CN114917900A - Eggshell type silver-silicon catalyst and preparation method and application thereof - Google Patents
Eggshell type silver-silicon catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- 102000002322 Egg Proteins Human genes 0.000 title claims abstract description 59
- 108010000912 Egg Proteins Proteins 0.000 title claims abstract description 59
- 210000003278 egg shell Anatomy 0.000 title claims abstract description 59
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 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 31
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
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- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 6
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
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- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
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- 239000004332 silver Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
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- 238000005470 impregnation Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 239000011148 porous material Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- 101100274274 Secale cereale rsca gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
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- 230000009849 deactivation Effects 0.000 description 1
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- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical compound COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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Images
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
-
- 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)
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Abstract
The invention provides an eggshell type silver silicon catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) soaking the silica particle carrier in a hydrophobic solvent; 2) drying the carrier treated in the step 1); 3) dipping the carrier treated in the step 2) in a silver salt water solution for 1-30 min; 4) and (3) drying the carrier treated in the step 3) at 50-150 ℃, and roasting in a muffle furnace at 200-600 ℃ for 1-6 hours to obtain the eggshell type silver-silicon catalyst. The eggshell type silver-silicon catalyst with controllable shell thickness can be prepared by the preparation method, and the preparation process is simple; the prepared eggshell type silver silicon catalyst is used for catalyzing the reaction of preparing methyl glycolate by hydrogenating dimethyl oxalate, and the utilization rate of an active component Ag can be improved.
Description
Technical Field
The invention relates to the technical field of preparation of catalysts, and particularly relates to a preparation method and application of an eggshell type silver-silicon catalyst.
Background
Glycolic acid methyl ester (HOCH) 2 COOCH 3 MG) is an important chemical raw material, and because it contains both ester group, α -H and hydroxyl functional group in its structure and has chemical properties of alcohol and ester, it can continue to produce catalytic hydrogenation to synthesize ethylene glycol, hydrolyze to produce glycolic acid, oxidize to produce methyl glyoxylate, carbonylate to prepare dimethyl malonate, aminolyze to prepare glycine, etc., and is attracting attention as an important fine chemical intermediate for preparing medicines, perfumes and polymers. In recent years, the preparation of MG by gas phase hydrogenation of dimethyl oxalate (DMO) based on the C1 route has received extensive attention from both academic and industrial circles due to its simple process and environmental advantages. With the increasing maturity and large-scale industrialization of the technology of preparing Ethylene Glycol (EG) by hydrogenating coal through oxalate in China, the production cost of DMO is greatly reduced, the process economy of preparing MG by hydrogenating DMO is further improved, and the process has industrial application prospect particularly considering the national conditions of rich coal, less oil and less gas of the energy structure in China.
The development of the technology for preparing methyl glycolate by DMO hydrogenation is focused on the development of a high-efficiency catalyst, which is still in the basic research and development stage at present, and the researched catalysts mainly comprise copper-based catalysts and silver-based catalysts. For example: CN 114054024A discloses a Cu-Ni loaded SiO 2 Under the optimal conditions, the conversion rate of dimethyl oxalate is 99.7%, and the selectivity of methyl glycolate is 99.1%. CN 113368867A discloses a silver-based catalyst for synthesizing methyl glycolate by hydrogenation of dimethyl oxalate through ultrasonic-assisted impregnation, wherein the main active components are Ag and Mo, the auxiliary active components are at least one or more of Fe, K, Na, Pd, Pt, Ru, Au, Ba, Cu, Mg, Ni, Co, Mn, Zn, Ca, Ce, La, Zr, Al and Cr, the carrier is a silicon, aluminum and titanium source, the conversion rate of DMO is 99.6% under the optimal condition, and the selectivity of methyl glycolate is 89.9%. However, the above results were all evaluated for the powder catalyst. As is known, powders for laboratory studiesThe catalyst can not meet the requirements of industrial application, for gas phase hydrogenation reaction, an actual industrial device usually adopts a fixed bed reactor, and the industrial catalyst is required to be a granular catalyst with a certain macroscopic size (3-8mm mostly) due to the limitation of the pressure drop of a catalyst bed layer. Most of the currently published research papers and patent documents on the preparation of MG catalysts by hydrogenation of DMO relate to the preparation and performance evaluation of powder catalysts, and only a few patents relate to the preparation of industrial catalysts. For example, CN 105688908A discloses a method for preparing MG catalyst by hydrogenation of DMO, which uses a composite oxide of alkaline earth metal and silicon oxide as a catalyst carrier, an active component is silver, and an auxiliary agent is at least one of Cu, Au, Ru, Pd, Pt, Rh, Ni, Zn, and Zr, and firstly, the active component and the auxiliary agent are loaded on the composite oxide carrier by an impregnation method to prepare a powder catalyst, and further, the powder catalyst is prepared into a cylinder of 5 × 5 or 5 × 3mm by a tablet forming technique, wherein the conversion rate of DMO is 99% and the selectivity of MG is 90% under the optimal conditions. CN 113398983A uses ZSM-5 molecular sieve powder as carrier, and carries active component copper and auxiliary active component silver by coprecipitation method, then the prepared powder catalyst is made into hollow cylinder with 5 (external diameter) × 2 (internal diameter) × 3-6 (length) by tabletting and forming. The prepared shaped catalyst has DMO conversion rate of 98.3% and MG selectivity of 91.1% under the optimal conditions.
