, reaction solutions are obtained, and through gas chromatographic analysis, the conversion rate of dimethyl oxalate is 100%, and the selectivity of Methyl Glycolate (MG) and Ethylene Glycol (EG) and ethanol (EtOH) are shown in Table 1:
TABLE 1
Example two
1. Preparation of the catalyst
(1) Preparation of copper nanoparticles (Cu-NPs)
9.8g of copper lactate [ (Cu (C) 3 H 5 O 3 ) 2 ]Nitrogen was dissolved in 100g of oleylamine (oAm), and after thoroughly mixing copper salt and oleylamine, the mixture was heated from 30 ℃ to 230 ℃ and kept at 230 ℃ for 5 hours, and then cooled to 30 ℃ to obtain a Cu nanoparticle (Cu-NPs) suspension.
(2) Preparation of silver-copper nanocomposite microspheres (Ag-CuNPs)
Dissolving 4.0g of silver citrate in 100g of oleylamine under the protection of nitrogen, dripping into the copper nanoparticle (Cu-NPs) suspension in (1), stirring homogeneously during dripping, oscillating ultrasonically, and passing Ag at room temperature (30deg.C) + And (I) and nano copper (Cu-NPs) are subjected to electric displacement, so that Ag grows on the surface of the Cu-NPs for 12 hours, silver-copper nano composite microspheres with stable silver clusters are formed, and after centrifugal separation, 3.5g of Ag-CuNPs composite microspheres are obtained by washing and drying with hexane and ethanol (V/V=1:1).
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
3.5g of the silver-copper nano composite microsphere (Ag-CuNPs) obtained in the step (2) is stirred in a solution of 60g of ethanol and 700g of water at 300 revolutions per minute, and assisted by ultrasonic vibration, 27.7g of tetraethyl silicate (TESO) is added dropwise at the speed of 30 drops per minute, and stirring is continued for 3 hours after the dripping is finished. And then the viscous colloid is subjected to rotary evaporation at 80-120 ℃ until the precursor of the catalyst is obtained, and then the precursor is transferred to a muffle furnace to be roasted for 4 hours at 350 ℃, and grinding, tabletting, crushing and obtaining the catalyst after roasting is finished: 11.4g of finished selective hydrogenation catalyst, which contains 19.0 percent of silver and 11.0 percent of copper, namely: 19.0% Ag-11.0% Cu@SiO 2 。
2. Application of selective hydrogenation catalyst
Mixing 5g of catalyst with 10g of quartz sand, filling the mixture into a constant temperature zone of a phi 14 mm and phi 400mm fixed bed reactor, and sealing the bottom of the reactor by 30mL of 10-mesh quartz sand; the upper part is sealed by 30mL of 10-mesh quartz sand, the catalyst is activated for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300mL/min and temperature of 300 ℃, then the feeding amount is 0.15mL/min, and the fed materials are as follows: 15% dimethyl oxalate in methanol. Under the parameters of different reaction temperatures, reaction pressures, hydrogen flow rates and the like, reaction solutions are obtained, and through meteorological chromatography analysis, the conversion rate of dimethyl oxalate is 100%, and the selectivity of Methyl Glycolate (MG) and Ethylene Glycol (EG) and the selectivity of ethanol (EtOH) are shown in Table 2.
TABLE 2
Example III
(1) Preparation of copper nanoparticles (Cu-NPs)
7.3g of copper glycolate [ (Cu (C) 2 H 3 O 2 ) 2 ]Nitrogen was dissolved in 100g of oleylamine (oAm), and after thoroughly mixing copper salt and oleylamine, the mixture was heated from 30 ℃ to 230 ℃ and kept at 230 ℃ for 5 hours, and then cooled to 30 ℃ to obtain a Cu nanoparticle (Cu-NPs) suspension.
