CN115007172A - 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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- CN115007172A CN115007172A CN202210875788.5A CN202210875788A CN115007172A CN 115007172 A CN115007172 A CN 115007172A CN 202210875788 A CN202210875788 A CN 202210875788A CN 115007172 A CN115007172 A CN 115007172A
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- copper
- silver
- catalyst
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- dimethyl oxalate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 146
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000010949 copper Substances 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000002105 nanoparticle Substances 0.000 claims description 32
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 claims description 31
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 25
- 239000004005 microsphere Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000004817 gas chromatography Methods 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- -1 orthosilicate ester Chemical class 0.000 claims description 13
- 150000001879 copper Chemical class 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 10
- 208000012839 conversion disease Diseases 0.000 claims description 9
- 238000002309 gasification Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 150000003378 silver Chemical class 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 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
- 229940071575 silver citrate Drugs 0.000 claims description 3
- 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 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 2
- HXXRDHUDBAILGK-UHFFFAOYSA-L copper;2-hydroxyacetate Chemical compound [Cu+2].OCC([O-])=O.OCC([O-])=O HXXRDHUDBAILGK-UHFFFAOYSA-L 0.000 claims description 2
- 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 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
- VLOSZTWKINRGHT-UHFFFAOYSA-N copper;4-cyclohexylbutanoic acid Chemical compound [Cu+2].OC(=O)CCCC1CCCCC1 VLOSZTWKINRGHT-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 2
- JIKVETCBELSHNU-UHFFFAOYSA-M silver;3-oxobutanoate Chemical compound [Ag+].CC(=O)CC([O-])=O JIKVETCBELSHNU-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims 2
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 34
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000011258 core-shell material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 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
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000004581 coalescence Methods 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 description 14
- 239000006004 Quartz sand Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000227 grinding 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
- 239000000084 colloidal system Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- FNBULQHGNNELGY-UHFFFAOYSA-K [Ag+3].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-] Chemical compound [Ag+3].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-] FNBULQHGNNELGY-UHFFFAOYSA-K 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
- 238000001514 detection method Methods 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
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation 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
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- JBAKCAZIROEXGK-LNKPDPKZSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O JBAKCAZIROEXGK-LNKPDPKZSA-N 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 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
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 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
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 239000007788 liquid Substances 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
- 239000003208 petroleum 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
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002390 rotary evaporation 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
- 239000010944 silver (metal) Substances 0.000 description 1
- RUJQWQMCBPWFDO-UHFFFAOYSA-M silver;2-hydroxyacetate Chemical compound [Ag+].OCC([O-])=O RUJQWQMCBPWFDO-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
-
- B01J35/393—
-
- 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
Abstract
The invention discloses a preparation method and application of a dimethyl oxalate selective hydrogenation catalyst. The catalyst provided by the invention is simple in preparation process, the active nano copper is uniformly dispersed, and Ag clusters are deposited on the surface of the catalyst to improve the stability, so that the migration and coalescence of copper in the use process of the catalyst are effectively prevented, and the activity and thermal stability of Ag-CuNPS are further improved by the synergistic coupling pore channel effect generated between the silicon dioxide core-shell structures. The catalyst prepared by the invention can be used for selective hydrogenation of dimethyl oxalate, the reaction conditions are changed according to the production requirements, and the co-production of Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) is realized by only using one catalyst of the invention 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 problems, a catalytic method for cleanly utilizing coal and plant resources and further synthesizing high-value-added chemicals is urgently needed to meet the challenging environmental needs and industrialization requirements; the energy structure of 'rich coal and little oil' in China determines an important development direction for developing a high-efficiency coal utilization technology to replace an oil route. Meanwhile, China is a big agricultural country, and generates huge amount of plant straws every year, and coal and straws are made into synthesis gas (H) 2 + CO), then obtaining dimethyl oxalate through coupling reaction of widely sourced synthesis gas and nitrite, and preparing Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) through dimethyl oxalate (DMO) catalytic selective hydrogenation is a more economical and environment-friendly non-petroleum-based route, and has great economic benefits and wide market prospects.
