CN105148907A - 1, 2-dichloroethane selective hydrodechlorination reaction catalyst and preparation method and application thereof - Google Patents
1, 2-dichloroethane selective hydrodechlorination reaction catalyst and preparation method and application thereof Download PDFInfo
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 94
- 239000002184 metal Substances 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
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- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 238000006298 dechlorination reaction Methods 0.000 claims description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 12
- 238000011549 displacement method Methods 0.000 claims description 11
- 238000001802 infusion Methods 0.000 claims description 11
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000006392 deoxygenation reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009938 salting Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
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- 238000006555 catalytic reaction Methods 0.000 description 13
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- 230000003197 catalytic effect Effects 0.000 description 10
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- 239000012159 carrier gas Substances 0.000 description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000036541 health Effects 0.000 description 3
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- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
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Classifications
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a 1, 2-dichloroethane selective hydrodechlorination reaction catalyst and a preparation method and application thereof. The catalyst uses oxide C as a carrier, metals A and B are loaded respectively through an impregnation method and a replacement method and an A-B/C catalyst is obtained, wherein the metal A is Ag or Cu, the metal B is Pd or Pt, and the oxide C is Al2O3, SiO2, TiO2 or ZrO2. The preparation method of the catalyst comprises the steps of adding oxide C into metal A salt solution for impregnation and evaporative drying, and then performing drying and roasting to obtain A/C; feeding H2 into A/C for reduction, adding deoxidized metal B salt solution into inert gas for replacement reaction, agitating for 0.5 to 3h, performing filtration to obtain solids and drying the solids to obtain an A-B/C catalyst. The A-B/C catalyst is used for 1, 2-dichloroethane selective hydrodechlorination reaction to obtain hydrocarbons dominated by ethylene, and the selectivity of ethylene is greater than 80 percent.
Description
Technical field
The present invention relates to a kind of loaded noble metal catalyst and preparation method thereof, be specifically related to a kind of catalysis 1, the Catalysts and its preparation method of 2-dichloroethanes selective hydrogenation dechlorination reaction, and the application of this catalyst in 1,2-dichloroethanes selective hydrogenation dechlorination catalytic reaction.
Background technology
1,2-dichloroethanes is at room temperature colourless volatile oily liquids, has a wide range of applications at chemical field, as 1,2-dichloroethanes is not only the making raw material of vinyl chloride, ethylene glycol, ethanedioic acid, dibenzoyl etc.; Also be a kind of widely used organic solvent, can be used as the solvent of cured, fatty, rubber etc.And in agriculture field, also can be used as grain, the fumigant of cereal and soil sterilants.
There is more safety problem in 1,2-dichloroethanes: 1,2-dichloroethanes is discharged in environment, not only can endanger environment and also can damage health.To environment aspect, 1,2-dichloroethanes has extremely strong destructive power to ozone layer; To health aspect, to eyes and respiratory tract, there is spread effect, suck a certain amount of after can cause pulmonary edema, suppress central nervous system, stimulating gastrointestinal road, cause the harm such as liver kidney and adrenal infringement; 1,2-dichloroethanes also has teratogenesis, and is suspicious carcinogenic substance.
In addition, due to less to the understanding of 1,2-dichloroethanes and be neglectful in taking precautions, the accident that therefore human body is poisoning occurs more, and most accident causes because human body sucks.Therefore, the safety standard regulation of labour health department of China, in workshop air, the highest permission mass concentration of 1,2-dichloroethanes is 15mg/m
3.
The steam of 1,2-dichloroethanes also can form explosive mixture with air, runs into naked light, high heat can cause combustion explosion, there is larger potential safety hazard.