In the existing preparation technology of industrial catalyst for preparing MG by DMO hydrogenation, active components are loaded on a carrier to prepare powder catalyst raw powder, and then the industrial granular catalyst meeting the requirements is obtained by a pelleting technology of tabletting, so that the active components in the obtained granular catalyst are uniformly distributed in the whole granular bulk. The obtained uniform particle catalyst has better catalytic activity and selectivity, but as the macroscopic size of the industrial catalyst is in the order of several millimeters to centimeters, the hydrogenation reaction generated on the surfaces of the active components in the deep part of the pore channels of the catalyst has larger internal diffusion resistance, and meanwhile, the overlong pore channels are easily blocked by large metal particles, so that the active components in the pore channels cannot play a catalytic role, and the active components are wasted (RSCA advances, 2016, 6, 12788-The catalyst is particularly disadvantageous. The eggshell type industrial catalyst distributes active components on the surface layer of the particle carrier, reduces diffusion resistance and coking, and can improve the utilization rate of the active components. For example, CN 103769094a discloses an eggshell type catalyst for selective hydrogenation of C ═ C bonds in unsaturated carbonyl compounds, which uses γ -Al 2 O 3 And theta-Al 2 O 3 The mixture particles of (1) are used as a carrier, and an active component Pd is loaded on the carrier by an impregnation method. The results show that the eggshell type catalyst exhibits high activity, and the active component loading is low and the target product selectivity is high, compared to the homogeneous type catalyst using noble metal Pd and the like. This shows that the eggshell catalyst can improve the utilization of the active component and improve the performance of the catalyst.
In the hydrogenation reaction of DMO, part of the hydrogenation is first performed to obtain MG, and MG is further subjected to hydrogenation to obtain Ethylene Glycol (EG), MG is an intermediate product of the series hydrogenation reaction, and the diffusion channel is too long, which not only increases the mass transfer resistance, but also easily causes excessive hydrogenation to generate EG to cause selectivity reduction, and also easily causes carbon deposition to cause catalyst deactivation. Therefore, the eggshell type DMO hydrogenation industrial catalyst is developed, and the active components are distributed on the surface layer of the carrier, so that the utilization rate of the active components can be improved, and the generation of EG by excessive hydrogenation of MG can be inhibited. CN 108325532B discloses a preparation method of eggshell type copper-based catalyst for preparing methyl glycolate by hydrogenation of dimethyl oxalate: spherical silica supports are first treated to partially desilicate the outer particle layer, which is rendered partially hydrophilic, while the inner particle layer remains hydrophobic, and the active component is impregnated with an aqueous solvent to produce an eggshell catalyst. The copper-based catalyst adopts one or more of Pt, Au, Pd, Ru, Zn, Mn, Mo, Al, Ni, Co and La as an auxiliary agent, and can obtain DMO conversion rate of 92.8% and MG selectivity of 91.4% under the optimal condition. However, the desilication alkylation operation of the outer layer of the silica carrier is complex in the process of preparing the eggshell type industrial catalyst by the method, the industrial production is not easy to realize, and the thickness of the shell layer is difficult to regulate and control.
