CN102211043B - Method for preparing palladium-silver bimetallic catalyst - Google Patents

Method for preparing palladium-silver bimetallic catalyst Download PDF

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CN102211043B
CN102211043B CN2011100861454A CN201110086145A CN102211043B CN 102211043 B CN102211043 B CN 102211043B CN 2011100861454 A CN2011100861454 A CN 2011100861454A CN 201110086145 A CN201110086145 A CN 201110086145A CN 102211043 B CN102211043 B CN 102211043B
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palladium
presoma
silver
organic polymer
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CN102211043A (en
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梁琨
谭都平
王建明
常晓昕
车春霞
高源�
梁玉龙
林宏
韩伟
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China Petroleum and Natural Gas Co Ltd
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Abstract

The invention discloses a method for preparing a palladium-silver bimetallic catalyst, which is characterized by comprising the following steps of: supporting organic polymer on a catalyst carrier, and grafting a functional group on a supported polymer chain through a complexing agent to obtain a functionalized-polymer/Al2O3 carrier; preparing a palladium-silver solution, immersing the carrier supported with the functionalized polymer in the prepared palladium-silver solution, performing complex reaction on palladium, silver and the functional group on the polymer chain, and making palladium, silver and the organic polymer form an organic polymer metal complex to obtain a (Pd-Ag)-polymer complex/Al2O3 precursor; and roasting the (Pd-Ag)-polymer complex/Al2O3 precursor at the temperature of between 380 and 550DEG C for 2 to 6 hours. The catalyst prepared by the method can be used for the selective hydrogenation process of C2-C4 fractions, and has high hydrogenation activity, excellent selectivity and high hydrogenation stability.

Description

A kind of palladium-silver bimetal method for preparing catalyst
Technical field
The present invention relates to a kind of preparation method of selective hydrogenation catalyst.
Background technology
Ethene is one of most important basic material of petro chemical industry, and as the monomer ethylene of synthetic various polymer, the overwhelming majority is made by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel etc.) steam cracking.Through this method obtain take ethene as main C 2The acetylene that contains 0.5%～2.3% (molar fraction) in the cut.Can make the polymerization process of ethene complicated if having in the ethene than the polyacetylene existence, worsen polymer performance.Reduce polymerization catalyst, increase the consumption of catalyst.So the acetylene content in the ethene must be dropped to below the certain value, could be as the monomer of synthetic high polymer.
At present industrial common employing selects hydrogenation and solvent extraction method to remove C 2Acetylene in the cut.Solvent extraction process both can obtain smart ethene, recyclable byproduct acetylene again, but its flow process is complicated, and operation easier is larger.At present, to make acetylene conversion be that ethene is most economical and the most received method to catalysis selective hydrogenation.
Catalysis selective hydrogenation technique comprises and is divided into front-end hydrogenation technique and back end hydrogenation technique in the ethylene unit, front-end hydrogenation and back end hydrogenation refer to that acetylene hydrogenation reactor is for the domethanizing column position, hydrogenation reactor is front-end hydrogenation before being positioned at domethanizing column, and hydrogenation reactor is back end hydrogenation after being positioned at domethanizing column.The back end hydrogenation method is owing to be more common in the small-sized ethylene unit that builds up in early days, and recent large-scale ethylene plant adopts carbon two front-end hydrogenation techniques more.
For carbon two back end hydrogenation techniques, coking can occur in catalyst in running, and the activity of catalyst and selectively gradually decay affect the yield of ethene, even cause acetylene to spill, and have a strong impact on downstream polymerization the production of material.For front-end hydrogenation technique, owing in the reaction mass a large amount of hydrogen is arranged, the undesirable meeting of catalyst selectivity causes the hydrogenation of too much ethene, and thermal discharge is large in the reactor, and the danger that temperature runaway occurs is arranged.
