CN103071494B - Hydrogenation catalyst with shell distribution and comprising silica auxiliary agent - Google Patents

Hydrogenation catalyst with shell distribution and comprising silica auxiliary agent Download PDF

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Publication number
CN103071494B
CN103071494B CN201110330410.9A CN201110330410A CN103071494B CN 103071494 B CN103071494 B CN 103071494B CN 201110330410 A CN201110330410 A CN 201110330410A CN 103071494 B CN103071494 B CN 103071494B
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catalyst
metal
hydrogenation
palladium
silica
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CN103071494A (en
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田保亮
黄龙
戴伟
彭晖
李宝芹
乐毅
杨溢
唐国旗
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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

Abstract

The invention discloses a hydrogenation catalyst. In order to satisfy requirement for reducing unsaturated hydrocarbon hydrogenation catalyst green oil yield and prolonging catalyst life, the invention provides a catalyst which comprises a carrier, a metal active component palladium, and silica. The metal active component palladium and silica both form eggshell-type distributions. The shell thickness of palladium is lower than 500mum. More than 90% of palladium element is positioned in the shell. The thickness difference between silica shell and palladium shell is lower than 80mum. When the catalyst provided by the invention is used in an unsaturated hydrocarbon hydrogenation reaction, the catalyst has the advantages of high activity and selectivity, and ultralow yield of carbon deposit and green oil.

Description

There is shell distribution and the hydrogenation catalyst containing silica auxiliary agent
Technical field
The present invention relates to a kind of hydrogenation catalyst, more particularly, the present invention relates to a kind of palladium group hydrogenation catalyst and the application in unsaturated hydrocarbons selective hydrogenation field thereof with special elements distribution.
Background technology
Unsaturated hydrocarbons selective hydrogenation is widely used, the process in the industry with important value comprise alkynes and alkadienes selective hydrogenation be in monoolefine, alkadienes micro-alkyne selec-tive hydrogenation removes, phenylacetylene hydrogenation is styrene etc., its conventional catalyst is load type palladium catalyst.
In alkynes and diene hydrogenation process, one of side reaction is alkynes or diene polymerization is high polymer (being called as green oil in industry).As in C-2-fraction hydrogenation and removing alkynes, acetylene can dimerization be alkadienes, and if acetylene can dimerization be butadiene, butadiene and acetylene or ethene continue to be polymerized to C 6-C 24high polymer green oil, these green oils can stick to catalyst surface, reduce catalyst activity; Also can block duct simultaneously, reduce the diffusion coefficient of catalyst, reduce the reactivity worth of catalyst further.Green oil also progressively can be converted into carbon distribution, can reduce the olefine selective (M.Larsson, J.Jansson, S.Asplund, J.Catal., 1998,178 (1): 49-57.) in the selective hydrogenation of alkynes and alkadienes.For making the acetylene exported remain qualified, need constantly to improve temperature of reactor, improve reaction temperature and also can reduce catalyst choice simultaneously, therefore catalyst needs to regenerate more frequently, causes production cost to improve.Above-mentioned problem equally also exists and other hydrogenation of unsaturated hydrocarbons processes, comprise C3 fraction hydrogenation and removing propine and allene, carbon four selective hydrogenation and removing butine to prepare butadiene, carbon four selective hydrogenation and removing butine and butadiene and prepare butylene etc., therefore developing green oil, to produce low hydrogenation catalyst significant.
CN1097480 discloses a kind of catalyst for selective acetylene hydrocarbon hydrogenation and forms, and active component is palladium, and co-catalyst is bismuth, and carrier is aluminium oxide.Bismuth add the generation significantly reducing green oil on catalyst, decrease the carbon distribution on catalyst, improve the service life of catalyst, simultaneously the activity and selectivity of catalyst is improved.
CN1665588 discloses a kind of Pd-Ag/Al 2o 3catalyst, catalyst contains the I of 10-1000ppm, and I is for preparing by its aqueous solution and catalyst exposure.Catalyst deactivation rate and the green oil generating amount of gained significantly reduce, and catalyst expected service life extends.
Such scheme, on some scheme palladium catalysts, green oil generating amount and deactivation rate decrease, but catalyst activity or selective decline more; Some scheme activity and selectivity aspects do not decline or increase, but the decreasing value of green oil generating amount and deactivation rate is less, and the life cycle of catalyst increases less.Therefore green oil is developed and the little high-performance hydrogenation catalyst of carbon distribution growing amount has important industrial significance.