Have multiple method to the process of 1,2-dichloroethanes at present, conventional has direct combustion method, biological treatment, chemisorption method, catalytic hydrogenation method etc.; Wherein, direct combustion method may cause incomplete combustion to generate the material having more toxicity; The degradation efficiency of biological treatment is lower and have selectivity; Chemisorbed rule cannot realize, to the real degraded of 1,2-dichloroethanes, it temporarily can only being removed from environment; And catalytic hydrogenation method not only can realize the degraded of 1,2-dichloroethanes, and due to this product with industrial value of ethene optionally can be generated, realize the recycling of product, and this process non-secondary pollution, economize energy, therefore obtains increasing concern.
Conventional catalysis 1, the catalyst of 2-dichloroethanes selective hydrogenation dechlorination reaction is bimetallic catalyst, the preparation method of conventional catalyst is co-impregnation, detailed process is as follows: A, B two kinds of metal salt solutions and a certain amount of support C are mixed in certain proportion, and with vigorous stirring, last evaporate to dryness, oven dry, roasting.The catalyst prepared of the method is bulk phase-doped due to A, B two kinds of metals, so the utilization rate of metal is low, cannot give full play to the H that dissociates of metal A g, the dechlorinating ability of Cu and metal Pd, Pt
2ability.
Summary of the invention
In order to overcome shortcoming of the prior art, the object of this invention is to provide a kind of catalyst of 1,2-dichloroethanes selective hydrogenation dechlorination reaction and preparing the method for this catalyst.
Another object of the present invention is to provide one and utilizes described catalyst to the method for 1,2-dichloroethanes selective hydrogenation dechlorination reaction.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of 1,2-dichloroethanes selective hydrogenation dechlorination reaction catalyst, it is characterized in that, with oxide C for carrier, carried metal A and B obtains A-B/C bimetallic catalyst successively, wherein, metal A is Ag or Cu, and first pass through infusion process load on oxide C carrier, metal B is Pd or Pt, the method load of being replaced by redox is on oxide C carrier, and oxide C is Al
2o
3, SiO
2, TiO
2or ZrO
2.
Described metal A accounts for 0.5% ~ 2% of catalyst gross mass, and metal B accounts for 0.01% ~ 0.5% of catalyst gross mass, and metal A is 1 ~ 200:1 with the atomic molar ratio of metal B.Preferably, when the mol ratio of A:B is more than or equal to 2:1, the ethylene selectivity higher than 80% can be obtained, the larger selective meeting to ethene of ratio of A:B is unreasonable to be thought, but consider that the activity of the content of metal B to catalysis plays a decisive role, the mol ratio of A:B can obtain desirable selective and active between 2:1 to 100:1 simultaneously.
Described bimetallic catalyst successively by infusion process and between metal and metal cation redox displacement method load on A, B two kinds of metals, due to metal B by with metal A generation direct oxidation reduction reaction and selective displacement to metal A surface, metal B can not enter metal particle bodies mutually in, therefore, this catalyst greatly improves the utilization ratio of metal B, and well disperse metal B, thus obtain catalytic stability selective, active and good preferably.
The preparation method of 1,2-described dichloroethanes selective hydrogenation dechlorination reaction catalyst, comprises the steps:
1) oxide C is added in metal A salting liquid flood, evaporate to dryness, carry out after evaporate to dryness drying, roasting obtain support type A/C catalyst, by the A/C catalyst logical H at 300 DEG C of temperature obtained
2reductase 12 ~ 5h;
2) by reduction after A/C catalyst in atmosphere of inert gases, put into deoxygenation deionized water, stir; Dropwise add the metal B salting liquid generation displacement reaction of deoxygenation simultaneously, stir 0.5 ~ 3h, reacted solution is filtered and is repeatedly washed till neutrality, drying filtering the solid obtained, namely obtaining described A-B/C bimetallic catalyst.
A-B/C catalyst of the present invention, wherein metal A is metal A g, Cu, and metal B is Pd, Pt, it is emphasized that metal A must be lower than the standard electrode EMF of metal B.
Described metal A salt is the nitrate of metal A, chloride or sulfate, and described metal B salt is the nitrate of metal B, chloride or sulfate.
