CN107199035A - A kind of normal pressure gas phase catalytic synthesis methyl formate catalyst and preparation method thereof - Google Patents
A kind of normal pressure gas phase catalytic synthesis methyl formate catalyst and preparation method thereof Download PDFInfo
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- CN107199035A CN107199035A CN201710411671.0A CN201710411671A CN107199035A CN 107199035 A CN107199035 A CN 107199035A CN 201710411671 A CN201710411671 A CN 201710411671A CN 107199035 A CN107199035 A CN 107199035A
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007792 addition Methods 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000012071 phase Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- -1 polyethylene pyrrole Polymers 0.000 abstract description 4
- 239000012808 vapor phase Substances 0.000 abstract description 4
- 239000010970 precious metal Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SVWLIIFHXFGESG-UHFFFAOYSA-N formic acid;methanol Chemical compound OC.OC=O SVWLIIFHXFGESG-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VTSWSQGDJQFXHB-UHFFFAOYSA-N 2,4,6-trichloro-5-methylpyrimidine Chemical compound CC1=C(Cl)N=C(Cl)N=C1Cl VTSWSQGDJQFXHB-UHFFFAOYSA-N 0.000 description 1
- MKXZASYAUGDDCJ-SZMVWBNQSA-N LSM-2525 Chemical compound C1CCC[C@H]2[C@@]3([H])N(C)CC[C@]21C1=CC(OC)=CC=C1C3 MKXZASYAUGDDCJ-SZMVWBNQSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- WMPXPUYPYQKQCX-UHFFFAOYSA-N Sulfamonomethoxine Chemical compound C1=NC(OC)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 WMPXPUYPYQKQCX-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960001985 dextromethorphan Drugs 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229950003874 sulfamonomethoxine Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/613—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
Abstract
The invention discloses a kind of normal pressure gas phase catalytic synthesis methyl formate catalyst and preparation method thereof.The preparation method of the catalyst is：Tetraethyl orthosilicate, zinc nitrate, the presoma of active component palladium, polyethylene pyrrole network alkanone, ethanol are added in acetum, vacuum distillation, which is carried out, after stirring and dissolving by Rotary Evaporators again obtains vitreosol, colloidal sol is dried, be calcined after obtain the precursor of the catalyst, the precursor is obtained into catalyst Pd/ (SiO through hydrogen or carbon monoxide gas reduction2+ZnO).The catalyst is using palladium as active component, SiO2+ ZnO composite oxides are carrier.Catalyst of the present invention shows preferable catalytic activity and methyl formate selectivity in the reaction of normal pressure vapor- phase synthesis methyl formate.The preparation method that the present invention is used can effectively improve the decentralization of precious metal palladium in the carrier by sol-gal process, significantly improve the catalytic efficiency of catalytic reaction, realize the efficient utilization of precious metal palladium.
Description
Technical field
Prepared the invention provides a kind of catalyst for normal pressure gas phase catalytic synthesis methyl formate and its collosol and gel
Method, belongs to the preparing technical field of methyl formate.
Background technology
Methyl formate is a kind of important C1 chemical intermediates, and tool has been widely used.In chemical industry, it may be used as
The raw material of machine sintetics, it is also possible to make the solvent in the manufacture of acetate fiber.In agricultural, it can be used as insecticide, cereal
Crop sterilizer, fumigant and agent for tobacco treatment etc..Pharmaceutically, it is being commonly used for sulfonic acid methyl pyrimidine, sulfonic acid Sulfamonomethoxine, antibechic
The synthesis material of the medicines such as agent dextromethorphan.