Summary of the invention
The present invention reduces hydrogenation of unsaturated hydrocarbons catalyst green oil generating amount and the requirement in extending catalyst life-span, provide a kind of palladium-based metal hydrogenation catalyst of improvement, also containing silica auxiliary agent on this catalyst, and the distribution of its silica auxiliary agent has eggshell type, described catalyst activity and selectivity is high, and green oil generating amount and deactivation rate low, long service life.
Certain described element eggshell type distribution is on a catalyst specifically defined as: this element is higher than internal layer concentration in the surface concentration (or being called content) of catalyst granules, and the level with high concentration is have neat shelly, concrete diagram as shown in Figure 1, d in figure prepresent shell thickness.
Supported metal hydrogenating catalyst of the present invention, it is characterized in that described catalyst at least containing carrier, be carried on metal active component palladium on carrier and silica auxiliary agent, described metal active component palladium is egg-shell type distribution, eggshell shell thickness is less than 500 μm, preferably be less than 350 μm, be more preferably less than 300 μm, and described silica is egg-shell type distribution, the difference of the eggshell shell thickness of its eggshell shell thickness and metal active component palladium is no more than 80 μm.
Preferably, the degree that described metal active component palladium accounts for overall catalyst weight is 0.05wt% ~ 1wt%; Described metal active component palladium be egg-shell type distribution, eggshell shell thickness is less than 250 μm, and wherein the palladium Elemental redistribution of more than 90% in described eggshell shell, within more preferably the palladium metal of more than 95% is distributed in described eggshell shell.The conversion ratio of catalyst and selective can be ensured by the distribution of such palladium.
Preferably, the degree that described silica accounts for overall catalyst weight is 0.5wt% ~ 5wt%; The eggshell shell thickness of silica differs with the eggshell shell thickness of metal active component palladium and is no more than 50 μm.
Described catalyst carrier can porous inorganic material known by those skilled in the art or material with carbon element, comprising: ZrO 2, Al 2o 3, TiO 2, active carbon, MCM-41 etc.Preferably described carrier is selected from ZrO 2, Al 2o 3and TiO 2in a kind of or two or more in them mixtures.Described mixture can be not only their mechanical impurity, can be also the mixed oxide having chemical bond to exist, as Al 2o 3-TiO 2.More preferably described carrier is Al 2o 3.
Preferably, described catalyst is also containing metal promoter I, and it to be selected from sodium, potassium, caesium, calcium, magnesium, barium and bismuth one or more, and its content is the 0.01wt% ~ 6wt% of overall catalyst weight.
More preferably, described metal promoter I is selected from one or more of sodium, potassium, calcium, magnesium and bismuth, and its content is the 0.05wt% ~ 2wt% of overall catalyst weight.
Preferably, described catalyst is also containing metal promoter II, and it to be selected from copper, silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and tungsten one or more, and its content is the 0.02wt% ~ 5wt% of overall catalyst weight.
More preferably, described metal promoter II to be selected from silver, gold, lanthanum, cerium and chromium one or more, and its content is the 0.1wt% ~ 3wt% of overall catalyst weight.
Preferably, described catalyst is also containing non-metal assistant III, and it to be selected from boron, phosphorus, sulphur, selenium, fluorine, chlorine and iodine one or more, and its content is the 0.01wt% ~ 3wt% of overall catalyst weight.
More preferably, described catalyst is also containing non-metal assistant III, and it to be selected from boron, phosphorus, fluorine and iodine one or more, and its content is the 0.02wt% ~ 1wt% of overall catalyst weight.
Described catalyst specific surface is 5 ~ 300cm 2/ g, preferable range is 15 ~ 150cm 2/ g, pore volume 0.05 ~ 1.5ml/g, preferably 0.1 ~ 0.8ml/g.Described catalyst shape does not have concrete restriction, can be spherical (comprising ball, tooth ball, oval ball etc.), strip (comprising clover, five leaf grass, random bar etc.) and special-shaped (comprising Raschig ring shape, wheel shape etc.).The particle size of catalyst can adjust according to type of reactor and size, and catalyst size scope of the present invention is 1.0 ~ 80mm, preferably 2 ~ 50mm, more preferably 3 ~ 35mm.
Catalyst solvent of the present invention also has silica, and its content accounts for 0.5 ~ 15wt% of overall catalyst weight, and preferable range is 1 ~ 10wt%.Its quality can obtain in the following manner by the quantitative silicone content of elemental analyser thus accurately obtain the silica quality on catalyst.