For the Ag-based catalyst for DMO hydrogenation, the eggshell type catalyst is developed, and the utilization rate of noble metal Ag can be further improved. Therefore, the invention develops the preparation technology of the eggshell type Ag catalyst taking silicon oxide as the carrier, has controllable shell thickness and simple preparation process, is applied to preparing MG by DMO hydrogenation, can reduce the loading of noble metal Ag, and has higher activity and MG selectivity compared with a uniform particle catalyst.
Disclosure of Invention
In view of the above problems, the present invention provides an eggshell type silver silicon catalyst and a preparation method thereof, and the shell thickness of the prepared eggshell type silver silicon catalyst is adjustable. The eggshell type silver silicon catalyst is used for catalyzing the reaction of preparing methyl glycolate by hydrogenating dimethyl oxalate, and the utilization rate of active components of the catalyst is higher.
The technical scheme of the invention is as follows: the preparation method of the eggshell type silver silicon catalyst comprises the following steps:
1) soaking the silica particle carrier in a hydrophobic solvent;
2) drying the carrier treated in the step 1);
3) dipping the carrier treated in the step 2) in a silver salt water solution for 1-30 min;
4) and (3) drying the carrier treated in the step 3) at 50-150 ℃, and roasting in a muffle furnace at 200-600 ℃ for 1-6 hours to obtain the eggshell type silver-silicon catalyst.
The preparation method of the eggshell type silver-silicon catalyst utilizes the immiscible property of a hydrophobic solvent and a hydrophilic solvent, the hydrophobic solvent occupies the interior of a carrier, and then a silver salt aqueous solution is intensively distributed on the surface layer of the carrier; and finally, removing the hydrophobic solvent for occupying, further roasting and reducing, and controlling the preparation process conditions to obtain the eggshell type silver-silicon catalyst with the adjustable shell thickness.
In the present invention, the shell size is represented by shell thickness/particle diameter ═ d s /d p The particle diameter is the diameter of the catalyst support particle, and the shell thickness is the thickness of the catalyst active metal diffused into the catalyst support particle.
Further, in the step 2), the drying temperature is 40-150 ℃, and the drying time is 1-60 min.
Further, in the step 2), the drying temperature is 80-140 ℃, and the drying time is 8-54 min.
Further, in step 1), the hydrophobic solvent is one or more of n-undecane, n-hexanol, ethyl hexanoate or n-heptane.
Further, in the step 3), the silver salt is one or more of silver nitrate, silver acetate, silver sulfate or silver lactate. Preferably, the silver salt is silver nitrate.
Furthermore, the mass ratio of the water to the silver salt in the silver salt aqueous solution is 1 to (0.01-0.5).
Further, the silica particle carrier is selected from spherical or columnar particles, and the diameter or equivalent diameter of the silica particle carrier is 2 to 8 mm. The silica particle carrier of the present invention can be prepared by a molding method such as tabletting, extruding or rolling, or a commercially available product can be used.
The invention provides an eggshell type silver-silicon catalyst prepared by the preparation method.
The invention also provides application of the eggshell type silver-silicon catalyst in catalyzing the reaction of preparing methyl glycolate by hydrogenating dimethyl oxalate.
Further, the reaction adopts a fixed bed reactor, the reaction temperature is 180-250 ℃, the reaction pressure is 2-4MPa, the molar ratio of hydrogen to dimethyl oxalate is (60-120) to 1, and the liquid hourly space velocity of the dimethyl oxalate is 0.2-3h -1 。
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the eggshell type silver-silicon catalyst, the Ag particles are intensively distributed in the appropriate shell layer, so that the utilization rate of the active component is improved, and the high catalytic activity can be maintained under the conditions of low loading capacity and high liquid hourly space velocity.
(2) The preparation method of the catalyst can obtain the eggshell type silver-silicon catalyst with controllable shell thickness by controlling the preparation process conditions, and has simple preparation method and good industrial application prospect.
Drawings
FIG. 1 is an SEM-EDX image of eggshell catalyst prepared in example 1 and examples 6-8 of the present invention.