The preparation method of methyl formate is a lot, common are：Formic acid methanol esterification method, methanol vapor phase catalytic dehydrogenation methods, first
Aldehyde catalytic dimerization method, methanol oxydehydro process, synthesis gas direct synthesis technique, methanol liquid phase carbonylation method etc..Up to now
Realize that industrialized technology has formic acid methanol esterification method, Liquid Phase Methanol carbonylation method and methanol vapor phase catalytic dehydrogenation methods.Wherein first
Sour methanol esterification method falls behind due to its technique, is gradually eliminated the shortcomings of high energy consumption and serious equipment corrosion.Liquid Phase Methanol carbonyl
Base method is the main method of current external production methyl formate, its advantage be it is not high to feed gas containing carbon monoxide purity requirement,
The selectivity of product formic acid methyl esters is high, but there is also serious shortcoming for the method：Sodium methoxide is unique catalyst, and it needs nothing
Water condition；Reaction needs to carry out in a kettle., and pressure requirements are high；Product separates trouble with catalyst；The technique methyl formate
Can not continuously it produce.Methanol vapor phase catalytic dehydrogenation methods do not obtain extensive also temporarily due to the also non-full maturity of its technology
Popularization and application.
China is the country of a rich coal resources, therefore development coal chemical technology is more conform with to synthesize methyl formate
The current fundamental realities of the country of China.Patent 201410141259.8 reports a kind of methyl nitrite formyl and is combined to methyl formate
Catalyst and preparation method thereof, the raw materials used technique is synthesis gas and methyl nitrite, and the technique is fixed bed atmospheric pressure gas phase
Catalytic reaction, can realize the continuous production of methyl formate, and product is mainly methyl formate, and accessory substance is mainly carbonic acid diformazan
Ester, dimethyl oxalate and methanol, the selectivity of product formic acid methyl esters are higher, and the separation of product formic acid methyl esters is relatively easy to.The work
Skill has extraordinary application prospect.In view of the defect of current existing methyl formate production technology and at present domestic methyl formate
Production capacity wretched insufficiency, we are necessary to develop a kind of catalyst of new high-activity high-selectivity to be applied to methyl nitrite first
Acylated synthesis methyl formate reaction.
The content of the invention
The defect existed for existing methyl formate production technology, can be used for normal pressure gas phase catalysis the invention provides one kind
Synthesize the catalyst and its sol-gel process for preparing of methyl formate.
Catalyst Pd/ (the SiO that the present invention is provided2+ZnO)：It is the SiO using Pd as active component2+ ZnO composite oxides are
The load capacity of the catalyst of carrier, wherein Pd is 0.05~0.5%, SiO of carrier quality2Two kinds of oxygen in+ZnO composite oxides
The mol ratio of compound is 1:1~4:1.The specific surface area of catalyst is 50~80m2/ g, average pore size is 12~25nm.
Its specific preparation process is as follows：
A. tetraethyl orthosilicate is dissolved in concentration in 5~10mol/L acetums, preparation concentration is 0.67~1mol/L
Tetraethyl orthosilicate acetum, abbreviation solution A；
B. zinc nitrate, ethanol, Pd presoma, polyvinylpyrrolidone (PVP) are added sequentially to obtain molten in solution A
Liquid B；Wherein the mol ratio of zinc nitrate and tetraethyl orthosilicate is 1~4:1；The addition of ethanol is the 0.25- of solution A volume
0.4；The addition of Pd presoma is according to 0.05~0.5% that Pd load capacity in the catalyst finally prepared is carrier quality
Addition, PVP addition is 5~10 times of additions of forerunner's weight according to Pd；
The presoma of the Pd is any one in palladium nitrate, palladium, the ammino palladium of nitric acid four；
C. solution B is continuously stirred into 2~6h at room temperature, vacuum distillation, solution evaporation is then carried out with Rotary Evaporators
Vitreosol is obtained after finishing, obtained colloidal sol is dried 400 in 12~24h, Muffle furnace respectively through at 80~120 DEG C of baking oven
After~600 DEG C of 2~6h of roasting, the catalyst precarsor is obtained；
D. catalyst precarsor step C obtained is small in 150~250 DEG C of reductase 12~6 under hydrogen or carbon monoxide atmosphere
When, that is, catalyst is obtained, Pd/ (SiO are expressed as2+ZnO)。
Catalyst prepared by the sol-gal process that the present invention is provided is combined to the anti-of methyl formate in methyl nitrite formyl
Preferable catalytic activity is shown in answering, and reaction condition is gentle, without obvious exothermic phenomenon, product formic acid methyl esters has higher
Selectivity.