Methyl Glycolate (MG) contains two functional groups of hydroxyl and ester in the molecule, so that the glycolate has the chemical properties of both alcohol and ester, has good biocompatibility and degradability, and is widely applied to the fields of chemical industry, medicines, spices 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 prior art, the method for preparing methyl glycolate by semi-hydrogenating dimethyl oxalate (DMO) has the advantages of simple process, lower cost and environmental protection, and has the development prospect.
Ethylene Glycol (EG) is an important chemical raw material (e.g., antifreeze, lubricant, plasticizer, surfactant, polyester, etc.) used in many industrial processes, and has many commercial applications, in which the generation of dimethyl oxalate (DMO) by coupling synthesis gas with nitrite and the subsequent full hydrogenation of dimethyl oxalate (DMO) to Ethylene Glycol (EG) is an important solution for the high-value utilization of coal and plant stalks.
Ethanol (EtOH) has been used in ethanol gasoline, and industrial ethanol is deeply hydrogenated from dimethyl oxalate (DMO) to produce ethanol (EtOH), effectively relieving the pressure of ethanol production by fermentation.
Semi-hydrogenating dimethyl oxalate (DMO) to generate Methyl Glycolate (MG); fully hydrogenating to Ethylene Glycol (EG); deep processing to produce ethanol. Therefore, the importance of dimethyl oxalate (DMO) on the performance and selectivity of the hydrogenation catalyst to obtain the target product is highlighted.
Catalysts for the production of ethylene glycol, copper being a recognized active ingredient, U.S. ARCO U.S. Pat. No. 5,54, 112245, NL7704734 and UCC series of copper-based catalysts for Ethylene Glycol (EG), U.S. Pat. No. 4677234, U.S. Pat. No. 4,28128, U.S. Pat. No. 4,4649226, U.S. Pat. No. 4,4628129, domestic CN101474561B, CN101455976A and CN1014111990B disclose different types of supports including MCM-14, ZSM-5, SiO 2 SAB-15, the above-mentioned patent publication discloses that 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%.
The synthesis of Methyl Glycolate (MG) from dimethyl oxalate (DMO) is a semi-hydrogenated product, requires mild reaction conditions and a catalyst with weak hydrogen dissociation, and generally employs a silver-based catalyst. Silver nitrate is used as a silver source, but the silver nitrate is easily decomposed by light, so that micro-scale uniform nano silver cannot be formed. The smaller the crystallite size of Ag, the better the conversion of selective semi-hydrogenated Methyl Glycolate (MG) appears, but the silver-based catalyst is very sensitive to Liquid Hourly Space Velocity (LHSV), i.e. the feed rate, with only LHSV lower than 0.6h -1 The catalyst has activity, the conversion rate is sharply reduced at high time, the service life of the catalyst is not high, and the industrial operation cost is increased.
According to 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 the target product, simple and easy preparation process, and the prepared catalyst can realize the production of three products of Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) in the same device by changing the operation conditions, and the selectivity of each product reaches more than 90.0 percent.
To achieve the above object, the present invention is achieved as described above.
A preparation method and application of a dimethyl oxalate selective hydrogenation catalyst comprise the following four steps:
(1) under the protection of nitrogen, mixing organic copper salt capable of being dissolved in oleylamine with a certain amount of oleylamine fully and homogeneously, then heating the mixed solution by program, preserving heat, reducing, and then cooling to obtain copper nano-particle (CuNPS) suspension.
(2) Adding soluble silver salt capable of being dissolved in oleylamine, such as silver citrate and the like, into a copper nanoparticle (CuNPS) suspension, carrying out homogeneous stirring and ultrasonic oscillation, carrying out electric displacement through Ag (I) copper nanoparticles (CuNPS), keeping constant temperature, growing silver on the surface of the CuNPS at a certain speed, and controlling the growth time to form the copper nanoparticles (Ag-CuNPs) with stable silver clusters. After centrifugation, washing with hexane and ethanol (V/V =1: 1) yielded silver-copper nanospheres (Ag-CuNPs).
(3) Stirring the obtained silver-copper nanoparticles in an alcohol/water solution, and slowly dropwise adding orthosilicate ester after ultrasonic oscillation; then stirring and crystallizing, and continuously and slowly evaporating to obtain a precursor;
(4) and combusting the precursor to obtain the dimethyl oxalate selective hydrogenation catalyst.