FIG. 2 is an XRD pattern of catalysts prepared according to example 1, examples 6 to 9 of the present invention and comparative example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The silicon dioxide carrier used in the embodiment of the invention is a commercial product which is a mesoporous material, the aperture of the particle is 2-3mm, the aperture is 7-9nm, and the specific surface area is 500-700m 2 g -1 。
EXAMPLE 1 preparation of eggshell type silver silicon catalyst
2g of silicon dioxide carrier is taken and placed in 30ml of n-undecane for soaking for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 18 min; 0.165g of AgNO was taken 3 Dissolving in 0.8ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then baking the catalyst in a 120 ℃ oven for 12 hours, and baking the catalyst in a muffle furnace at 400 ℃ for 4 hours to obtain the eggshell type silver-silicon catalyst which is marked as 5S-E40-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.4; the dispersion degree of Ag in the catalyst is 6.0% by adopting dynamic chemical adsorption method hydroxide titration.
Example 2 preparation of eggshell type silver silicon catalyst
Soaking 2g of silicon dioxide carrier in 30ml of n-undecane for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 18 min; take 0.162g C 2 H 3 AgO 2 Dissolving in 0.8ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5S-E40-2. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.4; hydrogen and oxygen by dynamic chemical adsorptionThe Ag dispersion in the catalyst was determined by titration to be 6.2%.
Example 3 preparation of eggshell type silver silicon catalyst
2g of silicon dioxide carrier is taken and placed in 30ml of n-undecane for soaking for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 18 min; 0.152g of Ag was taken 2 SO 4 Dissolving in 0.8ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5S-E40-3. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.4; the dispersion degree of Ag in the catalyst is 5.9 percent by adopting a dynamic chemical adsorption method of hydrogen-oxygen titration.
Example 4 preparation of eggshell type silver silicon catalyst
Soaking 2g of silicon dioxide carrier in 30ml of n-hexanol for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 18 min; 0.165g of AgNO was taken 3 Dissolving in 0.8ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 80 ℃ for 8h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5J-E40-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.4; the dispersion degree of Ag in the catalyst is 6.4% by adopting dynamic chemical adsorption method hydroxide titration.
Example 5 preparation of eggshell type silver silicon catalyst
Soaking 2g of silicon dioxide carrier in 30ml of ethyl caproate for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 18 min; taking 0.165g AgNO 3 Dissolving in 0.8ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 100 ℃ for 10h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5Y-E40-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.4; the dispersion degree of Ag in the catalyst is 6.3 percent by adopting a dynamic chemical adsorption method of hydrogen-oxygen titration.
Example 6 preparation of eggshell type silver-silicon catalyst
Soaking 2g of silicon dioxide carrier in 30ml of n-undecane for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 8 min; take 0.165gAgNO 3 Dissolving in 0.4ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5S-E20-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.2; the dispersion degree of Ag in the catalyst is 3.9 percent by adopting a dynamic chemical adsorption method of hydrogen-oxygen titration.
Example 7 preparation of eggshell-type silver silicon catalyst
2g of silicon dioxide carrier is taken and placed in 30ml of n-undecane for soaking for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 32 min; 0.165g of AgNO was taken 3 Dissolving in 1.2ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5S-E60-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.6; the dispersion degree of Ag in the catalyst is 6.4% by adopting dynamic chemical adsorption method hydroxide titration.
EXAMPLE 8 preparation of eggshell-type silver-silicon catalyst
2g of silicon dioxide carrier is taken and placed in 30ml of n-undecane for soaking for 20 min; drying the soaked silicon dioxide carrier at 120 ℃ for 54 min; take 0.165gAgNO 3 Dissolving in 1.6ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 5S-E80-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.8; the dispersion degree of Ag in the catalyst is 8.2 percent by adopting a dynamic chemical adsorption method of hydrogen-oxygen titration.