The advantage of preparation method of the present invention is：Catalyst is prepared using sol-gal process, active component Pd can be improved and existed
Decentralization on carrier, reduces the Pd of noble metal load capacity.In addition, in preparation process by changing PVP addition, not only
Can effective regulating catalyst specific surface area and average pore size, and can effectively reduce the average mark of active component Pd particles
Shot footpath.
Brief description of the drawings
The powder diagram for the catalyst sample that Fig. 1 embodiments 1 are obtained
Embodiment
The catalyst prepared with reference to specific embodiment to the present invention using sol-gal process is described in detail, still
The present invention is not limited to specific examples below.
Embodiment 1
0.04mol tetraethyl orthosilicates are dissolved in the acetum that 60mL concentration is 6mol/L, then sequentially added
0.04mol zinc nitrates, 20mL ethanol, 0.012g palladium nitrates and 0.06g PVP, persistently transfer them to circle after stirring 2h at room temperature
Vacuum distillation is carried out in the flask of bottom with Rotary Evaporators, solution obtains vitreosol after evaporating, by this colloidal sol in 100 DEG C of bakings
This solid matter is just obtained into institute through reductase 12 h under 200 DEG C of nitrogen atmospheres again after drying 12h, 450 DEG C of Muffle kiln roasting 4h in case
The catalyst sample needed, wherein active component Pd load capacity account for the 0.1% of carrier quality for it.
Phase structure analysis is carried out to catalyst sample obtained by embodiment 1 as powder diffraction, Fig. 1 is as a result seen.Can by Fig. 1
See only occur SiO in powder diagram2With the diffraction maximum of ZnO phases, there is not any PdO diffraction maximum, this explanation gained is urged
The carrier of agent sample is SiO2With ZnO mixed phase, and active component palladium is due to its high dispersive or load capacity is relatively low causes powder
Last diffraction characterizes the diffraction maximum that can't detect PdO.By inductive plasma coupling measurement, the catalyst component result shows, should
SiO in catalyst2Mass fraction be 42.37%, ZnO mass fraction be 57.28%.
Embodiment 2
0.04mol tetraethyl orthosilicates are dissolved in the acetum that 40mL concentration is 6mol/L, then sequentially added
0.06mol zinc nitrates, 20mL ethanol, 0.031g palladiums and 0.31g PVP, persistently transfer them to circle after stirring 4h at room temperature
Vacuum distillation is carried out in the flask of bottom with Rotary Evaporators, solution obtains vitreosol after evaporating, by this colloidal sol in 110 DEG C of bakings
Dried in case and this solid matter is just obtained into institute through reducing 4h under 250 DEG C of nitrogen atmospheres again after 12h, 500 DEG C of Muffle kiln roasting 2h
The catalyst sample needed, wherein active component Pd load capacity account for the 0.2% of carrier quality for it.Measure in the catalyst sample
SiO2Mass fraction be 33.08%, ZnO mass fraction be 57.87%.
Embodiment 3
0.04mol tetraethyl orthosilicates are dissolved in the acetum that 60mL concentration is 6mol/L, then sequentially added
0.05mol zinc nitrates, 20mL ethanol, the ammino palladium of 0.054g nitric acid four and 0.324g PVP, at room temperature persistently after stirring 6h by it
It is transferred in round-bottomed flask and vacuum distillation is carried out with Rotary Evaporators, solution obtains vitreosol after evaporating, by this colloidal sol
Dried in 80 DEG C of baking ovens after 12h, 600 DEG C of Muffle kiln roasting 4h again by this solid matter through under 200 DEG C of carbon monoxide atmospheres
Reductase 12 h just obtains required catalyst sample, and wherein active component Pd load capacity accounts for the 0.3% of carrier quality for it.Inductance
Plasmon coupling test shows SiO in the catalyst sample2Mass fraction be for 37.05%, ZnO mass fraction
62.61%.