(the Chem.Commun. such as Park, 1991, B1188-1189 and Ind.Eng.Chem.Res., 1992,31:469-474) load on palladium on the aluminium oxide and add the surface acidity that alkali metal potassium and/or alkaline earth metals calcium, magnesium etc. are regulated alumina support or catalyst, improve ethylene selectivity, reduced green oil generating amount, prolonged the cycle of operation.US5856262 has reported silica take potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) modification as carrier, and the method for the low acid palladium catalyst of preparation is at air speed 3000h -1, 35 ℃ of inlet temperatures, entrance acetylene molar fraction 0.71%, under the condition of hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 1 * 10-7, and ethylene selectivity reaches 56%.Patent US5587348 adds co-catalyst silver and palladium effect take aluminium oxide as carrier, adds alkali metal, and the fluorine of chemical bonding has prepared carbon two hydrogenation catalysts of function admirable.This catalyst has the green oil of minimizing and generates, and improves ethylene selectivity, reduces the characteristics of oxygenatedchemicals growing amount.
Above traditional hydrogenation catalyst all is to adopt the preparation of aqueous solution infusion process, is subject to the impact of solvation effect in the dipping of catalyst and dry processing procedure, and the metal active constituent presoma is deposited on carrier surface with aggregate form.Because the heterogeneity of disperseing, high-temperature roasting cause easily metallic migration gathering and form large crystal grain; Adopt the method Kaolinite Preparation of Catalyst of wet reducing for head it off US5510550, by in maceration extract, adding reducing agent, make Pd, Ag solution is not reduced when dry, reduced the active component dispersion problem of non-uniform that solvation effect causes, but because the capillary impact of solvent, Pd, the deposition of Ag metallic is still inhomogeneous, affect the repeatability of catalyst preparation, reduce the utilization rate of active component, adopt in addition the microemulsion method to carry out the preparation of your catalyst among the US 4714692, but the particle diameter of this emulsion molecule has certain distribution, so that the quantity of contained active component presoma is not identical in each emulsion particle, the active component presoma still exists with the aggregate form in addition, may form crystal grain not of uniform size in roasting, its crystal phase structure also can be had any different in addition, affects the selective of catalyst.
Summary of the invention
In view of above situation, the present invention proposes the preparation method that a kind of palladium-silver bimetal is the catalyst of active component.
The solution of the present invention is: palladium-silver bimetal is the preparation method of the catalyst of active component, is to make palladium and silver form the organic polymer metal complex with organic polymer by adding complexing agent, obtains Pd-Ag-macromolecule/Al 2O 3Presoma; At 380～550 ℃ to Pd-Ag-macromolecule/Al 2O 3Presoma carries out roasting, and the time is that 2～6h obtains.
Organic polymer of the present invention, require need to contain on its side chain can with the group of complexing agent reaction, the present invention is special requirement not, such as halogen, wherein one or more of the groups such as cyano group; Complexing agent of the present invention both can carry out functionalization with the organic macromolecule side-chain radical, ion that again can complexing Pd, Ag after reaction, and the present invention is special requirement not also, can be amido or two amidos such as the contained functional group of complexing agent.
The more specifically scheme that the present invention recommends is: organic polymer is loaded on the catalyst carrier, by complexing agent grafted functional group on the macromolecular chain of institute's load, obtain functionalized-macromolecule/Al 2O 3Carrier; The solution of preparation palladium-Yin, load there is functionalized high molecular carrier impregnation in the palladium of having prepared-Yin solution, carry out complex reaction, make the functional group on palladium, silver and the macromolecular chain carry out complex reaction, palladium and silver have formed the organic polymer metal complex with organic polymer, obtain (Pd-Ag)-high-molecular complex/Al 2O 3Presoma; At 380～550 ℃ to (Pd-Ag)-high-molecular complex/Al 2O 3Presoma carries out roasting, and the time is 2～6h, obtains required catalyst; Selected
Since the ion of palladium-Yin be by with the chemical reaction of functional group but not physical absorption be attached on the macromolecular chain, therefore the atom of palladium, silver is uniform sequential distribution at macromolecular chain, in the process of roasting, palladium-silver atoms can carry out oxidation reaction in position, in the process of oxidation reaction, form the oxide eutectic of palladium, silver.Catalyst prepared by this method is the alloy-type bimetallic catalyst, possesses the selective of excellence.Adopt this preparation method to overcome maceration extract surface tension and solvation effect to the impact of the dispersion of palladium-Yin, the catalyst with the regular palladium-Yin of preparation structure height reaches the effect that improves catalyst activity and selectivity.