The present inventor is surprised to find that silica and palladium metal all with eggshell state distribution on a catalyst, the shell thickness difference of palladium metal and silica is no more than 80 μm simultaneously, preferably more than 50 μm, the green oil generated in course of reaction significantly reduces, and carbon deposition quantity also obviously reduces simultaneously.Although do not want to receive theoretical restriction, inventor thinks that the reason that green oil and carbon distribution reduce may be that the dioxide-containing silica therefore increasing shell can reduce the generating rate of green oil and carbon distribution because the activity site of shell initiated polymerization is how fast at shell synthesis speed with the high green oil that causes of shell high unsaturated hydrocarbons content.Catalyst eggshell shell thickness adopts the mode such as ESEM-energy disperse spectroscopy (SEM-EDS) or energy translation analysis (EDXRF) to carry out the measurement of quantitative and qualitative analysis after can adopting and catalyst being cut half.
The preparation process of catalyst of the present invention is: (1) has the material of palladium metal eggshell shell distribution in the preparation of supported on carriers palladium metal, and adding each analog assistant, the material of gained becomes the ' presoma one ' (hereinafter referred presoma one) of catalyst of the present invention.
The palladium catalyst with the distribution of eggshell shell can adopt and be carried out being immersed on carrier by palladium salting liquid, shell distribution is realized (as bibliography: Liu Xiufang etc. by regulating the means such as pH value, the preparation of eggshell type Pd/α-Al2O3 catalyst and activity, catalysis journal, 2009, Vol30, Issue3, Page213-217.), spraying, metal or metallorganic evaporation, homogeneous precipitation deposition or reduction deposited suspension impregnating various ways also can be adopted to realize.For preparing shell distribution, those skilled in the art can select implementation according to alternative condition, and this does not affect essence of the present invention.
Auxiliary agent can improve the Hydrogenation of catalyst by the above-mentioned realization on carrier that loads to same with active metal.The joining day of auxiliary agent can be before the load of active metal palladium, add afterwards or together with active metal.Adding of auxiliary agent can also be in the forming process of carrier.In the forming process of carrier, the salt of metal promoter or oxide can add, and dispersion on a catalyst.
Citing, active component precursors is selected from chloride corresponding to active component element, nitrate, acetate, sulfate, oxide or metallo-organic compound and is prepared as solution, solvent is selected from one or more the mixture in water, hydrochloric acid, nitric acid, acetic acid, alcohols, is preferably water.The pH of maceration extract is regulated to carry out appropriate regulation to the activity and selectivity of obtained catalyst, preferably, metal active constituent precursor solution needs to use alkali compounds adjust ph to be 1 ~ 10, and described alkali compounds is one or more the mixture be selected from NaOH, potassium hydroxide, potash, sodium acid carbonate, sodium carbonate, ammoniacal liquor and organic amine.Gained mixed liquor is immersed on carrier and obtains required eggshell material and thickness requirement according to the invention.
(2) presoma two that namely silanization treatment obtains catalyst is carried out to catalyst precursor one.The grafting method of silane group is form silylating reagent being converted into gas or fine droplet, contacts subsequently under the carrying of carrier gas with catalyst, completes the silanization treatment to catalyst.The carrier gas used can be a kind of in nitrogen, air, hydrogen, oxygen, carbon dioxide, argon gas or their mixture, preferred hydrogen and nitrogen or both gaseous mixtures.Grafting temperature is between 85 DEG C ~ 280 DEG C.The content of silane group can realize point-device control by regulating type carrier gases and flow velocity, silane reagent raw material type, silylation processing time and silylation treatment temperature.Silane reagent raw material is at beds time of staying general control at 0.001 second ~ 400 seconds, and the silanization overall operation time was at 20 minutes ~ 80 hours.Vary because each Catalyst Production factory also exists, therefore concrete operation is for the technical staff of the industry, and can select according to concrete catalyst preparing factory scenario, operating process concrete is in a word for reaction result.
Described silylating reagent can for being selected from conventional silane, more specifically, be selected from MTES, ethyl triethoxysilane, propyl-triethoxysilicane, MTMS, ethyl trimethoxy silane, propyl trimethoxy silicane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyl diethoxy silane, dimethyldimethoxysil,ne, diethyldimethoxysilane, dipropyl dimethoxysilane, trimethylethoxysilane, triethyl-ethoxy-silicane alkane, tripropyl Ethoxysilane, trimethylmethoxysilane, triethyl group methoxy silane, tripropyl methoxy silane, HMDS, heptamethyldisilazane, 1, 3-dimethyl diethyldisilazane, trim,ethylchlorosilane, Trimethlyfluorosilane.
