CN116078399A - Copper-based catalyst for catalytic hydrogenation of dimethyl oxalate and preparation method and application thereof - Google Patents
Copper-based catalyst for catalytic hydrogenation of dimethyl oxalate and preparation method and application thereof Download PDFInfo
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- CN116078399A CN116078399A CN202211606617.9A CN202211606617A CN116078399A CN 116078399 A CN116078399 A CN 116078399A CN 202211606617 A CN202211606617 A CN 202211606617A CN 116078399 A CN116078399 A CN 116078399A
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- dimethyl oxalate
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- 239000010949 copper Substances 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 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 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- -1 silver ions Chemical class 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011946 reduction process Methods 0.000 abstract description 6
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 41
- 230000009467 reduction Effects 0.000 description 28
- 238000006722 reduction reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-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
- 230000003213 activating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002074 deregulated effect Effects 0.000 description 1
- YAGHEUQOAPDHKS-UHFFFAOYSA-N dimethyl oxalate;methanol Chemical compound OC.COC(=O)C(=O)OC YAGHEUQOAPDHKS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
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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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a copper-based catalyst for catalytic hydrogenation of dimethyl oxalate, and a preparation method and application thereof. The preparation method comprises the steps of preparing nano silicon spheres by using tetraethyl orthosilicate as a silicon source through a hydrothermal synthesis method, forming mixed solution with soluble copper salt and silver salt, and performing hydrothermal synthesis to prepare the copper-silver loaded nano silicon sphere catalyst. The catalyst has high activity and high stability at lower reaction temperature. The novel copper-based catalyst releases part of Cu in the hydrogen pre-reduction process + The active site ensures that the catalyst can be activated quickly, and the catalyst can be activated in the reaction processCu is also continuously released + The active site not only can make the catalyst show higher catalytic hydrogenation performance, but also can improve the service life of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a copper-based catalyst for catalytic hydrogenation of lower fatty acid esters, which can gradually release active sites in the process of hydrogen pre-reduction and reaction. In particular to a preparation method of a copper-based catalyst for catalytic hydrogenation of dimethyl oxalate, which can gradually release active sites in the hydrogen pre-reduction and reaction process.
Background
The technology for preparing glycol from coal is to prepare synthetic gas from coal; and then uses CO and H in the synthesis gas 2 The process technology for preparing glycol by further hydrogenation is used for synthesizing oxalic ester as a raw material. The catalyst used for preparing glycol by hydrogenating dimethyl oxalate is mainly a copper-based catalyst, has good performance in industry, and has the problems of short service life and the like, so that how to improve the service life of the catalyst for hydrogenating the dimethyl oxalate is a key technical problem in the technology of preparing glycol by coal and is a technical problem in the field. Cu Xu Dixi (Huttig) is far lower than the reaction temperature (180-200 ℃) for the hydrogenation of dimethyl oxalate (134 ℃) and is liable to cause the sintering of the catalyst, which is also the main cause of the deactivation of the copper-based catalyst. Is widely regarded as Cu 0 Active site plays a role in activating and dissociating H 2 Is Cu + The active site plays a role in promoting the activation and adsorption of methoxy or acyl in ester molecules, and the active site cooperatively catalyze the hydrogenation reaction of esters. Ma Xinbin et al (ACS Catalysis,2015, 5:6200-6208) consider Cu as the catalyst surface 0 When the species are relatively sufficient, cu + Species play the dominant role. Ma Xiangang et al (RSC Advances,2015, 5:37581-37584) found that esters (methyl acetate, ethyl acetate, dimethyl oxalate) could convert Cu/SiO during the reaction 2 Cu in catalyst 0 Oxidation to Cu + ，Cu + Will be again reacted with H in the atmosphere 2 Reduction to Cu 0 Cu in this way + And Cu 0 Will switch to each other to achieve a dynamic redox cycle. Due to Cu 0 Xu Dixi of the catalyst is low in temperature, and is easy to agglomerate and grow into large particles in the reduction reaction process, so that part of active sites are lost, and Cu is destroyed + /Cu 0 Dynamic redox cycling of Cu + /Cu 0 The ratio is deregulated, thereby degrading or even deactivating the catalyst.