The concentration of described metal A salt or metal B salt is 1 × 10
-6~ 0.001g/mL.
The present invention prepares A-B/C catalyst by the method for dipping-displacement, this catalyst can be used for the reaction of catalysis 1,2-dichloroethanes selective hydrogenation dechlorination, and optionally can generate ethene, namely the invention still further relates to the application of described catalyst, the technical scheme adopted is:
A kind of method of 1,2-dichloroethanes selective hydrogenation dechlorination reaction, it is characterized in that, with described A-B/C for catalyst, carry out hydrogenation-dechlorination in the gas phase to 1,2-dichloroethanes, the dechlorination of 1,2-dichloroethanes is converted into the hydrocarbon that ethene is primary product.
Described method comprises the steps:
1) successively by infusion process and redox displacement method at the area load metal A of oxide C and B, the A-B/C bimetallic catalyst obtained, wherein, metal A is Ag or Cu, and metal B is Pd or Pt, and oxide C is Al
2o
3, SiO
2, TiO
2or ZrO
2.
2) take A-B/C as catalyst, by 1,2-dichloroethanes, H after gasification
2after He mixing, carry out gas-phase catalytic hydrogenation dechlorination reaction to 1,2-dichloroethanes, the temperature of reaction is 200 ~ 300 DEG C, and being converted into ethene is the hydrocarbon of primary product.
In described A-B/C catalyst, described metal A accounts for 0.5% ~ 2% of catalyst gross mass, and metal B accounts for 0.01% ~ 0.5% of catalyst gross mass, and metal A is 1 ~ 200:1, preferably 2 ~ 100:1 with the atomic molar ratio of metal B.
In described catalytic hydrogenation and dechlorination reaction, in volumetric concentration, H
2concentration be the concentration of 30000 ~ 40000ppm, 1,2-dichloroethanes be 7000 ~ 7500ppm, the flow velocity of gaseous mixture is 40 ~ 50ml/min.
The time of described catalytic hydrogenation and dechlorination reaction is 30 ~ 40h.
Bimetallic catalyst of the present invention is in its preparation process, first metal A is loaded on oxide C carrier by the method for dipping, recycle the feature that the electrode potential of metal B is higher than the electrode potential of metal A, the metal A of catalyst surface metallic state is displaced with the metal B of cation state, metal A enters in solution with cation form simultaneously, thus obtaining A-B/C catalyst, the order of load is B after first A.Because metal B salting liquid by with metal A generation redox reaction and replace metal A surface, metal B can not enter metal particle bodies mutually in, there will not be bulk phase-doped phenomenon, all right well dispersed metal B, greatly improve the utilization ratio of metal B, thus obtain catalytic stability selective, active and good preferably.
According to the A-B/C catalyst that dipping-displacement method of the present invention is prepared, it is to 1, the selective hydrogenation dechlorination catalysis of 2-dichloroethanes shows obvious effect, and the selective height of target product ethene (ethylene selectivity that the inventive method obtains is greater than 80%), having good stability of catalyst.
In addition, catalysis method of the present invention is to the degradation process of 1,2-dichloroethanes selective hydrogenation dechlorination, ripe technically, and this process non-secondary pollution, environmental protection, and can the ethene with larger industrial value be generated, good economic benefit can be produced.
Accompanying drawing explanation
Fig. 1 Ag-Pd/ γ of the present invention-Al
2o
3the ultraviolet-visible light spectrogram of bimetallic catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1 catalyst and preparation thereof
Ag-Pd/ γ-Al
2o
3the preparation of catalyst: prepare Ag-Pd/ γ-Al by dipping-displacement method
2o
3catalyst, its concrete steps are as follows: by the γ-Al of certain mass
2o
3join a certain amount of AgNO
3in solution, after dipping stirs 2h, by solution evaporate to dryness under 90 DEG C of water-baths, 105 DEG C of oven dry, at 300 DEG C, in Muffle furnace, roasting 4h is for subsequent use.Ag/ γ-the Al that infusion process is prepared
2o
3300 DEG C of reductase 12 h, transfer in atmosphere of inert gases afterwards under an atmosphere of hydrogen.Under atmosphere of inert gases, by a certain amount of Ag/ γ-Al
2o
3add in the deionized water of deoxygenation, while vigorous stirring, dropwise add the Pd (NO of certain volume and certain density deoxygenation
3)
2solution, after being added dropwise to complete, the suspension of gained continues to stir 1.5h, is filtered by suspension afterwards, and washes for several times by deionized water, namely obtains Ag-Pd/ γ-Al after the material oven dry of gained
2o
3catalyst.