(2) Preparation of silver-copper nanocomposite microspheres (Ag-CuNPs)
4.0g of silver glycolate (C) 2 H 3 O 2 Ag), under the protection of nitrogen, dissolving in 100g of oleylamine, dripping into the copper nanoparticle (Cu-NPs) suspension in (1), stirring homogeneously and oscillating ultrasonically during the dripping, passing through Ag at room temperature (30 ℃) + And (I) and nano copper (Cu-NPs) are subjected to electric displacement, so that Ag grows on the surface of the Cu-NPs for 12 hours, silver-copper nano composite microspheres with stable silver clusters are formed, and after centrifugal separation, 3.6g of Ag-CuNPs composite microspheres are obtained by washing and drying with hexane and ethanol (V/V=1:1).
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
Silver obtained in step (2)Copper nanocomposite microspheres (Ag-CuNPs) 3.6g in a solution of 60g ethanol and 700g water, stirred at 300 rpm, and assisted with ultrasonic shaking, tetraethyl silicate (TESO) 27.7g was added dropwise at a rate of 30 drops/min, and stirring was continued for 3h after completion of the dropwise addition. And then the viscous colloid is subjected to rotary evaporation at 80-120 ℃ until the precursor of the catalyst is obtained, and then the precursor is transferred to a muffle furnace to be roasted for 4 hours at 350 ℃, and grinding, tabletting, crushing and screening are carried out after roasting is finished, so that the catalyst is obtained: 11.4g of finished selective hydrogenation catalyst, which contains 20.0 percent of silver and 12.0 percent of copper, namely: 20.0% Ag-12.0% Cu@SiO 2 。
2. Application of selective hydrogenation catalyst
Mixing 5g of catalyst with 10g of quartz sand, filling the mixture into a constant temperature zone of a phi 14 mm and phi 400mm fixed bed reactor, and sealing the bottom of the reactor by using 30ml of 10-mesh quartz sand; the upper part is sealed by 30ml of 10-mesh quartz sand, the catalyst is activated for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300ml/min and temperature of 300 ℃, then the feeding amount is 0.15ml/min, and the fed materials are as follows: 15% dimethyl oxalate in methanol. Under the parameters of different reaction temperatures, reaction pressures, hydrogen flow rates and the like, reaction solutions are obtained, and through meteorological chromatography analysis, the conversion rate of dimethyl oxalate is 100%, and the selectivity of Methyl Glycolate (MG) and Ethylene Glycol (EG) and the selectivity of ethanol (EtOH) are shown in Table 3.
TABLE 3 Table 3
Example IV
1. Preparation of the catalyst
Weighing 1.27g of nano copper powder (10-30 nm) purchased in the market; weighing 2.16g of nano silver powder (25-50 nm) purchased in the market; weighing 8.0g of nano silicon dioxide purchased in the market, mixing, grinding, tabletting, crushing and screening to obtain a 40-60-mesh catalyst, wherein the catalyst contains Ag18.9% and Cu11.1%, namely: 18.9% Ag-11.1% Cu@SiO 2 。
2. Catalyst hydrogenation application:
mixing 5g of catalyst with 10g of quartz sand, filling the mixture into a constant temperature zone of a phi 14 mm and phi 400mm fixed bed reactor, and sealing the bottom of the reactor by using 30ml of 10-mesh quartz sand; the upper part is sealed by 30ml of 10-mesh quartz sand, the catalyst is activated for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300ml/min and temperature of 300 ℃, then the feeding amount is 0.15ml/min, and the fed materials are as follows: 15% dimethyl oxalate in methanol. Under the parameters of different reaction temperatures, reaction pressures, hydrogen flow rates and the like, reaction solutions are obtained, and through meteorological chromatography analysis, the conversion rate of dimethyl oxalate is 47.8%, and the selectivity of Methyl Glycolate (MG) and Ethylene Glycol (EG) and the selectivity of ethanol (EtOH) are shown in Table 4.