Example 9 n-undecane as hydrophobic solvent d s /d p Preparation of eggshell catalyst ═ 0.2
Soaking 2g of silicon dioxide carrier in 30ml of n-undecane for 20 min; drying the soaked silicon dioxide carrier at 120 deg.C for 54min, and collecting 0.099g AgNO 3 Dissolving in 1.6ml water to prepare silver salt water solution, and soaking the dried carrier in the silver salt water solution for 20 min; and then drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the eggshell type silver-silicon catalyst, which is marked as 3S-E20-1. The catalyst obtained is characterized and d of the catalyst is determined s /d p 0.2; the dispersion degree of Ag in the catalyst is 5.9 percent by adopting a dynamic chemical adsorption method of hydrogen-oxygen titration.
Comparative example 1 preparation of silver silicon catalyst
0.165g of AgNO 3 Dissolving in 2ml water to obtain silver salt water solution, soaking 2g of silica carrier in the above silver salt water solution for 20 min. And then drying in a 120 ℃ oven for 12H, and roasting in a muffle furnace at 400 ℃ for 4H to obtain the silver-silicon catalyst, which is marked as H. The prepared catalyst is characterized, and the dispersion degree of Ag in the catalyst is measured to be 8.7 percent by adopting a dynamic chemical adsorption method and hydrogen-oxygen titration.
Fig. 1 is a SEM-EDX diagram of the eggshell-type silver-silicon catalysts prepared in the above examples 1 and 6-8, and the eggshell-type silver-silicon catalysts with different shell thicknesses can be obtained by controlling the process conditions for preparing the catalysts as shown in fig. 1. Fig. 2 is an XRD pattern of the catalysts prepared in the above examples 1, 6 to 9 and comparative example 1, and as shown in the XRD pattern, the half widths of the catalysts H, 5S-E80-1, 5S-E60-1 and 5S-E40-1 are consistent at 38.2 ° 2 θ, and the Ag particle size is also consistent as known from Scherrer' S formula. The catalyst 5S-E20-1 prepared in example 6 had a larger half-value width and larger Ag particles at 2 θ of 38.2 ° than the above-mentioned four catalysts because the catalyst active component was distributed in a smaller region, resulting in Ag agglomeration. The catalyst 3S-E20-1 prepared in example 9 can reduce the agglomeration of Ag by reducing the loading of Ag, so that the Ag particle size of the catalyst is similar to the particle sizes of the above four catalysts H, 5S-E80-1, 5S-E60-1 and 5S-E40-1.
Example 10 evaluation of catalytic Performance of catalyst
The catalysts prepared in the above examples 1 to 9 and comparative example 1 were used to catalyze the hydrogenation of dimethyl oxalate to produce methyl glycolate, respectively, and the conversion rate of dimethyl oxalate (C) was measured DMO ) Selectivity to methyl glycolate (S) MG ) And yield (Y) MG ) The catalytic performance of the catalyst on the hydrogenation reaction of dimethyl oxalate was evaluated, wherein:
C DMO the amount of DMO converted (mol)/the amount of DMO initiated (mol);
S MG the amount of DMO consumed (mol) to MG/amount of DMO converted (mol);
Y MG ＝C DMO ×S MG 。
evaluation of catalytic hydrogenation activity for dimethyl oxalate prepared in examples 1 to 9 and comparative example 1 was carried out on a stainless steel fixed bed reactor having an inner diameter of 3.2 cm. The reaction conditions are as follows: the loading of the catalyst is 1.3g, the temperature of the reactor is 220 ℃, and the liquid hourly space velocity is 1.0h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 100: 1, and the reaction pressure is 2.5 MPa. The specific evaluation method is as follows:
1.3g of catalyst is loaded into the isothermal section of the fixed bed reactor, and then 100ml/min of H is added at 350 DEG C 2 The atmosphere was reduced for 4h to activate the Ag due to oxidation during storage. H with hydrogen-ester ratio of 100 at 220 ℃ and 2.5MPa 2 And a methanol solution of dimethyl oxalate (the content of dimethyl oxalate is 10 wt%) respectively enters an evaporator through a mass flow meter and a high performance liquid chromatography constant flow pump, is fully mixed by a gas mixer and then enters a reactor for reaction, and the liquid hourly space velocity is controlled to be 1.0h -1 . The outlet gas stream was sampled using an automatic six-way valve system and then quantitatively analyzed using an on-line gas chromatograph, a hydrogen flame ionization detector and a DB-624 type capillary column (30m x 0.45mm x 0.85 μm). The interval time is 30 min. Calculating C DMO 、S MG And Y MG The parameters and performance evaluation results of the catalysts are shown in table 1.