In recent years, various measures are adopted to improve the service life of the copper-based catalyst, one important measure is that a second metal auxiliary agent is introduced into the copper-based catalyst, and the Cu-M bimetallic alloy phase formed by the second metal auxiliary agent and copper species can regulate and control the charge state and distribution of active species, such as trace metal elements and copper forming bimetallic species, thereby being beneficial to obtaining proper Cu + /Cu 0 The ratio can also promote the adsorption and activation of C=O/C-O bonds in ester molecules, effectively prevent aggregation of metal copper nano particles (Cu NPs), and remarkably improve the ester hydrogenation performance of the catalyst. Chinese patent CN114054024a reports a dimethyl oxalate hydrogenation catalyst, a preparation method and application thereof, wherein the main active component is copper, the auxiliary active component is a metal selected from Ni, in, mo, W, fe, zn and/or oxide thereof, in the catalytic hydrogenation reaction of dimethyl oxalate, the conversion rate of dimethyl oxalate is greater than 99.8%, and the selectivity of ethylene glycol is up to 99.0%. Chinese patent CN110142048A reports a silver-copper catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, and a preparation method and a use method thereof, wherein an active component Ag-Cu, and a carrier is MgO-Al 2 O 3 In the catalytic hydrogenation reaction of synthesizing methyl glycolate by hydrogenating dimethyl oxalate, the reaction temperature is 220 ℃, the hydrogen pressure is 3MPa, the conversion of the dimethyl oxalate can reach 86.6% under the condition that the hydrogen-ester ratio is 250, and the selectivity of the methyl glycolate can reach 84.4%. Chinese patent CN105457631a reports a silver-silicon catalyst, in which in the hydrogenation reaction of dimethyl oxalate, the conversion of dimethyl oxalate can reach 95%, and the selectivity of methyl glycolate can reach 91%. Chinese patent CN107303488B reports a silver siliconThe catalyst has the reaction temperature of 210 deg.c, hydrogen pressure of 3.5MPa, dimethyl oxalate converting rate up to 100% and glycol selectivity up to 95.5% in hydrogen-ester ratio of 150.
Many research work reports that the introduction of new metal elements as additives can possibly change Cu 0 And Cu + Equal number of active sites, cu + /Cu 0 The ratio and the synergistic effect of different active sites on the basis, and the active sites are mainly obtained by pre-reduction in a hydrogen atmosphere, no report is made concerning the gradual release of the active sites during the reduction and reaction. The present invention will introduce a method for gradually releasing monovalent copper (Cu + ) Process for preparing active site copper-based catalysts, i.e. Cu + The active site is gradually released in the hydrogen pre-reduction and reaction process, and the invention not only can ensure that the copper-based catalyst gradually releases monovalent copper (Cu) in the catalytic hydrogenation reaction of the lower fatty acid ester + ) Active site, also can maintain higher Cu in the reaction process + /Cu 0 The proportion effectively inhibits Cu + The species is reduced to Cu during the reaction 0 Species, thereby maintaining higher activity and stability of the copper-based catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-based silicon catalyst for catalytic hydrogenation of lower fatty acid ester, which can gradually release active sites in the hydrogen pre-reduction and reaction process. The catalyst releases part of Cu in the hydrogen pre-reduction process + The active site ensures that the catalyst can be activated quickly, and Cu can be released continuously in the reaction process + The active site not only can make the catalyst show higher catalytic hydrogenation performance, but also can improve the service life of the catalyst.
The technical scheme of the invention is as follows: the preparation method comprises the steps of preparing nano silicon spheres by using tetraethyl orthosilicate as a silicon source through a hydrothermal synthesis method, forming mixed liquid with soluble copper salt and silver salt, and performing hydrothermal synthesis to prepare the copper-silver loaded nano silicon sphere catalyst. The catalyst has high activity and high stability at lower reaction temperature.
The preparation steps of the copper-based catalyst of the invention are as follows:
A. adding a certain volume of tetraethyl orthosilicate and absolute ethyl alcohol into a certain volume of deionized water, adding a certain volume of ammonia water, and continuously stirring at 40 ℃ for 3 hours to obtain a suspension containing nano silicon spheres. And (3) carrying out repeated centrifugal washing on the suspension by using an ethanol water solution with the volume ratio of ethanol to water of 1:1 to obtain nano silicon sphere powder. The volume ratio of tetraethyl orthosilicate to absolute ethyl alcohol is 1:4-1:10, the volume ratio of tetraethyl orthosilicate to deionized water is 1:2-1:6, the mass percentage concentration of ammonia water is 25%, and the volume ratio of tetraethyl orthosilicate to ammonia water is 1:0.5-1:1.5.