Embodiment 4
0.04mol tetraethyl orthosilicates are dissolved in the acetum that 60mL concentration is 6mol/L, then sequentially added
0.05mol zinc nitrates, 20mL ethanol, 0.012g palladium nitrates and 0.12g PVP, persistently transfer them to circle after stirring 3h at room temperature
Liquid is evaporated with Rotary Evaporators in the flask of bottom and obtains clear gel, this gel is dried into 12h, 600 DEG C in 120 DEG C of baking ovens
This solid matter is just obtained into required catalyst sample through reducing 4h under 150 DEG C of carbon monoxide atmospheres again after Muffle kiln roasting 4h
Product, wherein active component Pd load capacity account for the 0.1% of carrier quality for it.Inductive plasma coupling measurement shows the catalysis
SiO in agent sample2Mass fraction be 37.12%, ZnO mass fraction be 62.58%.
The performance evaluation of catalyst
The catalyst sample of embodiment 1~4 is sieved into the particle of 10~20 mesh, 2mL embodiments 1~4 are measured with graduated cylinder
Catalyst sample be loaded on internal diameter be 5mm stainless steel reaction pipe in, be re-introduced into 20mL/min methyl nitrites, 20mL/min
Carbon monoxide, 10mL/min hydrogen, reaction velocity is 1500h-1, it is 135 DEG C to control heating-up temperature, and reaction product and tail gas are through dividing
Not through online gas chromatographic analysis, the results are shown in Table 1 for concrete analysis.
The Evaluation results of the catalyst sample of 1 embodiment of table 1~4
It can be seen that the catalyst sample prepared using the inventive method in carbon monoxide, hydrogen from the evaluation result of upper table
With preferable catalytic activity is shown in the normal pressure gas phase reaction of methyl nitrite, the conversion per pass of carbon monoxide can reach
More than 85%, the selectivity of methyl formate can reach more than 90%, particularly in the case where Pd load capacity is 0.1%, first
The space-time yield of sour methyl esters still is able to reach 710g/Lcat·h。
Claims (2)
1. a kind of preparation method of normal pressure gas phase catalytic synthesis methyl formate catalyst, its specific preparation process is as follows：
A. tetraethyl orthosilicate is dissolved in concentration in 5~10mol/L acetums, prepare concentration be 0.67~1mol/L just
The acetum of tetraethyl orthosilicate, abbreviation solution A；
B. zinc nitrate, ethanol, Pd presoma, polyvinylpyrrolidone are added sequentially in solution A obtain solution B；Wherein
The mol ratio of zinc nitrate and tetraethyl orthosilicate is 1~4:1；The addition of ethanol is the 0.25-0.4 of solution A volume；Before Pd
The addition for driving body is 0.05~0.5% addition for carrier quality, poly- second according to Pd load capacity in the catalyst finally prepared
The addition of alkene pyrrolidone is 5~10 times of additions of forerunner's weight according to Pd；
The presoma of the Pd is any one in palladium nitrate, palladium, the ammino palladium of nitric acid four；
C. solution B is continuously stirred into 2~6h at room temperature, then carries out vacuum distillation with Rotary Evaporators, solution evaporates
After obtain vitreosol, by obtained colloidal sol respectively through being dried at 80~120 DEG C of baking oven 400 in 12~24h, Muffle furnace~
After 600 DEG C of 2~6h of roasting, the catalyst precarsor is obtained；
D. catalyst precarsor step C obtained under hydrogen or carbon monoxide atmosphere in 150~250 DEG C of reductase 12~6 hour,
Catalyst is obtained, Pd/ (SiO are expressed as2+ZnO)。
2. a kind of normal pressure gas phase catalytic synthesis methyl formate catalyst prepared according to the method described in claim 1, its table
It is shown as Pd/ (SiO2+ ZnO), wherein Pd is active component, SiO2+ ZnO composite oxides are carrier, and Pd load capacity is carrier matter
0.05~0.5%, SiO of amount2The mol ratio of two oxides is 1 in+ZnO composite oxides:1~4:1；The catalyst compares table
Area is 50~80m2/ g, average pore size is 12~25nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021164135A1 (en) * | 2020-02-21 | 2021-08-26 | 陕西华大骄阳能源环保发展集团有限公司 | Catalyst for low-temperature plasma catalytic conversion of gaseous alkane and preparation method therefor |
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|---|---|---|---|---|
| CN85105647A (en) * | 1984-05-07 | 1987-01-28 | 希普莱有限公司 | Catalytic metal of reduced particle size |
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