Prepare described Ag-Pd/ γ-Al as stated above
2o
3bimetallic catalyst, wherein metal A g accounts for 0.5% ~ 2% of catalyst gross mass, and metal Pd accounts for 0.01% ~ 0.5% of catalyst gross mass.
The ultraviolet-visible spectrum of described catalyst as shown in Figure 1.At the plasmaresonance absworption peak (because Pd does not have plasmaresonance absworption peak, the UV-vis spectrum of monometallic Pd material not being put in Fig. 1) that about 490nm is Ag.As we can see from the figure, along with the raising of Pd replacement amount, the absworption peak of Ag weakens gradually, can infer thus, covering due to Pd causes the disappearance of the absworption peak of Ag, also the bimetallic Pd-Ag material namely prepared by redox displacement method defines a kind of is core with Ag, the surface enrichment nano particle of Pd atom.This material, owing to being that the first load of Ag is on carrier, displacement reaction is there is and in load in Pd by redox reaction and Ag, therefore Pd is mainly present in the surface of catalyst, but not body phase, the utilization ratio of the precious metals pd greatly improved compared with the bimetallic catalyst synthesized with additive method like this, also just reduces the load capacity of Pd.And due to the existence of Ag, good diluting effect is served to Pd, therefore compare monometallic Pd catalyst and can obtain higher selective.
The preparation of single-metal reforming catalyst: as a comparison, uses infusion process to prepare γ-Al respectively
2o
3pd and the Ag single-metal reforming catalyst of load.With Pd/ γ-Al
2o
3for example, concrete preparation method is by a certain amount of γ-Al
2o
3add Pd (NO
3)
2at 90 DEG C of water bath methods after solution stirring 2h, 105 DEG C of oven dry, 300 DEG C of roastings.
Embodiment 21,2-dichloroethanes selective hydrogenation dechlorination reaction
According to the method for embodiment 1, flooding-the Ag-Pd/ γ-Al for preparing of displacement method
2o
3catalyst, wherein, after displacement reaction load P d, the actual negative carrying capacity of Ag is the actual negative carrying capacity of 0.88wt%, Pd is 0.08wt%.With the gas phase selective hydrogenation dechlorination reaction of this catalyst 1,2-dichloroethanes; Selective hydrogenation dechlorination reaction process is the process of reaction in-situ, and catalyst is first at H
2atmosphere is after 300 DEG C of reductase 12 ~ 5h, and temperature is adjusted to the hydrogenation-dechlorination reaction that reaction temperature carries out 1,2-dichloroethanes again.The consumption of catalyst is 100mg, and reaction temperature is 250 DEG C, H
2concentration be 30000 ~ 40000ppm, 1, the concentration of 2-dichloroethanes is 7000 ~ 7500ppm, using He as carrier gas, hydrogen is as reaction gas, the total flow of gas is 40 ~ 50ml/min, reacts 30 ~ 40h at ambient pressure, and reactant and product are by being furnished with the gas-chromatography on-line checkingi of fid detector.The result of catalytic reaction is be always 85 ~ 90% to the selective of target product ethene, and the reactivity after molecular balance is 2.9%.