B. And D, dissolving the nano silicon spheres obtained in the step A in a certain volume of deionized water to form turbid liquid containing the nano silicon spheres.
C. And B, dissolving a certain mass of soluble copper salt and silver salt in a certain volume of deionized water to form a copper ion and silver ion solution with a certain concentration, adding a certain volume of ammonia water, stirring, adding the turbid liquid containing the nano silicon spheres in the step B, and stirring until the turbid liquid and the turbid liquid are fully mixed to form a uniform mixed liquid. The soluble copper salt is one of copper nitrate or copper oxalate, the soluble silver salt is silver nitrate, wherein the concentration of copper ions is 0.05 mol/L-0.4 mol/L, the concentration of silver ions is 0.005 mol/L-0.1 mol/L, the ratio of the amounts of substances of silver element and copper element is 0.02-0.4, and the ratio of the amounts of substances of silver element and silicon element is 0.02-0.3.
D. Transferring the mixed solution in the step C into a hydrothermal kettle, placing the hydrothermal kettle in an oven for hydrothermal synthesis at a certain temperature for a certain time, obtaining a solid-liquid mixture after the hydrothermal kettle is naturally cooled, centrifugally filtering, washing with deionized water for three times to obtain a filter cake, wherein the temperature of the hydrothermal synthesis is 120-200 ℃, and the hydrothermal synthesis time is 12-48 h.
E. And D, placing the filter cake obtained in the step D into an oven, drying for a plurality of hours at a certain temperature, transferring into a muffle furnace, and roasting for a certain time at a certain temperature to obtain solid powder. Finally, the solid powder is pressed, molded and screened to obtain the particles with the particle diameter of 0.25-0.40 mm, wherein the drying temperature is 60-100 ℃, the time is 6-24 h, the roasting temperature is 300-600 ℃, and the time is 3-12 h.
The reduction and reaction method for synthesizing glycol by hydrogenating dimethyl oxalate by using a copper-based catalyst comprises the following steps: putting a catalyst sample into a tubular fixed bed reactor, heating the catalyst sample from room temperature to 150 ℃ at a flow rate of 2 ℃/min in a nitrogen atmosphere, switching to hydrogen gas, continuously heating the catalyst sample to 300 ℃ until the catalyst sample is kept for 3 to 10 hours, reducing the temperature of the system to a reaction temperature, introducing a prepared methanol solution containing 0.2g/ml dimethyl oxalate into a gasification chamber and mixing the methanol solution with hydrogen gas, reacting the mixture for 24 to 7 hours at the reaction temperature of 170 to 200 ℃ at a liquid hourly space velocity of 0.2 to 2.0 g/g.h at the hydrogen/dimethyl oxalate mass ratio of 20 to 100.
The content of the monovalent copper on the surface of the copper-based catalyst after the dimethyl oxalate hydrogenation reaction is obviously increased compared with the content of the monovalent copper on the surface of the copper-based catalyst before the reaction, and the difference between the content of the monovalent copper on the surface of the catalyst after the reaction and the content of the monovalent copper on the surface of the catalyst before the reaction is 15-40%.
The invention has the beneficial effects that: the invention adopts a simpler method to lead monovalent copper (Cu) + ) The active site of (2) is gradually released in the pre-reduction and reaction process of the catalytic hydrogenation of dimethyl oxalate, and the monovalent copper (Cu) in the reaction process is slowed down + ) The active site is reduced and agglomerated at a rate which ensures that the Cu in the catalyst is kept high + /Cu 0 The proportion of the catalyst is such that the copper-based catalyst maintains higher activity and stability.
Drawings
FIG. 1 shows X-ray diffraction patterns of comparative example 1 and example 1 after reduction (before reaction) and 72 hours of reaction, curve A represents example 1 after reduction (before reaction), curve B represents example 1 after reduction, curve C represents comparative example 1 after reduction (before reaction), and curve D represents comparative example 1 after reaction.
FIG. 2 shows the X-ray photoelectron spectra of comparative example 1 and example 1 after reduction (before reaction) and after 72 hours of reaction, curve A represents example 1 after reduction (before reaction), curve B represents example 1 after reduction (before reaction), curve C represents comparative example 1 after reduction (before reaction), and curve D represents comparative example 1 after reaction.