Palladium-the palladium-silver system supported catalyst of method preparation provided by the invention has the highly equally distributed structure of palladium-Yin.
This process can be divided into 3 the step carry out:
(1). at first prepare functionalized-macromolecule/Al 2O 3Presoma;
(2). preparation (Pd-Ag)-high-molecular complex/Al 2O 3Presoma;
(3). carry out roasting 2～6h at 380～550 ℃ of presomas to step 2 preparation.
Carrier of the present invention is the alumina series carrier, mainly contains Al 2O 3, as being Al 2O 3Or Al 2O 3In be doped with other hopcalite, other oxide can be silica, titanium oxide, magnesia, calcium oxide etc.Al among the present invention 2O 3Crystal formation is preferably θ, α or it mixes crystal formation.
Al among the present invention 2O 3Carrier can be sphere, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc.
The preparation method of this catalyst comprises the steps:
A. functionalized-macromolecule/Al 2O 3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms Polymer Solution, again with carrier impregnation in mentioned solution, leave standstill and make organic polymer (polymer) be deposited on Al 2O 3The surface, drying; Add again the complexing agent backflow 0.5～300min that contains functional group, prepare functionalized-macromolecule/Al 2O 3Presoma;
More specifically method as: under 20～35 ℃, the organic polymer that has reactive group on the side chain is dissolved in the organic solvent, carrier impregnation in mentioned solution, is left standstill 2～6h, make described organic polymer be deposited on Al 2O 3The surface is after the drying, at 20～35 ℃ of lower complexing agents that add, described complexing agent both can carry out functionalization with the organic macromolecule side-chain radical, and ion that again can complexing Pd, Ag after reaction is with the above-mentioned solution 1～4h that refluxes, be cooled to 20～35 ℃, with deionized water washing, drying.
B. (Pd-Ag)-high-molecular complex/Al 2O 3The preparation of presoma
Preparation palladium-Yin solution, and with inorganic acid for adjusting pH value 1～4 takes by weighing prepared functionalized-macromolecule/Al 2O 3Presoma joins the solution of preparing palladium-Yin in the presoma, 20～35 ℃ of lower dipping 0.5～2h, and washing, drying obtain (Pd-Ag)-high-molecular complex/Al 2O 3Presoma.
C. the preparation of catalyst
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain (Pd-Ag)/Al 2O 3Catalyst.Above-mentioned roasting can be carried out in oxygen atmosphere is arranged, and effect is better.
When catalyst used, the catalyst that above method can be made used H in reactor 2Reduce processing, obtain the reduction-state catalyst.
Also can prepare first functionalized polymer with in the above-mentioned A process, prepare again functionalized-polymer/Al 2O 3Presoma.
In steps A, described organic solvent plays the high molecular effect of dissolving, and the present invention does not limit the kind of solvent, as long as possess above-mentioned functions.
In step B, palladium in the described mixed solution, silver salt consumption to be making the Pd of final catalyst, and Ag content can be determined according to the different purposes of catalyst the Pd of catalyst, Ag content; In molal quantity, the reactive group molal quantity preferably 100～1 in complexing agent molal quantity/macromolecule; The molal quantity of functional group's molal quantity on the functionalized rear macromolecular chain/(Pd+Ag) preferably 100～1; The molal quantity of complexing agent molal quantity/(Pd+Ag) preferably 10000～1.