Further, the soluble copper salt in the step (1) is one or a mixture of more than two of copper acetoacetate, copper lactate, copper glycolate, copper isooctanoate, copper cyclohexylbutyrate, copper methacrylate, copper ethylenediamine double hydroxide and copper bis (hexafluoroacetylacetone) complex.
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 a mixture of more than two of methanol, ethanol, isopropanol or ethylene glycol and glycerol, and the volume ratio of the alcohol to the water is 1: 0.1-10.
Further, the dissolving molar concentration of the organic copper salt capable of being dissolved in the oleylamine in the step (1) and the oleylamine is 0.01-1 mol/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 step (1); the heat preservation reduction refers to the temperature of the programmed temperature rise of 200 ℃ and 230 ℃ for 1-12 hours.
Further, the cooling in the step (1) can be natural cooling, medium cooling temperature is 60-0 ℃, and cooling time is 6-48 h.
Further, when the nano-copper particles (CuNPs) are subjected to electric displacement in the step (2), the constant temperature growth time of silver atoms plays an important role in the quality of the silver-copper nano-particles (Ag-CuNPs), the constant temperature range is 60-20 ℃, and the growth time is 24-48 h.
The electrokinetic displacement is electrokinetic deposition generated by galvanic couple between two nanoscale metal atoms under a microscale. For example: electrode potential difference Cu between copper 2+ /Cu 0 Is 0.34V; ag + /Ag 0 (0.8V), adding promoter (such as oleylamine), Cu 2+ /Cu/Ag + the/Ag will generate electrokinetic displacement, which is 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 adding speed of the orthosilicate ester in the step (3) is 10-60 drops/min; the weight/mole ratio of copper-silver nanoparticles to silicate ester is: 1:0.5-5.
Further, the re-stirring time in the step (3) is 3-24h, and the re-stirring speed is 300-800 rpm; the evaporation temperature is 80-120 ℃.
Further, the combustion temperature in the step (4) is 300-600 ℃ for 2-8 hours.
As a second aspect of the present invention, the present invention provides a selective hydrogenation catalyst for dimethyl oxalate prepared according to the aforementioned method.
As a third aspect of the present invention, the present invention provides an application of the dimethyl oxalate selective hydrogenation catalyst, which can be applied to the preparation of Methyl Glycolate (MG), Ethylene Glycol (EG), and/or ethanol (EtOH) by catalyzing the hydrogenation of dimethyl oxalate.
According to the application of the invention, the specific steps of the application are as follows:
filling the dimethyl oxalate selective hydrogenation catalyst into 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 reaction liquid obtained under the conditions of gasification temperature 180 ℃, reaction temperature 200 ℃, hydrogen flow 300mL/min and pressure 2.5MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of methyl glycolate is higher than 90 percent;
reaction conditions (2): the reaction liquid obtained under the conditions of gasification temperature 190 ℃, reaction temperature 230 ℃, hydrogen flow rate 600mL/min and pressure 2.5MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of Ethylene Glycol (EG) is higher than 90 percent;
reaction conditions (3): the reaction liquid obtained under the conditions of gasification temperature 210 ℃, reaction temperature 260 ℃, hydrogen flow rate 700mL/min and pressure 4.0MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of ethanol (EtOH) is higher than 90 percent.
The reaction formula can be represented as follows:
compared with the prior art, the invention has the following characteristics:
(1) the invention develops a preparation method of a dimethyl oxalate selective hydrogenation catalyst and a new process route of application, the preparation process of the catalyst in the process is simple, the active nano copper is uniformly dispersed, and the problems of migration, coalescence and sintering deactivation of copper particles of most of traditional copper catalysts are serious. According to the invention, Ag clusters are deposited on the surfaces of the nano-copper particles (CuNPs) to improve the stability, and the activity and the thermal stability of the Ag-CuNPs are further improved by generating a synergistic coupling pore channel effect between the silicon load and Cu, Ag, copper ions and silver ions.
(2) The target products of methyl glycolate, glycol and ethanol are all acted by dimethyl oxalate in a selective hydrogenation catalyst, and are realized by changing operation parameters, the conversion rate is 100 percent, the selectivity of the corresponding target object is more than 90 percent, and the requirement of the industrial application field on the selective hydrogenation catalyst of 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) in 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
Fig. 1 to 3 are SEM images of the dimethyl oxalate selective hydrogenation catalyst 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 selective hydrogenation catalyst for dimethyl oxalate prepared in example 1.