FIG. 3 shows the results of 500h activity evaluation at 180℃for comparative example 1 and example 1, curves A and C represent the conversion of dimethyl oxalate for example 1 and comparative example 1, respectively, and curves B and D represent the selectivity of ethylene glycol for example 1 and comparative example 1, respectively.
Detailed Description
Example 1:
the preparation method comprises the following steps:
A. 8mL of tetraethyl orthosilicate and 45mL of absolute ethyl alcohol are added into 25mL of deionized water, then 9mL of 25wt% ammonia water is added, stirring is continued for 3 hours at 40 ℃ to obtain suspension containing nano silicon spheres, and the suspension is subjected to repeated centrifugal washing by ethanol water solution with the volume ratio of ethanol to water being 1:1 to obtain nano silicon sphere powder.
B. And (C) adding the nano silicon sphere powder obtained in the step (A) into 35mL of deionized water to form turbid liquid containing nano silicon spheres.
C. Dissolving 0.42g of silver nitrate and 4.5g of copper nitrate in 100g of deionized water, then adding 16mL of 25wt% ammonia water, stirring for 15 minutes, then adding the turbid liquid containing the nano silicon spheres in the step B, and stirring until the turbid liquid and the turbid liquid are fully mixed to form a uniform mixed liquid.
D. The mixture in C was transferred to a 200mL hydrothermal kettle and placed in an oven and heated at 160℃for 20h. And (3) obtaining a solid-liquid mixture after the hydrothermal kettle is naturally cooled, centrifugally filtering, and washing with deionized water for three times to obtain a filter cake.
E. And D, drying the filter cake obtained in the step D in an oven at 70 ℃ for 24 hours, transferring the filter cake into a muffle furnace, roasting the filter cake at 400 ℃ for 5 hours to obtain solid powder, and finally tabletting, forming and screening the obtained solid powder into particles with the diameter of 0.25-0.40 mm.
Evaluation of performance:
loading copper-based catalyst precursor particles with the diameter of 0.25-0.40 mm into a tubular fixed bed reactor, heating to 150 ℃ from room temperature at 2 ℃/min in a nitrogen atmosphere with the pressure of 1.0MPa and the flow rate of 50ml/min, switching to hydrogen, continuously heating to 300 ℃ and keeping for 5 hours, cooling to the reaction temperature of 180 ℃, heating the reaction hydrogen to 2.0MPa, and performing performance evaluation; simultaneously, the prepared 0.2g/ml dimethyl oxalate methanol solution is introduced into a vaporization chamber and mixed with hydrogen to carry out oxalate hydrogenation reactionIn which H should be 2 Dmo=50 (mol/mol), and the liquid hourly space velocity of dimethyl oxalate was 1.0g (DMO)/gcat·h. The results of selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate for 72 hours are shown in Table 1, surface Cu before the reaction (after the reduction) and after the reaction for 72 hours and 500 hours + The content and the increment results are shown in tables 2 and 3. The X-ray diffraction pattern and X-ray photoelectric energy pattern after reduction (before reaction) and after 72 hours of reaction and the activity evaluation result at 180 ℃ for 500 hours are respectively shown in the accompanying figures 1,2 and 3 of the specification.
Example 2:
in example 1, the mass of silver nitrate in step C was changed to 0.13g, i.e., this example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1. Surface Cu before reaction (after reduction) and after reaction for 72 hours + The content and the increment result are shown in Table 2.
Example 3:
in example 1, the mass of silver nitrate in step C was changed to 1.0g, i.e., this example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1, the surface Cu before the reaction (after the reduction) and after the reaction for 72 hours + The content and the increment result are shown in Table 2.
Example 4:
in example 1, step D was placed in an oven at 160 ℃ instead of 180 ℃, i.e. this example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1, the surface Cu before the reaction (after the reduction) and after the reaction for 72 hours + The content and the increment result are shown in Table 2.
Example 5:
in example 1, the heating in step D was changed to be carried out in an oven for 36h, i.e. the cost example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1, the surface Cu before the reaction (after the reduction) and after the reaction for 72 hours + The content and the increment result are shown in Table 2.
Comparative example 1
In example 1, the mass of silver nitrate in step C was changed to 0g, i.e., this example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1, the surface Cu before the reaction (after the reduction) and after the reaction for 72 hours, 500 hours + The content and the increment results are shown in tables 2 and 3. The X-ray diffraction pattern and X-ray photoelectric energy pattern after reduction (before reaction) and after 72 hours of reaction and the activity evaluation result at 180 ℃ for 500 hours are respectively shown in the accompanying figures 1,2 and 3 of the specification.