(3) silane group of grafting on presoma two is oxidized to silica and namely obtains catalyst of the present invention.This oxidation step is to be oxidized to for the purpose of silica by silane group, and realization rate is less on invention impact.For example, silane group is oxidized by the presoma two that oxidizing process adopts air, oxygen or other oxygenous gas to pass into intensification.More specifically example is, the presoma two being loaded on fixed bed is passed at 0.05 ~ 100vol% gas by oxygenous, preferred oxygen content gas 0.1 ~ 10%, oxidizing temperature is slowly warming up to 400 DEG C from 100 DEG C, and progressively raising oxygen content is all oxidized to silane group, in process, make oxidizing temperature lower than 600 DEG C by control oxygen content, gas flow.Can judge by water outlet in oxygen content in detection tail gas and gas cooler the degree be oxidized in industrial implementation process, this is conventional means for those skilled in the art.
It is the hydrogenation reaction of unsaturated hydrocarbon of primary raw material that catalyst of the present invention can be applied to hydro carbons, it is monoolefine that hydrogenation reaction comprises alkynes selective hydrogenation, alkynes and alkadienes selective hydrogenation are monoolefine, in alkadienes, the selective hydrogenation of alkynes is monoolefine, concrete course of reaction, comprise cracking gas selective hydrogenation and removing alkynes and the alkadienes of steam cracking furnace generation, C3 fraction hydrogenation and removing propine and allene, C-2-fraction hydrogenation and removing acetylene, C-4-fraction selective hydrogenation, C5 fraction selective hydrogenation, styrene hydrogenation removes phenylacetylene, more specifically conventional process has cracking gas gas phase selec-tive hydrogenation, cracking gas mixed phase hydrogenation, predepropanization front-end hydrogenation, front-end deethanization front-end hydrogenation, front debutanization front-end hydrogenation, front depentanize front-end hydrogenation, carbon two back end hydrogenation, carbon three back end hydrogenation, carbon four selec-tive hydrogenation acetylene removal and alkadienes, the acetylene removal of carbon four selec-tive hydrogenation, C 5 hydrogenated acetylene removal hydrocarbon, styrene hydrogenation acetylene removal, Performance Test of First Stage Hydrogenation Catalyst of Pyrolysis Gasoline.
Catalyst be applicable to gas-liquid-solid, vapor solid is gentle-reaction of the system such as supercritical fluid-solid phase.In the type of reactor, catalyst of the present invention can be used in any one in fixed bed, fluid bed, slurry bed system, moving bed and Magnetic suspension float bed, preferred fixed bed.
Catalyst of the present invention is when for hydrogenation reaction of unsaturated hydrocarbon, and it is high that catalyst has activity and selectivity, carbon distribution and the minimum advantage of green oil generating amount.
Accompanying drawing explanation
Fig. 1 is the schematic diagram explaining eggshell type distribution.
Fig. 2 is palladium and the element silicon distribution map of embodiments of the invention 1.
Fig. 3 is palladium and the element silicon distribution map of comparative example 2 of the present invention.
Fig. 4 is palladium and the element silicon distribution map of comparative example 3 of the present invention.
Specific embodiment
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.
Embodiment 1
(Beijing Chemical Research Institute produces 320 grams, the short strip shape aluminium oxide of cut-off footpath 2.0X3.0mm, be 0.2wt% containing Ce element, volume 500ml), be respectively 0.02wt%, 0.3wt% and 1.5wt% according to the mass percent of Pd, Ag, Bi and K, surplus is Al 2o 3quality proportioning and incipient impregnation demand prepare the aqueous solution of a palladium bichloride and potassium nitrate, a bismuth nitrate, step impregnation, dry rear 450 DEG C of roastings, obtained catalyst precursor one, gained catalyst precursor one is eggshell type.This catalyst precursor is loaded in fixed bed reactors, in nitrogen atmosphere, be warming up to 140 DEG C, pass into the hydrogen treat 3 hours containing MTES steam, obtain catalyst precursor two.Switch to nitrogen to purge hydrogen, pass into air subsequently, and by the heating rate to 450 DEG C of reactor according to 1 DEG C/min, and constant temperature 3 hours, the catalyst of gained is Cat-1.
Use SEM-EDS analysis palladium and element silicon distribution as shown in Figure 2, the shell thickness of palladium metal and silica is respectively 75 and 58 μm.Elementary analysis shows that dioxide-containing silica is 2.1%.