FIG. 6 shows the selective hydrogenation catalyst Ag-CuNPs @ SiO for dimethyl oxalate prepared in example 1 2 SEM image of core-shell structure; "@" means coated, meaning: the silver-copper nano microsphere is a core and is arranged in the center; the silica is the shell, at the outer layer.
Detailed Description
The present invention will be further described with reference to the following embodiments, but the scope of the present invention is not limited to the following descriptions.
The invention designs a catalyst material with a core-shell structure, which is prepared by electrically displacing copper nanoparticles (CuNPs) in an oleylamine solution through a novel chemical preparation method to form copper in-situ grown silver clusters and then coating a layer of silicon dioxide nano material.
The catalyst material after roasting is ground, tableted, crushed and sieved by hydrogen with the flow rate of 300mL/min and the temperature of 300 ℃ at 100 ℃ for 6-12 hours, and is cooled and then subjected to different reaction pressures, temperatures and hydrogen-ester ratios. Under the condition of liquid-time speed control (LHSV), a methanol solution of dimethyl oxalate with the mass concentration of 15% is pumped into a reactor at different speeds for reaction by a high-pressure constant flow pump, the obtained reaction liquid is subjected to quantitative analysis and detection by corrected gas chromatography, and the performance of the corresponding catalyst is evaluated.
The method comprises the steps of forming nano silver-copper particles (Ag-CuNPs) from organic copper and silver salts which can be dissolved in oleylamine through electric displacement in-situ growth; mixing in alcohol/water solution, slowly dropping silicate ester, sol-gel reacting, and heat treating to obtain Ag-Cu nanoparticles (Ag-CuNPs) @ silicon dioxide (SiO) 2 ) And (3) a precursor with a core-shell structure, and roasting the obtained precursor to obtain the target product.
The specific preparation steps of the catalyst of the invention are as follows:
(1) preparation of copper nanoparticles (Cu-NPS)
Dissolving soluble metal copper organic salt in oleylamine under the protection of nitrogen, wherein the molar concentration is 0.01-1 mol/L; the mass percentage concentration of the soluble organic metal copper salt and the oleylamine is as follows: 0.2 to 15.0 percent. And carrying out temperature programming at the temperature rising rate of 2-10 ℃/h, keeping the final temperature at 200 ℃ and 230 ℃ for 1-12 hours, and cooling to obtain the copper nanoparticle (Cu-NPS) suspension.
(2) Preparation of copper-silver nano composite microspheres (Ag-CuNPs)
Dissolving soluble silver salt capable of being dissolved in oleylamine in the presence of nitrogen gas, wherein the mass percent concentration of the soluble silver salt is 5.0-15.0%, dropwise adding the soluble silver salt into the copper nanoparticle (Cu-NPS) suspension, homogenizing and stirring the mixture in the dropwise adding process, ultrasonically oscillating the mixture, and allowing the mixture to pass through Ag at the temperature of 30 DEG C + Performing electrokinetic displacement with nano copper (Cu-NPS),and growing Ag on the surface of the Cu-NPS, controlling the growth time at constant temperature to form silver-copper nano composite microspheres with stable silver clusters, centrifuging, and washing with ethanol (V/V =1: 1) after hexane to obtain the silver-copper nano (Ag-CuNPS) composite microspheres.
(3) Preparation of silver-copper nanoparticle @ silicon dioxide spherical core-shell structure precursor
Stirring the obtained silver-copper nanoparticle microspheres in an alcohol/water solution for 3-4 hours at the stirring speed of 300-800 rpm, ultrasonically oscillating for 3-6 hours, and then slowly dripping silicate ester at the speed of 10-60 drops/minute. The mass mol ratio of the Ag-CuNPs to the silicate ester is as follows: 1:0.5-5, then stirring for 3-24 hours, and then stirring at the speed of 300-800 rpm. Slowly evaporating at 80-120 deg.C to obtain 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 roasting time is 3-6 hours, thus obtaining the silver-copper nanoparticle @ silicon dioxide core-shell structure catalyst (Ag-CuNPs @ SiO) 2 ）。
As shown in fig. 1-6, the catalyst performance for selective hydrogenation of dimethyl oxalate of example 1 of the present invention was characterized. The test result shows that the diameter of the particle ball is 1-3 μm, and the diameter of the silver-copper nano particle is 10-30 nm. 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 core-shell structures of silver-copper nanoparticles @ silica of the present invention, resulting in core material silver-copper nanoparticle spheres of 10-30nm diameter; the shell material being silicon dioxide (SiO) 2 ) The thickness is 5-10 nm.