TABLE 1 evaluation of catalytic Properties of catalysts
As shown in the results of Table 1, it can be seen from the comparison of the catalytic performances of the catalysts prepared in example 1 and examples 6 to 8 that the shell thickness of the catalyst varies for the eggshell type catalysts having the same metal loading, i.e., d in the above example s /d p The change in value has a significant effect on the catalytic performance of the catalyst.
The eggshell type silver silicon catalysts prepared in examples 1-5 and examples 7-9 have obviously higher catalytic effect on the reaction for catalyzing the hydrogenation of dimethyl oxalate to prepare methyl glycolate than the non-eggshell type silver silicon catalyst in comparative example 1. Compared with a uniform catalyst, the eggshell layer structure catalyst prepared by the invention forms active sites on the surface layer of the catalyst, inhibits the deep hydrogenation of dimethyl oxalate, and improves the selectivity of methyl glycolate. In addition, the active components of the eggshell type catalyst are distributed on the outer layer, and the active components also exist in the uniform type catalyst, so that the eggshell type silver-silicon catalyst prepared by the invention has higher utilization rate of the active components of the catalyst compared with the uniform type catalyst under the same condition because the utilization rate of the active components in the catalyst is very low in the reaction.
In addition, as seen from the catalyst evaluation results of examples 6 and 9, although the loading amount of the active component Ag in the catalyst 3S-E20-1 was lower than that of the catalyst 5S-E20-1, the catalyst 3S-E20-1 still exhibited more excellent catalytic performance than the catalyst 5S-E20-1. Therefore, the catalyst preparation method provided by the invention can reduce the loading of the active components of the catalyst and simultaneously has excellent catalytic performance by controlling and optimizing the thickness of the shell layer of the catalyst, thereby reducing the industrial production cost of the catalyst.
In conclusion, the preparation method of the eggshell type silver-silicon catalyst has the advantages of simple steps, cheap and easily-obtained raw materials, and the shell layer of the catalyst prepared by the method is easy to control. The eggshell-type silver-silicon catalyst prepared by the invention is applied to the reaction of preparing methyl glycolate by hydrogenating dimethyl oxalate, has good catalytic activity and high selectivity, is environment-friendly and has strong industrial prospect.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to the practice would be obvious to those skilled in the art and are intended to be within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (9)
1. The preparation method of the eggshell type silver-silicon catalyst is characterized by comprising the following steps:
1) soaking the silica particle carrier in a hydrophobic solvent;
2) drying the carrier treated in the step 1);
3) dipping the carrier treated in the step 2) in a silver salt water solution for 1-30 min;
4) and (3) drying the carrier treated in the step 3) at 50-150 ℃, and roasting in a muffle furnace at 200-600 ℃ for 1-6 hours to obtain the eggshell type silver-silicon catalyst.
2. The method for preparing the eggshell type silver silicon catalyst as claimed in claim 1, wherein in the step 2), the drying temperature is 40-150 ℃ and the drying time is 1-60 min.
3. The method for preparing the eggshell type silver silicon catalyst as claimed in claim 1, wherein in the step 1), the hydrophobic solvent is one or more of n-undecane, n-hexanol, ethyl hexanoate or n-heptane.
4. The method for preparing the eggshell type silver-silicon catalyst as claimed in claim 1, wherein in the step 3), the silver salt is one or more of silver nitrate, silver acetate, silver sulfate or silver lactate.
5. The method of claim 1, wherein the mass ratio of water to silver salt in the aqueous silver salt solution is 1: 0.01-0.5.
6. The method of claim 1, wherein the silica particle carrier is selected from spherical or columnar particles, and the diameter or equivalent diameter of the silica particle carrier is 2-8 mm.
7. An eggshell type silver-silicon catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The use of the eggshell-type silver silicon catalyst as claimed in claim 7 for catalyzing the reaction of preparing methyl glycolate by the hydrogenation of dimethyl oxalate.
9. The use of the eggshell type silver-silicon catalyst as claimed in claim 8, wherein a fixed bed reactor is used, the reaction temperature is 180- -1 。
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