Comparative example 1
The trilobes Al of cut-off footpath 1.0 ~ 2.0mm 2o 3310 grams as carrier, (Beijing Chemical Research Institute produces, calcic 0.5wt%, volume 500ml), 0.02%, 0.8% and 2.0% is respectively according to the mass percent of Pd, Au and Na, surplus is that the proportional quantity of carrier and equi-volume impregnating are got palladium nitrate, silver nitrate, magnesium nitrate and sodium acid carbonate and be prepared as the corresponding aqueous solution, according to the order step impregnation of sodium, palladium and silver, after drying and 480 DEG C of roastings, obtain Cat-2.The palladium of catalyst is shell distribution, and shell thickness is 31 μm.
Comparative example 2
The spherical Al of tooth of cut-off footpath 3.0 ~ 4.0mm 2o 3290 grams as carrier, (Beijing Chemical Research Institute produces, volume 500ml, be 1.2wt% and 0.02wt% containing magnesium and fluorine, silicone content is less than 0.02wt%), 0.05%, 0.3% and 1.0% is respectively according to the mass percent of Pd, Ag and Bi, surplus is that the aqueous solution prepared by proportional quantity configuration palladium nitrate, silver nitrate and the bismuth nitrate of carrier, adopts the mode of spraying to prepare, obtains a catalyst precursor after drying and 480 DEG C of roastings.Added in 1000ml paraxylene liquid phase by 150 DEG C of dried catalyst precursors, and add trim,ethylchlorosilane 20.0g, be warming up to 110 DEG C of process 3 hours, take out roasting in atmosphere 3 hours, sintering temperature 400 DEG C, gained catalyst is Cat-3.Wherein palladium is eggshell distribution, and shell thickness is greater than 500 μm, and silicon is for being uniformly distributed, as shown in Figure 3.Elementary analysis shows that dioxide-containing silica is 3.1%.
Comparative example 3
(Beijing Chemical Research Institute produces to get spherical alumina, containing silica 2.0wt%) as carrier, according to the method Kaolinite Preparation of Catalyst of embodiment 1, gained palladium catalyst shell thickness is 21 μm, and silica is for being uniformly distributed (as Fig. 4).Silica in this alumina catalyst support for add in forming process, using ethyl orthosilicate as silicon source.Gained catalyst is Cat-4.
Embodiment 3 (carbon two back end hydrogenation)
Embodiment 1 and comparative example 1 ~ 3 are applied to the reaction that carbon two back end hydrogenation removes acetylene respectively, and in its Raw, acetylene accounts for 1.3% (mass fraction), hydrogen: acetylene=1.05: 1 (mol ratio), gas space velocity 5500h -1.Hydrogenation reactor is 150ml adiabatic reactor reactor, Catalyst packing 50.0g, and the Entrance Problem all by controlling catalyst ensures that acetylene outlet is less than 5ppm.Compare carbon deposition quantity by TG-MS combination after reaction 1000h terminates, and collect the green oil amount of reaction generation.Wherein, acetylene conversion ratio and optionally computational methods be:
C 2 H 2 Conversion = ( C 2 H 2 ) in - ( C 2 H 2 ) out ( C 2 H 2 ) in × 100
C 2 H 2 Selectivity = ( C 2 H 4 ) out - ( C 2 H 4 ) in ( C 2 H 2 ) in - ( C 2 H 2 ) out × 100
As shown in Table 1, experiment shows relative to existing method result, and catalyst green oil generating amount of the present invention reduces, carbon accumulation resisting ability significantly strengthens, and therefore inlet temperature improvement value is significantly less than other catalyst, makes the reactivity worth of catalyst steady.
Table one embodiment 1 and comparative example catalytic perfomance

Claims (13)

1. a supported metal hydrogenating catalyst, it is characterized in that described catalyst at least containing carrier, be carried on metal active component palladium on carrier and silica auxiliary agent, described metal active component palladium is egg-shell type distribution, eggshell shell thickness is less than 300 μm, and described silica is egg-shell type distribution, and the difference of the eggshell shell thickness of its eggshell shell thickness and metal active component palladium is no more than 80 μm.
2. supported metal hydrogenating catalyst as claimed in claim 1, is characterized in that the degree that described metal active component palladium accounts for overall catalyst weight is 0.05wt% ~ 1wt%; Described metal active component palladium be egg-shell type distribution, eggshell shell thickness is less than 250 μm, and wherein the palladium Elemental redistribution of more than 90% in described eggshell shell.