Mixing Ag-CuNPs @ SiO 2 Grinding, tabletting, crushing and sieving to obtain small granular catalyst of 40-60 meshes, filling in the constant temperature region of a fixed bed reactor, reducing for 6-12 h with hydrogen gas with the flow rate of 100 plus materials of 300mL/min at the temperature of 100 plus materials of 300 ℃, cooling, and then carrying out different reaction pressures, temperatures and hydrogen-ester ratios. Under the condition of liquid-time speed control (LHSV), pumping a methanol solution of dimethyl oxalate with the mass concentration of 15% into a reactor at different speeds for reaction by a high-pressure constant flow pump to obtain a reaction liquid, carrying out quantitative analysis and detection by using a corrected gas chromatography, and carrying out catalyst performance corresponding to the reaction liquidAnd (6) evaluating.
According to production requirements and reaction conditions, the co-production of three products, namely Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) is realized by using only one catalyst in the same device, so that the method has important significance and value and wide application prospect.
(1) The feeding conditions are as follows:
the feed rate was 0.15mL/min, and the feed was 15% dimethyl oxalate in methanol.
Reaction conditions are as follows: the reaction liquid obtained under the conditions of gasification temperature 180 ℃, reaction temperature 200 ℃, hydrogen flow 300mL/min and pressure 2.5MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of methyl acetate is higher than 90 percent.
Therefore, the selective hydrogenation catalyst prepared by the invention is one of the applications of preparing Methyl Glycolate (MG) by hydrogenating dimethyl oxalate.
(2) The feeding conditions are as follows:
the feed rate was 0.15mL/min, and the feed was 15% dimethyl oxalate in methanol.
The reaction conditions are as follows: the reaction liquid obtained under the conditions of gasification temperature 190 ℃, reaction temperature 230 ℃, hydrogen flow rate 600mL/min and pressure 2.5MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of Ethylene Glycol (EG) is higher than 90 percent.
Therefore, the selective hydrogenation catalyst prepared by the invention is the second application of preparing Ethylene Glycol (EG) by hydrogenating dimethyl oxalate.
(3) The feeding conditions are as follows:
the feed rate was 0.15mL/min, and the feed was 15% dimethyl oxalate in methanol.
The reaction conditions are as follows: the reaction liquid obtained under the conditions of gasification temperature 210 ℃, reaction temperature 260 ℃, hydrogen flow rate 700mL/min and pressure 4.0MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of ethanol (EtOH) is higher than 90 percent.
Therefore, the selective hydrogenation catalyst prepared by the invention is the third application of preparing ethanol (EtOH) by hydrogenating dimethyl oxalate.
Example one
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 a homogenizing mixer and carrying out ultrasonic oscillation to thoroughly mix copper salt and oleylamine, heating to 230 ℃ from 30 ℃ and keeping at 230 ℃ for 5 hours, and then cooling to 30 ℃ to obtain Cu nanoparticle (Cu-NPs) suspension.
(2) Preparation of silver-copper nano composite microspheres (Ag-CuNPs)
Dissolving 11.6g of silver citrate salt in 100g of oleylamine under the protection of nitrogen, dropwise adding the solution into the suspension of copper nanoparticles (Cu-NPs) in the step (1), carrying out homogeneous stirring and ultrasonic oscillation in the dropwise adding process, and passing through Ag at room temperature (30℃) + And (I) performing electrokinetic displacement with nano-copper (Cu-NPs) to enable Ag to grow on the surface of the Cu-NPs for 12 hours to form silver-copper nano composite microspheres with stable silver clusters, and washing and drying the silver-copper nano composite microspheres with hexane and ethanol (V/V =1: 1) after centrifugal separation to obtain 3.4g of Ag-CuNPs composite microspheres.