Complexing agent mainly plays complexing Pd, Ag ion among the present invention, and the present invention does not limit the kind of complexing agent, as long as can possess above-mentioned functions, consumption is not limited especially yet, can regulate according to Pd, Ag content difference.
Macromolecule only plays skeleton or template among the present invention, complexing agent can be grafted on its side chain, and the present invention does not limit high molecular kind, as long as can possess above-mentioned functions, for the organic macromolecule addition, the present invention does not limit, and can regulate according to Pd, Ag content difference.
Aluminium oxide only plays carrier among the present invention, and therefore, the present invention does not limit the kind of carrier yet.
Using plasma emission spectrometer or atomic absorption spectrum can record this catalyst P d content and Ag content (standard GB/T 15337-94).
Catalyst of the present invention can be used for carbon two to the selective hydrogenation process of C-4-fraction, has the selective and good stabilized hydrogenation performance of good hydrogenation activity, excellence.
The specific embodiment
Analysis test method:
The using plasma emission spectrometer records this catalyst P d content and Ag content.Standard GB/T 15337-94.
Embodiment 1:
A. functionalized poly vinyl chloride (PVC)/Al 2O 3The preparation of presoma
Take by weighing Φ 4.5mm, length is 4.5mm, and specific area is 15m 2/ g, pore volume are 0.25ml/g, and bulk density is 1.1g/cm 3Column Al 2O 3Carrier 250g.
PVC4.450g is dissolved in the 400ml oxolane (THF) fully, the carrier impregnation that weighed up in mentioned solution, is left standstill behind the ultrasonic processing of the carrier 0.5h and makes PVC be deposited on Al 2O 3The surface, drying.Obtain 255gPVC/Al 2O 3
Add 59.64g dicyandiamide and 2.0gNa 2CO 3, add 255gPVC/Al 2O 3Refluxed 2 hours, and be cooled to room temperature, to neutral, drying obtains functionalized PVC/Al with the deionized water washing 2O 3Presoma.
B (Pd-Ag)-polymer/Al 2O 3The preparation of presoma
Take by weighing 0.055gPd (NO 3) 2, 0.08gAgNO 3, measure 0.5ml nitric acid, be mixed with the mixed solution of 1200ml, take by weighing prepared functionalized-macromolecule/Al 2O 3Presoma 255g joins Pd (NO 3) 2, AgNO 3Mixed solution in, absorption 0.5h, inclining raffinate, with above-mentioned product with deionized water washing to neutral, obtain (Pd-Ag)-polymer/Al 2O 3Presoma.
The preparation of C catalyst
With the presoma of above-mentioned preparation, 500 ℃ of roasting 4h in air atmosphere obtain oxidation state (Pd-Ag)/Al 2O 3Catalyst.Being positioned over before the use in the fixed-bed reactor, is N with mol ratio 2: H 2=0.1: 1 mist, 120 ℃ of temperature, 12h is processed in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is that 0.01%, Ag content is 0.02%.
Comparative Examples 1
Take by weighing Φ 4.5mm, length is 4.5mm, and specific area is 15m 2/ g, pore volume are 0.25ml/g, and bulk density is 1.1g/cm 3Column Al 2O 3Carrier 250g.
Take by weighing 0.055gPd (NO 3) 2, 0.08gAgNO 3, measure 0.5ml nitric acid, be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, ultrasonic vibration 0.5h, dry rear at 500 ℃ of roasting temperature 4h, obtain (Pd-Ag)/Al 2O 3Catalyst.Being positioned over before the use in the fixed-bed reactor, is N with mol ratio 2: H 2=0.1: 1 mist, 120 ℃ of temperature, 12h is processed in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is that 0.01%, Ag content is 0.02%.
Embodiment 2
A, functionalized polystyrene acrylonitrile (SAN)/Al 2O 3Preparation
Take by weighing Φ 2.5mm, specific area is 100m 2/ g, pore volume are 0.87ml/g, and bulk density is 0.65g/cm 3Spherical Al 2O 3Carrier 250g.