3. supported metal hydrogenating catalyst as claimed in claim 1, is characterized in that the degree that described silica accounts for overall catalyst weight is 0.5wt% ~ 5wt%; The eggshell shell thickness of silica differs with the eggshell shell thickness of metal active component palladium and is no more than 50 μm.
4. supported metal hydrogenating catalyst as claimed in claim 1, is characterized in that described carrier is selected from ZrO 2, Al 2o 3and TiO 2in a kind of or two or more in them mixtures.
5. supported metal hydrogenating catalyst as claimed in claim 4, is characterized in that described carrier is Al 2o 3.
6. supported metal hydrogenating catalyst as claimed in claim 1, it is characterized in that described catalyst also containing metal promoter I, it to be selected from sodium, potassium, caesium, calcium, magnesium, barium and bismuth one or more, and its content is the 0.01wt% ~ 6wt% of overall catalyst weight.
7. supported metal hydrogenating catalyst as claimed in claim 6, it is characterized in that described metal promoter I is selected from one or more of sodium, potassium, calcium, magnesium and bismuth, its content is the 0.05wt% ~ 2wt% of overall catalyst weight.
8. supported metal hydrogenating catalyst as claimed in claim 1, it is characterized in that described catalyst also containing metal promoter II, it to be selected from copper, silver, gold, zinc, lanthanum, cerium, chromium, molybdenum and tungsten one or more, and its content is the 0.02wt% ~ 5wt% of overall catalyst weight.
9. supported metal hydrogenating catalyst as claimed in claim 8, it is characterized in that described metal promoter II to be selected from silver, gold, lanthanum, cerium and chromium one or more, its content is the 0.1wt% ~ 3wt% of overall catalyst weight.
10. supported metal hydrogenating catalyst as claimed in claim 1, it is characterized in that described catalyst also containing non-metal assistant III, it to be selected from boron, phosphorus, sulphur, selenium, fluorine, chlorine and iodine one or more, and its content is the 0.01wt% ~ 3wt% of overall catalyst weight.
11. supported metal hydrogenating catalysts as claimed in claim 10, is characterized in that described catalyst also containing non-metal assistant III, and it to be selected from boron, phosphorus, fluorine and iodine one or more, and its content is the 0.02wt% ~ 1wt% of overall catalyst weight.
12. as the application of the supported metal hydrogenating catalyst as described in one of in claim 1 ~ 11, it is characterized in that, described catalyst application, in hydrogenation reaction of unsaturated hydrocarbon, comprises that alkynes selective hydrogenation is monoolefine, alkynes and alkadienes selective hydrogenation is monoolefine or in alkadienes, alkynes selective hydrogenation is monoolefine.
13. apply as claimed in claim 12, it is characterized in that, the cracking gas selective hydrogenation and removing alkynes that described catalyst application produces in steam cracking furnace and alkadienes, C3 fraction hydrogenation and removing propine and allene, C-2-fraction hydrogenation and removing acetylene, C-4-fraction selective hydrogenation, C5 fraction selective hydrogenation or styrene hydrogenation remove phenylacetylene.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101433853A (en) * 2008-12-08 2009-05-20 中国石油天然气股份有限公司 Hydrogenation catalyst, preparation method and uses thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101433853A (en) * 2008-12-08 2009-05-20 中国石油天然气股份有限公司 Hydrogenation catalyst, preparation method and uses thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
M.莫尔比代利等.2.6.2加氢反应.《催化剂设计:活性组分在颗粒、反应器和膜中的最优分布》.2004,(第1版),第6页倒数第1段-第7页第1段,第66页第1段—第67页第3段. *
Performance of Si-modified Pd catalyst in acetylene hydrogenation: catalyst deactivation behavior;Woo Jae Kim等;《Applied Catalysis A: General》;20030930;第251卷(第2期);第305–313页:摘要，第306页左栏第3-4段，第2.1节，第3-5节 *
Performance of Si-modified Pd catalyst in acetylene hydrogenation: the origin of the ethylene selectivity improvement;Eun Woo Shin等;《Applied Catalysis A: General》;20020131;第223卷(第1-2期);第 161–172页:摘要，第2.1节，第3节—第5节 *
Properties of Si-modified Pd catalyst for selective;Eun W. Shin等;《Catalysis Today》;19980930;第44卷(第1-4期);第137—143页:摘要，第2.1节，第3-4节 *

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