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
Adding 3.4g of the silver-copper nano composite microspheres (Ag-CuNPs) obtained in the step (2) into a solution of 60g of ethanol and 700g of water, stirring at 300 revolutions per minute, ultrasonically oscillating, dropwise adding 27.7g of tetraethyl silicate (TESO) at the speed of 30 drops per minute, and continuously stirring for 3 hours after dropwise adding. And then carrying out rotary evaporation on the viscous colloid at the temperature of 80-120 ℃ to obtain a precursor of the catalyst, transferring the precursor to a muffle furnace, roasting the precursor for 4 hours at the temperature of 350 ℃, and grinding, tabletting and crushing the calcined precursor to obtain: the final product of the selective hydrogenation catalyst is 11.4g, wherein the silver content is 18.9%, and the copper content is 11.1%, 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 area of a fixed bed reactor with the diameter of 14 x 400mm, and sealing the bottom of the reactor by using 30mL of 10-mesh quartz sand; the upper part of the catalyst is sealed by 30mL of 10-mesh quartz sand, the catalyst is firstly 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 different parameters of reaction temperature, reaction pressure, hydrogen flow and the like, reaction liquid is obtained, the conversion rate of dimethyl oxalate is 100 percent through gas chromatography analysis, the selectivity of Methyl Glycolate (MG) and Ethylene Glycol (EG) and ethanol (EtOH) is shown in the 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 ]Dissolving in 100g oleylamine (oAm) under nitrogen protection, starting a homogenizing mixer and carrying out ultrasonic oscillation to thoroughly mix copper salt and oleylamine, heating to 230 ℃ from 30 ℃ and keeping at 230 ℃ for 5 hours, and then cooling to 30 ℃ to obtain Cu nanoparticle (Cu-NPs) suspension.
(2) Preparation of silver-copper nano composite microspheres (Ag-CuNPs)
Dissolving 4.0g of silver citrate salt in 100g of oleylamine under the protection of nitrogen, dropwise adding the solution into the suspension of the copper nanoparticles (Cu-NPs) in the step (1), carrying out homogeneous stirring and ultrasonic oscillation in the dropwise adding process, and passing through Ag at room temperature (30℃) + And (I) performing electrokinetic displacement with nano-copper (Cu-NPs) to enable Ag to grow on the surface of the Cu-NPs for 12 hours to form silver-copper nano composite microspheres with stable silver clusters, and washing and drying the silver-copper nano composite microspheres with hexane and ethanol (V/V =1: 1) after centrifugal separation to obtain 3.5g of Ag-CuNPs composite microspheres.
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
3.5g of the silver-copper nano composite microspheres (Ag-CuNPs) obtained in the step (2) are stirred in a solution of 60g of ethanol and 700g of water at the speed of 300 r/min, ultrasonic oscillation is assisted, 27.7g of tetraethyl silicate (TESO) is dripped at the speed of 30 d/min, and stirring is continued for 3 hours after dripping. Then the viscous colloid is rotated at 80-120 ℃ and evaporated to dryness to obtainAnd transferring the precursor of the catalyst to a muffle furnace to roast for 4 hours at 350 ℃, and grinding, tabletting and crushing after roasting to obtain: 11.4g of a finished selective hydrogenation catalyst, wherein the finished selective hydrogenation catalyst contains 19.0% of silver and 11.0% 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 area of a fixed bed reactor with the diameter of 14 x 400mm, and sealing the bottom of the reactor by using 30mL of 10-mesh quartz sand; the upper part of the catalyst is sealed by 30mL of 10-mesh quartz sand, the catalyst is firstly 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 different parameters of reaction temperature, reaction pressure, hydrogen flow and the like, reaction liquid is obtained, the conversion rate of dimethyl oxalate is 100 percent through gas chromatography analysis, and the selectivity of Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) is shown in the 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 ]Dissolving in 100g oleylamine (oAm) under nitrogen protection, starting a homomixer and performing ultrasonic oscillation to thoroughly mix copper salt and oleylamine, heating to 230 ℃ from 30 ℃ and keeping at 230 ℃ for 5 hours, and then cooling to 30 ℃ to obtain Cu nanoparticles (Cu-NPs) suspension.