Take by weighing SAN resin 1.1g, be dissolved in the 300ml DMF solvent, stirring is dissolved the SAN resin fully under the room temperature, adds above-mentioned weighing carrier in this solution, leaves standstill 1 hour after fully stirring, and drying behind the separation solvent obtains SAN/Al 2O 3
With SAN/Al obtained above 2O 3, join in the 500ml deionized water, add the 28.8g ethylenediamine, take out product behind the backflow 4h after the cooling, washing is to neutral, and drying obtains functionalized SAN/Al 2O 3
B, (Pd-Ag)-polymer/Al 2O 3The preparation of presoma
Take by weighing 0.47gPd (NO 3) 2, 0.8gAgNO 3, measure 0.5ml nitric acid, be mixed with the mixed solution of 1200ml, take by weighing prepared functionalized-SAN/Al 2O 3Presoma 251.1g is with functionalized-macromolecule/Al 2O 3Join Pd (NO 3) 2, AgNO 3Mixed solution in, absorption 2h, inclining raffinate, with above-mentioned product with deionized water washing to neutral, obtain (Pd-Ag)-polymer/Al 2O 3Presoma.
The preparation of C, catalyst
With the presoma of above-mentioned preparation, 380 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere 2O 3Catalyst.Recording this catalyst P d content is that 0.06%, Ag content is 0.2%.
Comparative Examples 2
Method according to patent US 4484015 embodiment 1:
Take by weighing Φ 2.5mm, specific area is 100m 2/ g, pore volume are 0.87ml/g, and bulk density is 0.65g/cm 3Spherical θ-Al 2O 3Carrier 250g.
Take by weighing 0.47gPd (NO 3) 2Being dissolved in the 100ml deionized water, is 2.8 with the pH value of watery hydrochloric acid regulator solution, and described carrier impregnation in the solution that has prepared, 120 ℃ of dryings 10 hours, is obtained catalyst A, and 90% Pd is distributed in the scope of surperficial 300 μ m in this catalyst.
Take by weighing 0.8gAgNO 3, measure 0.5ml nitric acid and be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, absorption 1h, dry rear at 500 ℃ of roasting temperature 8h, obtain Pd-Ag/Al 2O 3Catalyst, recording this catalyst P d content is that 0.06%, Ag content is 0.2%.
Embodiment 3
A, functionalized SAN/Al 2O 3Preparation
Take by weighing 4.5*4.5mm, specific area is 2m 2The cylindric carrier A l of/g 2O 3Carrier 250g.
Take by weighing SAN resin 5.15g, be dissolved in 300ml dimethyl formamide (DMF) solvent, stirring is dissolved the SAN resin fully under the room temperature, adds the 0.13g hydroxylamine hydrochloride, 5gK 2CO 3, be heated to it and dissolve fully.After stirring half an hour, with Al 2O 3Carrier 250g adds above solution, drips 200ml ethanol, and constantly stirs, and takes out product after 1 hour, and washing obtains functionalized SAN/Al to neutral after the drying 2O 3
B, (Pd-Ag)-polymer/Al 2O 3The preparation of presoma
Take by weighing 0.11gPd (NO 3) 2, 0.30gAgNO 3, be mixed with the mixed solution of 1200ml, take by weighing prepared functionalized-SAN/Al 2O 3Presoma 255g is with functionalized SAN/Al 2O 3Join Pd (NO 3) 2, AgNO 3Mixed solution in, absorption 1h, inclining raffinate, with above-mentioned product with deionized water washing to neutral, obtain (Pd-Ag)-polymer/Al 2O 3Presoma.
The preparation of C, catalyst
With the presoma of above-mentioned preparation, 550 ℃ of roasting 2h obtain Pd-Ag/Al in air atmosphere 2O 3Catalyst.Recording this catalyst P d content is Pd 0.02%, and Ag content is 0.07%.