Embodiment 31,2-dichloroethanes selective hydrogenation dechlorination reaction
According to the method for example 1, flooding-the Ag-Pd/ γ-Al for preparing of displacement method
2o
3catalyst, wherein, after displacement reaction load P d, the actual negative carrying capacity of Ag is the actual negative carrying capacity of 0.6wt%, Pd is 0.18wt%.With the gas phase selective hydrogenation dechlorination reaction of this catalyst 1,2-dichloroethanes; Selective hydrogenation dechlorination reaction process is the process of reaction in-situ, and catalyst is first at H
2atmosphere is after 300 DEG C of reductase 12 ~ 5h, and temperature is adjusted to the hydrogenation-dechlorination reaction that reaction temperature carries out 1,2-dichloroethanes again.The consumption of catalyst is 100mg, and reaction temperature is 250 DEG C, H
2concentration be 30000 ~ 40000ppm, 1, the concentration of 2-dichloroethanes is 7000 ~ 7500ppm, using He as carrier gas, hydrogen is as reaction gas, the total flow of gas is 40 ~ 50ml/min, reacts 30 ~ 40h at ambient pressure, and reactant and product are by being furnished with the gas-chromatography on-line checkingi of fid detector.The result of catalytic reaction is be always 85 ~ 90% to the selective of target product ethene, and the reactivity after molecular balance is 5.9%.
Comparative example 1
The monometallic Pd/ γ-Al prepared with infusion process
2o
3catalyst, wherein, the load capacity of Pd is 0.095wt%, and in load capacity and embodiment 2, the load capacity of metal Pd is close.With this catalyst, gas phase selective hydrogenation catalysis is carried out to 1,2-dichloroethanes; The consumption of catalyst is 100mg, and reaction temperature is 250 DEG C, H
2concentration be 30000 ~ 40000ppm, 1, the concentration of 2-dichloroethanes is 7000 ~ 7500ppm, using He as carrier gas, hydrogen is as reaction gas, the total flow of gas is 40 ~ 50ml/min, reacts 30 ~ 40h at ambient pressure, and reactant and product are by being furnished with the gas-chromatography on-line checkingi of fid detector.The result of catalytic reaction is the reactivity after molecular balance is 2.7%, is 10 ~ 15% to the selective of target product ethene.Compared with embodiment 2, monometallic Pd/ γ-Al
2o
3reactivity ratio's bimetallic catalyst of catalyst is on the low side, and catalytic selectivity is then obviously lower.
As can be seen here, by Ag-Pd/ γ-Al that dipping-displacement method is prepared
2o
3monometallic Pd/ γ-Al prepared by catalyst and infusion process
2o
3catalyst is compared, and not only catalytic activity is higher, also can obtain better selective, and the bimetallic catalyst namely prepared by dipping-displacement method can better dispersed metal Pd, and obtains higher catalytic selectivity by the synergy of Pd, Ag.
Comparative example 2
The monometallic Ag/ γ-Al prepared with infusion process
2o
3catalyst, wherein, the load capacity of Ag is about 0.9wt%, suitable with the load capacity of Ag in the catalyst in embodiment 2.With the gas phase selective hydrogenation dechlorination reaction of this catalyst 1,2-dichloroethanes; The consumption of catalyst is 100mg, and reaction temperature is 250 DEG C, H
2concentration be 30000 ~ 40000ppm, 1, the concentration of 2-dichloroethanes is 7000 ~ 7500ppm, using He as carrier gas, hydrogen is as reaction gas, the total flow of gas is 40 ~ 50ml/min, reacts 30 ~ 40h at ambient pressure, and reactant and product are by being furnished with the gas-chromatography on-line checkingi of fid detector.The result of catalytic reaction is that after molecular balance, reactivity is 0.7%.
As can be seen here, by Ag/ γ-Al that infusion process is prepared
2o
3the catalytic hydrogenation reaction of catalyst to 1,2-dichloroethanes does not almost have activity.