TABLE 4 Table 4
In the fourth example, the nano copper powder, the nano silver powder and the nano silica carrier of the synthetic catalyst are all purchased in the market, and the gas chromatographic analysis is carried out on the prepared product corresponding to the same operation condition, so that the result shows that the conversion rate of dimethyl oxalate is 47.8%, and under different conditions, the maximum selectivity of Methyl Glycolate (MG), ethylene Glycol (EG) and ethanol (EtOH) is below 50.0%, and the obtained product cannot be separated and purified and has no value of practical industrial application.
The above embodiments are only some of the examples and are not intended to limit the present invention. Any modifications, equivalent substitutions, etc. which are within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (4)
1. The application of the dimethyl oxalate selective hydrogenation catalyst is characterized in that the catalyst is applied to catalyzing the hydrogenation of dimethyl oxalate to prepare ethanol;
the preparation method of the dimethyl oxalate selective hydrogenation catalyst comprises the following steps:
(1) Fully and homogeneously mixing an organic copper salt capable of being dissolved in oleylamine with a certain amount of oleylamine under the protection of nitrogen, then programming the mixed solution to be high in temperature, preserving heat, reducing, and cooling to obtain copper nanoparticle CuNPS suspension;
(2) Adding an organic silver salt solution dissolved in oleylamine into a copper nanoparticle CuNPS suspension, homogenizing and stirring, performing ultrasonic vibration, performing electric displacement on the Ag (I) copper nanoparticle CuNPS, growing silver on the surface of the nano copper CuNPS at a certain speed at constant temperature, controlling the growth time to form silver-copper nanoparticle Ag-CuNPS with stable silver clusters, centrifuging, using hexane and hexanol, and washing with V/V=1:1 to obtain the silver-copper nanoparticle Ag-CuNPS;
(3) Stirring the silver-copper nanoparticle Ag-CuNPS in an alcohol/water solution, slowly dropwise adding orthosilicate after ultrasonic oscillation, then stirring for crystallization, and continuously and slowly evaporating to obtain a precursor;
(4) Roasting the obtained precursor to obtain the dimethyl oxalate selective hydrogenation catalyst;
the organic copper salt soluble in oleylamine in the step (1) is: one or more of copper acetoacetate, copper lactate and copper glycolate; and/or
The organic silver salt in the step (2) is as follows: silver citrate; and/or
The alcohol in the alcohol/water solution in the step (3) is ethanol, and the volume ratio of the alcohol to the water is 1:0.1-10; the silicate in the step (3) is tetraethyl orthosilicate;
when the nano copper particles CuNPs in the step (2) carry out electric displacement, the constant temperature range is 60-20 ℃ and the growth time is 24-48h;
the specific steps for preparing ethanol by catalyzing dimethyl oxalate hydrogenation are as follows:
taking the dimethyl oxalate selective hydrogenation catalyst, filling a constant temperature interval of a fixed bed reactor, and activating, wherein the material feeding amount is 0.15mL/min, and the material is a methanol solution of 15% dimethyl oxalate;
reaction conditions (3): the gasification temperature is 210 ℃, the reaction temperature is 260 ℃, the hydrogen flow is 700mL/min, the reaction liquid is obtained under the pressure of 4.0MPa, after cooling, the reaction conversion rate reaches 100% by gas chromatography analysis, and the selectivity of ethanol is higher than 90%.
2. The use according to claim 1, wherein the organic copper salt and oleylamine in step (1) are dissolved in a molar concentration of 0.01-1mol/L; and/or
The temperature is raised at the temperature raising rate of 2-10 ℃/h in the procedure of the step (1); the thermal insulation reduction means that the final temperature of programmed heating is kept for 1-12 hours at 200-230 ℃.
3. The use according to claim 1, wherein the orthosilicate drop acceleration in step (3) is 10-60 drops/min; the weight/mole ratio of copper-silver nanoparticles to silicate is: 1g of 0.5 to 5mol; and/or
The stirring time in the step (3) is 3-24h, and the stirring speed is 300-800 r/min; the evaporation temperature is 80-120 ℃.
4. The use according to claim 1, wherein the calcination temperature in step (4) is 300-600 ℃ for 2-8 hours.
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