Comparative Examples 3 adopts the catalyst of the method preparation of US 5510566B1
Getting commercial catalyst G-83C (German southern chemical company produce), to be called No. 0 catalyst 300ml for subsequent use.
Take by weighing the 300ml0 catalyst, 6ml glucose, 9.6mlKOH is dissolved in the 300ml aqueous solution, stirs 1 hour, and inclining unnecessary liquid, and the catalyst sample of wet reducing was 538 ℃ of roastings 2 hours, and this catalyst contains Pd 0.02%, and Ag 0.07%.
Embodiment 4
A, functionalization polypropylene acid amides/Al 2O 3Preparation
Take by weighing Φ 2.5mm, specific area is 50m 2/ g, pore volume are the ball type carrier 250g of 0.75ml/g, wherein contain θ-Al 2O 3220g, titanium oxide 30g.
Take by weighing polyacrylamide resin 8.0g, be dissolved in the 300ml water, stirring is dissolved polyacrylamide resin fully under the room temperature, adds above-mentioned weighing carrier in this solution, leaves standstill 1 hour after fully stirring, and drying behind the separation solvent obtains polyacrylamide/Al 2O 3
With polyacrylamide/Al obtained above 2O 3, join in the 500ml deionized water, add the 25g hydroxylamine hydrochloride, add 5.0gNa 2CO 3, being heated to it and dissolving fully, backflow 1h takes out product after the cooling, and washing is to neutral, drying obtains functionalized-polyacrylamide/Al 2O 3
B, (Pd-Ag)-polymer/Al 2O 3The preparation of presoma
Take by weighing 0.275gPd (NO 3) 2, 0.40gAgNO 3, measure 0.5ml nitric acid, be mixed with the mixed solution of 1200ml, take by weighing the functionalization polypropylene acid amides/Al that has prepared 2O 3Presoma 258g is with functionalized-polyacrylamide/Al 2O 3Join Pd (NO 3) 2, AgNO 3Mixed solution in, absorption 1h, inclining raffinate, with above-mentioned product with deionized water washing to neutral.Obtain (Pd-Ag)-polymer/Al 2O 3Presoma.
The preparation of C, catalyst
With the presoma of above-mentioned preparation, 500 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere 2O 3Catalyst.Recording this catalyst P d content is that 0.05%, Ag content is 0.1%.
Comparative Examples 4
Take by weighing Φ 2.5mm, specific area is 50m 2/ g, pore volume are the ball type carrier 250g of 0.75ml/g, wherein contain θ-Al 2O 3220g, titanium oxide 30g.
Take by weighing 0.275gPd (NO 3) 2, adding 0.5ml nitric acid, obtain solution 300ml adds above-mentioned carrier in this solution, shakes 0.5 hour, and inclining remaining liquid, after the drying, gets catalyst A.
Take by weighing again 0.40gAgNO 3, adding 0.5ml nitric acid, obtain solution 300ml adds catalyst A in this solution, shakes after 0.5 hour, and inclining remaining liquid, and after the drying, 500 ℃ of roasting 8h obtain (Pd-Ag)/Al in air atmosphere 2O 3Catalyst, recording this catalyst P d content is that 0.05%, Ag content is 0.1%.
Embodiment 5
A, functionalization polypropylene/Al 2O 3Preparation
Take by weighing Φ 2.5mm, specific area is 50m 2/ g, pore volume are 0.87ml/g, and bulk density is 0.65g/cm 3Spherical Al 2O 3Carrier 250g.