Embodiment 41,2-dichloroethanes selective hydrogenation dechlorination reaction
According to the method for embodiment 1, flooding-the Ag-Pd/ γ-Al for preparing of displacement method
2o
3catalyst, wherein, after displacement reaction load P d, the actual negative carrying capacity of Ag is the actual negative carrying capacity of 0.60wt%, Pd is 0.30wt%.With the gas phase selective hydrogenation dechlorination reaction of this catalyst 1,2-dichloroethanes; The consumption of catalyst is 100mg, and reaction temperature is 250 DEG C, H
2concentration be 30000 ~ 40000ppm, 1, the concentration of 2-dichloroethanes is 7000 ~ 7500ppm, using He as carrier gas, hydrogen is as reaction gas, the total flow of gas is 40 ~ 50ml/min, reacts 30 ~ 40h at ambient pressure, and reactant and product are by being furnished with the gas-chromatography on-line checkingi of fid detector.The result of catalytic reaction is, during reaction 1h, the selective of target product ethene is 5 ~ 15%, and this catalyst is not ideal enough at the catalytic selectivity of reaction starting stage.Along with the carrying out of reaction, the selective meeting of catalyst improves constantly, and catalytic activity can constantly reduce, and the ethylene selectivity after molecular balance is greater than 80%, and reactivity is 5.9%.
Compare with the bimetallic catalyst in example 3 with embodiment 2, when the replacement amount of metal Pd increases, catalytic activity significantly improves, selective, reduces along with the raising of the replacement amount of metal Pd; This is because along with the raising of metal Pd replacement amount, the active sites of continuous print Pd increases, and catalytic selectivity will be made to reduce.Therefore, there is an optimum interval in the selection for Pd load capacity, and can obtain ideal selective when namely Ag:Pd mol ratio is more than or equal to 2:1, consider catalytic activity, Ag:Pd mol ratio is maximum is no more than 100:1 simultaneously.
Claims (10)
1. one kind 1,2-dichloroethanes selective hydrogenation dechlorination reaction catalyst, it is characterized in that, with oxide C for carrier, carried metal A and B obtains A-B/C bimetallic catalyst successively, wherein, metal A is Ag or Cu, and first pass through infusion process load on oxide C carrier, metal B is Pd or Pt, the method load of being replaced by redox is on oxide C carrier, and oxide C is Al
2o
3, SiO
2, TiO
2or ZrO
2.
2. according to claim 11,2-dichloroethanes selective hydrogenation dechlorination reaction catalyst, it is characterized in that, described metal A accounts for 0.5% ~ 2% of catalyst gross mass, metal B accounts for 0.01% ~ 0.5% of catalyst gross mass, and metal A is 1 ~ 200:1 with the atomic molar ratio of metal B.
3. 1,2-dichloroethanes selective hydrogenation dechlorination reaction catalyst according to claim 2, it is characterized in that, described metal A is 2 ~ 100:1 with the atomic molar ratio of metal B.
4. the preparation method of 1,2-dichloroethanes selective hydrogenation dechlorination reaction catalyst according to claim 1, it is characterized in that, described method comprises the steps:
1) oxide C is added in metal A salting liquid flood, evaporate to dryness, carry out after evaporate to dryness drying, roasting obtain support type A/C catalyst, by the A/C catalyst logical H at 300 DEG C of temperature obtained
2reductase 12 ~ 5h;
2) by reduction after A/C catalyst in atmosphere of inert gases, put into deoxygenation deionized water, stir; Dropwise add the metal B salting liquid generation displacement reaction of deoxygenation simultaneously, stir 0.5 ~ 3h, reacted solution is filtered and is repeatedly washed till neutrality, drying filtering the solid obtained, namely obtaining described A-B/C bimetallic catalyst.
5. preparation method according to claim 4, is characterized in that, described metal A salt is the nitrate of metal A, chloride or sulfate, and described metal B salt is the nitrate of metal B, chloride or sulfate.
6. preparation method according to claim 4, is characterized in that, the concentration of described metal A salt or metal B salt is 1 × 10
-6~ 1 × 10
-3g/mL.