(2) Preparation of silver-copper nano composite microspheres (Ag-CuNPs)
4.0g of silver glycolate (C) 2 H 3 O 2 Ag) is dissolved in 100g of oleylamine under the protection of nitrogen, the solution is dripped into the suspension of the copper nanoparticles (Cu-NPs) in the step (1), the mixture is homogenized and stirred during the dripping process and is subjected to ultrasonic oscillation, and the Ag passes through the solution at room temperature (30℃) + Performing electrokinetic displacement replacement on the (I) and nano copper (Cu-NPs) to ensure thatAnd growing the obtained Ag on the surface of the Cu-NPs for 12 hours to form silver-copper nano composite microspheres with stable silver clusters, and washing and drying the silver-copper nano composite microspheres by using hexane and ethanol (V/V =1: 1) after centrifugal separation to obtain 3.6g of the Ag-CuNPs composite microspheres.
(3) Preparation of silver-copper nano microsphere @ silicon dioxide sphere core-shell structure precursor
3.6g of the silver-copper nano composite microspheres (Ag-CuNPs) obtained in the step (2) are stirred in a solution of 60g of ethanol and 700g of water at the speed of 300 r/min, ultrasonic oscillation is assisted, 27.7g of tetraethyl silicate (TESO) is dripped at the speed of 30 d/min, and stirring is continued for 3 hours after dripping. And then the viscous colloid is rotated and evaporated to dryness at 80-120 ℃ to obtain a precursor of the catalyst, 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 to obtain: 11.4g of finished selective hydrogenation catalyst, wherein the finished product contains 20.0% of silver and 12.0% 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 area of a fixed bed reactor with the diameter of 14 x 400mm, and sealing the bottom of the reactor by using 30ml of 10-mesh quartz sand; sealing the upper part with 30ml of 10-mesh quartz sand, activating the catalyst for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300ml/min and temperature of 300 ℃, and then feeding the catalyst with the feed rate of 0.15ml/min, wherein the fed materials are as follows: 15% dimethyl oxalate in methanol. Under different parameters of reaction temperature, reaction pressure, hydrogen flow and the like, reaction liquid is obtained, the conversion rate of dimethyl oxalate is 100 percent through gas chromatography analysis, and the selectivity of Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) is shown in the table 3.
TABLE 3
Example four
1. Preparation of the catalyst
Weighing 1.27g of commercially available nano copper powder (10-30 nm); weighing 2.16g of commercially available nano silver powder (25-50 nm); weighing commercially available nanosilicon dioxide 8.0g, and mixingGrinding, tabletting, crushing and screening to obtain the catalyst with 40-60 meshes, wherein the catalyst contains Ag18.9% and Cu11.1%, namely: 18.9% Ag-11.1% Cu @ SiO 2 。
2. The catalyst hydrogenation application:
mixing 5g of catalyst with 10g of quartz sand, filling the mixture into a constant temperature area of a fixed bed reactor with the diameter of 14 x 400mm, and sealing the bottom of the reactor by using 30ml of 10-mesh quartz sand; sealing the upper part with 30ml of 10-mesh quartz sand, activating the catalyst for 8 hours under the conditions of normal pressure, hydrogen flow rate of 300ml/min and temperature of 300 ℃, and then feeding the catalyst with the feed rate of 0.15ml/min, wherein the fed materials are as follows: 15% dimethyl oxalate in methanol. The reaction solution was obtained under different parameters of reaction temperature, reaction pressure, hydrogen flow rate, etc., and the conversion of dimethyl oxalate was 47.8% by gas chromatography, and the selectivity of Methyl Glycolate (MG), Ethylene Glycol (EG), and ethanol (EtOH) was as shown in table 4.
TABLE 4
In the fourth comparative example, the copper nanoparticles, silver nanoparticles and silica nanoparticles as carriers of the synthetic catalyst were all commercially available, and gas chromatography analysis of the prepared product under the same operating conditions showed that the conversion of dimethyl oxalate was 47.8%, and the maximum selectivities of Methyl Glycolate (MG), Ethylene Glycol (EG) and ethanol (EtOH) were 50.0% or less under different conditions, and the obtained product could not be isolated and purified, and thus, had no practical industrial value.