Take by weighing polypropylene 8.0g, be dissolved in the 300mlDMF solvent, stirring is dissolved polypropylene fully under the room temperature, adds above-mentioned weighing carrier in this solution, leaves standstill 1 hour after fully stirring, and drying behind the separation solvent obtains polypropylene SAN/ Al 2O 3
With polypropylene/Al obtained above 2O 3, join in the 500ml deionized water, add the 100g ethylenediamine, backflow 2h.Take out product after the cooling, washing is to neutral, and drying obtains functionalization polypropylene/Al 2O 3
B, (Pd-Ag)-polymer/Al 2O 3The preparation of presoma
Take by weighing 0.275gPd (NO 3) 2, 0.59gAgNO 3, measure 0.5ml nitric acid, be mixed with the mixed solution of 1200ml, take by weighing prepared functionalized-polypropylene/Al 2O 3Presoma 258g is with functionalized-polypropylene/Al 2O 3Join Pd (NO 3) 2, AgNO 3Mixed solution in, absorption 1h, inclining raffinate, with above-mentioned product with deionized water washing to neutral, obtain (Pd-Ag)-polymer/Al 2O 3Presoma.
The preparation of C, catalyst
With the presoma of above-mentioned preparation, 500 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere 2O 3Catalyst.Recording this catalyst P d content is that 0.05%, Ag content is 0.15%.
Comparative Examples 5
Take by weighing Φ 2.5mm, specific area is 50m 2/ g, pore volume are 0.87ml/g, and bulk density is 0.65g/cm 3Spherical Al 2O 3Carrier 250g.
Take by weighing 0.59gAgNO 3, measure 0.5ml nitric acid, prepare to get solution 300ml with deionized water, above-mentioned carrier is added in this solution shook 0.5 hour, inclining remaining liquid, after the drying, gets catalyst B.Take by weighing 0.275gPd (NO 3) 2, prepare to get solution 300ml, catalyst B is added in this solution, shook 0.5 hour, inclining remaining liquid, and after the drying, 500 ℃ of roasting 8h obtain (Pd-Ag)/Al in air atmosphere 2O 3Catalyst.Recording this catalyst P d content is that 0.05%, Ag content is 0.15%.
Implementation result:
Adopt the process conditions of predepropanization front-end hydrogenation, to the resulting catalyst of the preparation method of above embodiment and Comparative Examples, carry out Performance Ratio.Reaction mass forms as shown in table 1.
Table 1 reaction mass forms
Reaction mass H 2 C 2H 2 C 2H 4 C 2H 6 C 3H 6 C 3H 8 PDMA CO C 4+
Content (v/v%) 17 0.63 40 10 29 2 0.77 0.3 0.3
Reaction condition: material air speed: 5000/h, operating pressure: 3.9MPa, loaded catalyst: 200ml.Reaction result is as shown in table 2.
Table 2 predepropanization front-end hydrogenation reaction result
Catalyst Inlet temperature (℃) Temperature rise (℃) C 2H 2Conversion ratio (%) Selectively (%)
Embodiment 1 67 21 51 75
Comparative Examples 1 71 23 42 58
Embodiment 2 50 35 78 42
Comparative Examples 2 46 40 70 32
Embodiment 3 50 35 78 42
Comparative Examples 3 46 40 72 35
Embodiment 4 51 43 82 68
Comparative Examples 4 56 35 42 41
Embodiment 5 56 38 64 76
Comparative Examples 5 50 32 45 29
Because embodiment can find out, catalyst provided by the present invention when active component content is identical, have better activity with selective, and catalyst can be applicable to the selection hydrogenation of carbon two and C3 fraction.

Claims (13)

1. palladium-silver bimetal method for preparing catalyst is characterized in that adding complexing agent and makes palladium and silver form the organic polymer metal complex with organic polymer, obtains Pd-Ag-high-molecular complex/Al 2O 3Presoma: be about to organic polymer and load on the catalyst carrier, and by complexing agent grafted functional group on the macromolecular chain of institute's load, obtain functionalized-high-molecular complex/Al 2O 3Carrier; The solution of preparation palladium-Yin, load there is functionalized high molecular carrier impregnation in the palladium of having prepared-Yin solution, make the functional group on palladium, silver and the macromolecular chain carry out complex reaction, palladium and silver have formed the organic polymer metal complex with organic polymer, obtain (Pd-Ag)-high-molecular complex/Al 2O 3Presoma; At 380～550 ℃ to (Pd-Ag)-high-molecular complex/Al 2O 3Presoma carries out roasting, and the time is 2～6h, obtains catalyst; Wherein the contained functional group of complexing agent is amido or two amidos.