7. the method for a dichloroethanes selective hydrogenation dechlorination reaction, is characterized in that, with A-B/C according to claim 1 for catalyst, in the gas phase hydrogenation-dechlorination is carried out to 1,2-dichloroethanes, the dechlorination of 1,2-dichloroethanes is converted into the hydrocarbon that ethene is primary product.
8. method according to claim 7, is characterized in that, described method comprises the steps:
1) successively by infusion process and redox displacement method at the area load metal A of oxide C and B, the A-B/C bimetallic catalyst obtained, wherein, metal A is Ag or Cu, metal B is Pd or Pt, and metal A is lower than the standard electrode EMF of metal B, and oxide C is Al
2o
3, SiO
2, TiO
2or ZrO
2;
2) take A-B/C as catalyst, by 1,2-dichloroethanes, H after gasification
2after He mixing, carry out gas-phase catalytic hydrogenation dechlorination reaction to 1,2-dichloroethanes, the temperature of reaction is 200 ~ 300 DEG C, and being converted into ethene is the hydrocarbon of primary product.
9. method according to claim 8, it is characterized in that, in described A-B/C catalyst, described metal A accounts for 0.5% ~ 2% of catalyst gross mass, metal B accounts for 0.01% ~ 0.5% of catalyst gross mass, and metal A is 1 ~ 200:1 with the atomic molar ratio of metal B.
10. method according to claim 8, is characterized in that, in described catalytic hydrogenation and dechlorination reaction, in volumetric concentration, and H
2concentration be the concentration of 30000 ~ 40000ppm, 1,2-dichloroethanes be 7000 ~ 7500ppm, the flow velocity of gaseous mixture is 40 ~ 50ml/min; The time of described catalytic hydrogenation and dechlorination reaction is 30 ~ 40h.
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| CN107224982A (en) * | 2016-12-19 | 2017-10-03 | 浙江大学 | Cu/Pd alloys for reduction dechlorination material modify TiO2The preparation method of catalyst |
| CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
| CN107282048A (en) * | 2017-06-26 | 2017-10-24 | 厦门大学 | A kind of method that high-stability nano catalyst is prepared by atomic substitutions |
| CN108911968A (en) * | 2018-05-24 | 2018-11-30 | 西安凯立新材料股份有限公司 | A kind of method of catalytic distillation purifying chloroacetic acid |
| CN111193037A (en) * | 2019-10-22 | 2020-05-22 | 超威电源集团有限公司 | Preparation method of aluminum-air battery cathode reduction catalyst |
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| CN107224982B (en) * | 2016-12-19 | 2019-08-23 | 浙江大学 | Cu/Pd alloy for reduction dechlorination material modifies TiO2The preparation method of catalyst |
| CN107282048A (en) * | 2017-06-26 | 2017-10-24 | 厦门大学 | A kind of method that high-stability nano catalyst is prepared by atomic substitutions |
| CN107282048B (en) * | 2017-06-26 | 2019-05-10 | 厦门大学 | A method of high-stability nano catalyst is prepared by atomic substitutions |
| CN107282086A (en) * | 2017-07-06 | 2017-10-24 | 南京大学 | A kind of catalyst of catalytic methane dry reforming reaction and its preparation method and application |
| CN108911968A (en) * | 2018-05-24 | 2018-11-30 | 西安凯立新材料股份有限公司 | A kind of method of catalytic distillation purifying chloroacetic acid |
| CN108911968B (en) * | 2018-05-24 | 2021-03-05 | 西安凯立新材料股份有限公司 | Method for purifying monochloroacetic acid by catalytic rectification |
| CN111193037A (en) * | 2019-10-22 | 2020-05-22 | 超威电源集团有限公司 | Preparation method of aluminum-air battery cathode reduction catalyst |
| CN111193037B (en) * | 2019-10-22 | 2022-02-22 | 超威电源集团有限公司 | Preparation method of aluminum-air battery cathode reduction catalyst |
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