Comparative example 2
The procedure of example 1 was changed to: and C, transferring the mixed solution in the step C into a beaker, placing the beaker into a water pot at 80 ℃ for ammonia distillation until the liquid is neutral, carrying out suction filtration on the solid-liquid mixture obtained after ammonia distillation, and washing the solid-liquid mixture with deionized water for three times to obtain a filter cake, namely the cost example.
The results of the selective hydrogenation of ethylene glycol synthesized from dimethyl oxalate under the same performance evaluation conditions as in example 1 for 72 hours are shown in Table 1 for surface Cu before the reaction (after the reduction) and after the reaction for 72 hours + The content and the increment result are shown in Table 2.
Table 1 results of evaluation of catalyst Activity
| Conversion of oxalate% | Glycol selectivity,% | |
| Example 1 | 99.98 | 97.20 |
| Example 2 | 99.98 | 90.71 |
| Example 3 | 99.93 | 88.50 |
| Example 4 | 99.98 | 97.07 |
| Example 5 | 99.98 | 96.53 |
| Comparative example 1 | 98.85 | 65.24 |
| Comparative example 2 | 96.75 | 59.19 |
TABLE 2 surface Cu after reduction (before reaction) and after 72h of reaction for each example of catalyst + Content and increment results thereof
Note that: surface Cu + The content is calculated based on X-ray photoelectron spectroscopy, and the Cu on the surface after reaction + Content and surface Cu before reaction (after reduction) + The difference of the content is the surface Cu + The increase in the content, surface Cu, is seen in Table 2 + The content is increased by 19-30.7%.
TABLE 3 surface Cu after 500h reaction for example and comparative example 1 + Content results
| Cu after 500h reaction + Content of% | |
| Example 1 | 64.2 |
| Comparative example 1 | 56.2 |
Note that: surface Cu + The content is calculated based on X-ray photoelectron spectroscopy.
Claims (3)
1. A preparation method of a copper-based catalyst for catalytic hydrogenation of dimethyl oxalate is characterized by comprising the following steps:
A. tetraethyl orthosilicate and absolute ethyl alcohol are added into deionized water, ammonia water is added, and stirring is continued for 3 hours at 40 ℃ to obtain a suspension containing nano silicon spheres; the suspension is centrifugally washed for a plurality of times through ethanol water solution with the volume ratio of ethanol to water being 1:1 to obtain nano silicon spheres; the volume ratio of tetraethyl orthosilicate to absolute ethyl alcohol is 1:4-1:10, the volume ratio of tetraethyl orthosilicate to deionized water is 1:2-1:6, the mass percentage concentration of ammonia water is 25%, and the volume ratio of tetraethyl orthosilicate to ammonia water is 1:0.5-1:1.5;
B. dissolving the nano silicon spheres obtained in the step A in deionized water to form turbid liquid containing the nano silicon spheres; the volume ratio of tetraethyl orthosilicate to deionized water is 8:35;
C. dissolving soluble copper salt and silver salt in deionized water to form a solution containing copper ions and silver ions, adding ammonia water, stirring, and then adding the turbid liquid containing nano silicon spheres obtained in the step B, wherein the mass percentage concentration of the ammonia water is 25%, and the volume ratio of tetraethyl orthosilicate to ammonia water is 1:4; stirring until the materials are fully mixed to form uniform mixed solution; the soluble copper salt is one of copper nitrate or copper oxalate, the soluble silver salt is silver nitrate, wherein the concentration of copper ions is 0.05 mol/L-0.4 mol/L, the concentration of silver ions is 0.005 mol/L-0.1 mol/L, the ratio of the amounts of substances of silver element and copper element is 0.02-0.4, and the ratio of the amounts of substances of silver element and silicon element is 0.02-0.3;
D. transferring the mixed solution obtained in the step C into a hydrothermal kettle for hydrothermal synthesis, obtaining a solid-liquid mixture after the hydrothermal kettle is naturally cooled, centrifugally filtering, washing with deionized water for three times to obtain a filter cake, wherein the temperature of the hydrothermal synthesis is 120-200 ℃, and the hydrothermal synthesis time is 12-48 h;
E. d, placing the filter cake obtained in the step D into an oven for drying, and then transferring the filter cake into a muffle furnace for roasting to obtain solid powder; finally, the solid powder is pressed, molded and sieved to obtain particles with the particle diameter of 0.25-0.40 mm, the drying temperature is 60-100 ℃, the time is 6-24 h, the roasting temperature is 300-600 ℃, and the time is 3-12 h.