2. palladium according to claim 1-silver bimetal method for preparing catalyst, it is characterized in that containing on the organic macromolecule side chain can with the group of complexing agent reaction.
3. palladium according to claim 2-silver bimetal method for preparing catalyst is characterized in that the group that contains on the organic macromolecule side chain is one or more in halogen, the cyano group.
4. palladium according to claim 1-silver bimetal method for preparing catalyst is characterized in that carrier is Al 2O 3Or Al 2O 3In be doped with other hopcalite, other oxide is silica, titanium oxide, magnesia and/or calcium oxide.
5. palladium according to claim 1-silver bimetal method for preparing catalyst is characterized in that Al 2O 3Crystal formation be that θ, α or its mix crystal formation.
6. palladium according to claim 1-silver bimetal method for preparing catalyst, it is characterized in that organic polymer is loaded on the catalyst carrier, and by complexing agent grafted functional group on the macromolecular chain of institute's load, refer to: organic polymer is loaded on the catalyst carrier, then grafted functional group on the macromolecular chain of institute's load.
7. palladium according to claim 1-silver bimetal method for preparing catalyst, it is characterized in that organic polymer is loaded on the catalyst carrier, and by complexing agent grafted functional group on the macromolecular chain of institute's load, refer to: first with after the organic polymer grafted functional group, be carried on again on the catalyst carrier, prepare functionalized-macromolecule/Al 2O 3Presoma.
8. palladium according to claim 1-silver bimetal method for preparing catalyst is characterized in that the preparation method of catalyst comprises the steps:
A. functionalized-macromolecule/Al 2O 3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms Polymer Solution, again with carrier impregnation in mentioned solution, leave standstill and make organic polymer be deposited on Al 2O 3The surface, drying; Add again the complexing agent backflow 0.5～300min that contains functional group, prepare functionalized-macromolecule/Al 2O 3Presoma;
B.Pd-Ag-high-molecular complex/Al 2O 3The preparation of presoma
Preparation palladium-Yin solution, and with inorganic acid for adjusting pH value 1～4 takes by weighing prepared functionalized-macromolecule/Al 2O 3Presoma joins the solution of preparing palladium-Yin on the predecessor, 20～35 ℃ of lower dipping 0.5～2h, and washing, drying obtain Pd-Ag-high-molecular complex/Al 2O 3Presoma;
C. the preparation of catalyst
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h.
9. palladium according to claim 8-silver bimetal method for preparing catalyst, it is characterized in that (A) step is: under 20～35 ℃, the organic polymer that has reactive group on the side chain is dissolved in the organic solvent, with carrier impregnation in mentioned solution, leave standstill 2～6h, make described organic polymer be deposited on Al 2O 3The surface, after the drying, at 20～35 ℃ of lower complexing agents that add, the solution backflow 1～4h with above-mentioned is cooled to 20～35 ℃, with deionized water washing, drying.
10. palladium according to claim 8-silver bimetal method for preparing catalyst, it is characterized in that on the functionalized rear macromolecular chain functional group's molal quantity/(Pd+Ag) molal quantity is 100～1.
11. palladium according to claim 8-silver bimetal method for preparing catalyst is characterized in that in molal quantity, the reactive group molal quantity is 100～1 in complexing agent molal quantity/macromolecule.
12. palladium according to claim 8-silver bimetal method for preparing catalyst is characterized in that the molal quantity of complexing agent molal quantity/(Pd+Ag) is 10000～1.
13. palladium according to claim 8-silver bimetal method for preparing catalyst is characterized in that roasting carries out in oxygen atmosphere is arranged.
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