The above description is only a few examples, and is not intended to limit the present invention. Any modification, equivalent replacement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the dimethyl oxalate selective hydrogenation catalyst is characterized by comprising the following steps of:
(1) fully and homogeneously mixing organic copper salt dissolved in oleylamine under the protection of nitrogen, then heating the mixed solution by a program, preserving heat, reducing, and cooling to obtain a copper nanoparticle CuNPS suspension;
(2) adding an organic silver salt solution dissolved in oleylamine into a copper nanoparticle CuNPS suspension, carrying out homogeneous stirring and ultrasonic oscillation, carrying out electric displacement on 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, and washing with hexane and hexanol at V/V =1:1 to obtain the silver-copper nanoparticle Ag-CuNPS;
(3) stirring the obtained silver-copper nano microsphere Ag-CuNPS in an alcohol/water solution, carrying out ultrasonic oscillation, slowly dropwise adding orthosilicate ester, then stirring for crystallization, and continuously and slowly evaporating to obtain a precursor;
(4) and roasting the obtained precursor to obtain the dimethyl oxalate selective hydrogenation catalyst.
2. The method according to claim 1, wherein the organic copper salt dissolved in oleylamine in the step (1) is: one or more of copper acetoacetate, copper lactate, copper glycolate, copper isooctanoate, copper cyclohexylbutyrate, copper methacrylate, copper ethylenediamine dihydrate and copper bis (hexafluoroacetylacetone) complex; and/or
The organic silver salt in the step (2) is: one or more of silver lactate, silver acetoacetate, silver citrate and silver amine complex; and/or
The alcohol in the alcohol/water solution in the step (3) is one or a mixture of more than two of methanol, ethanol, isopropanol or ethylene glycol and glycerol, and the volume ratio of the alcohol to the water is 1: 0.1-10.
3. The preparation method according to claim 1, wherein the organic copper salt and oleylamine dissolved molar concentration in the step (1) is 0.01 to 1 mol/L; and/or
The temperature is raised at the temperature raising rate of 2-10 ℃/h in the step (1); the heat preservation reduction refers to keeping the temperature at the programmed final temperature of 200 ℃ and 230 ℃ for 1-12 hours; and/or
The cooling in the step (1) can be natural cooling or medium cooling to 60-0 ℃, and the cooling time is 6-48 h.
4. The preparation method according to claim 1, wherein the nano-copper particles CuNPs in the step (2) are subjected to electrokinetic displacement at a constant temperature of 60-20 ℃ for 24-48 h.
5. The method according to claim 1, wherein the silicate in the step (3) is one or a mixture of two or more of methyl orthosilicate (TMDS), tetraethyl orthosilicate (TEOS), or Tetrapropoxysilane (TPDS); and/or
The dripping speed of the orthosilicate ester in the step (3) is 10-60 drops/min; the weight/mole ratio of copper-silver nanoparticles to silicate ester is: 1g, 0.5-5 mol; and/or
The re-stirring time in the step (3) is 3-24h, and the re-stirring speed is 300-800 r/min; the evaporation temperature is 80-120 ℃.
6. The method as claimed in claim 1, wherein the calcination temperature in step (4) is 300-600 ℃ for 2-8 hours.
7. A selective hydrogenation catalyst for dimethyl oxalate prepared according to the method of any one of claims 1 to 6.
8. The application of the catalyst for selective hydrogenation of dimethyl oxalate in claim 7 is characterized in that the catalyst is used for catalyzing hydrogenation of dimethyl oxalate to prepare Methyl Glycolate (MG), Ethylene Glycol (EG) and/or ethanol (EtOH).
9. The application of claim 8, wherein the application comprises the following specific steps:
filling the dimethyl oxalate selective hydrogenation catalyst into 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 pressure of 2.5MPa, the reaction conversion rate reaches 100 percent after cooling, and the selectivity of the methyl glycolate is higher than 90 percent;
reaction conditions (2): the reaction liquid obtained under the conditions of gasification temperature 190 ℃, reaction temperature 230 ℃, hydrogen flow rate 600mL/min and pressure 2.5MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of Ethylene Glycol (EG) is higher than 90 percent;
reaction conditions (3): the reaction liquid obtained under the conditions of gasification temperature 210 ℃, reaction temperature 260 ℃, hydrogen flow rate 700mL/min and pressure 4.0MPa is cooled and analyzed by gas chromatography, the reaction conversion rate reaches 100 percent, and the selectivity of ethanol (EtOH) is higher than 90 percent.
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