2. A copper-based catalyst prepared according to the method of claim 1, characterized in that the content of monovalent copper on the surface of the copper-based catalyst is significantly increased after the hydrogenation reaction of dimethyl oxalate, and the content of monovalent copper on the surface of the catalyst after the reaction is increased by 15 to 40% compared with the content of monovalent copper on the surface of the catalyst before the reaction.
3. Use of the copper-based catalyst according to claim 2, characterized in that: putting a catalyst sample into a tubular fixed bed reactor, heating the catalyst sample from room temperature to 150 ℃ at a flow rate of 2 ℃/min in a nitrogen atmosphere, switching to hydrogen gas, continuously heating the catalyst sample to 300 ℃ until the catalyst sample is kept for 3 to 10 hours, reducing the temperature of the system to a reaction temperature, introducing a prepared methanol solution containing 0.2g/ml dimethyl oxalate into a gasification chamber and mixing the methanol solution with hydrogen gas, reacting the mixture for 24 to 72 hours at the reaction temperature of 170 to 200 ℃ at a liquid hourly space velocity of 0.2 to 2.0 g/g.h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020008600A (en) * | 2000-07-24 | 2002-01-31 | 김충섭 | A catalyst for the gas phase hydrogenation, the method thereof, and the method for preparing r-butyrolactone using the same catalyst |
| CN102463122A (en) * | 2010-11-18 | 2012-05-23 | 中国科学院福建物质结构研究所 | Cu-Ag/SiO2 catalyst for hydrogenating oxalate |
| CN107417649A (en) * | 2017-04-06 | 2017-12-01 | 中国科学院山西煤炭化学研究所 | The hydroxymethylfurfural of aqueous catalysis 5 prepares catalyst and preparation method and the application of 2,5 furans dicarbaldehydes |
| CN110711592A (en) * | 2019-09-05 | 2020-01-21 | 宁夏大学 | Preparation method, pretreatment method and application of propylene epoxidation catalyst |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
-
2022
- 2022-12-13 CN CN202211606617.9A patent/CN116078399A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020008600A (en) * | 2000-07-24 | 2002-01-31 | 김충섭 | A catalyst for the gas phase hydrogenation, the method thereof, and the method for preparing r-butyrolactone using the same catalyst |
| CN102463122A (en) * | 2010-11-18 | 2012-05-23 | 中国科学院福建物质结构研究所 | Cu-Ag/SiO2 catalyst for hydrogenating oxalate |
| CN107417649A (en) * | 2017-04-06 | 2017-12-01 | 中国科学院山西煤炭化学研究所 | The hydroxymethylfurfural of aqueous catalysis 5 prepares catalyst and preparation method and the application of 2,5 furans dicarbaldehydes |
| CN110711592A (en) * | 2019-09-05 | 2020-01-21 | 宁夏大学 | Preparation method, pretreatment method and application of propylene epoxidation catalyst |
| CN111715226A (en) * | 2020-07-20 | 2020-09-29 | 大连瑞克科技有限公司 | Nano catalyst for preparing ethylene glycol by gas phase hydrogenation of oxalate and preparation method thereof |
| CN113856700A (en) * | 2021-11-10 | 2021-12-31 | 太原理工大学 | Preparation method and application of copper-silver bimetallic catalyst |
Non-Patent Citations (3)
| Title |
|---|
| HUABO LI ET AL: ""Highly efficient Ag-modified copper phyllosilicate nanotube:Preparation by co-ammonia evaporation hydrothermal method and application in the selective hydrogenation of carbonate"", 《JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY》, vol. 47, 21 February 2020 (2020-02-21), pages 29 - 37, XP086136646, DOI: 10.1016/j.jmst.2020.02.020 * |
| 王登豪;张传彩;朱明远;于锋;代斌;: "高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用", 化工学报, no. 07, pages 2739 - 2745 * |
| 赵玉军;赵硕;王博;吕静;马新宾;: "草酸酯加氢铜基催化剂关键技术与理论研究进展", 化工进展, no. 04, 5 April 2013 (2013-04-05), pages 6 - 16 * |
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