CN100512955C - Selective hydrogenation catalyst of alkine and diolefin, preparation method and application - Google Patents

Selective hydrogenation catalyst of alkine and diolefin, preparation method and application Download PDF

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CN100512955C
CN100512955C CNB2005101174393A CN200510117439A CN100512955C CN 100512955 C CN100512955 C CN 100512955C CN B2005101174393 A CNB2005101174393 A CN B2005101174393A CN 200510117439 A CN200510117439 A CN 200510117439A CN 100512955 C CN100512955 C CN 100512955C
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catalyst
solution
palladium
inert carrier
coating layer
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CN1958155A (en
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戴伟
卫国宾
彭晖
穆玮
房艳
刘海江
戚文新
卢红亮
何耕云
郭彦来
朱警
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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

A selective hydrocatalyst for the alkine and diolefin in C2-10 fraction is composed of a inertial carrier chosen from silicon carbide, talc powder and fire-proof earth and a coated alumina layer containing Pd, Ag, Bi and at least one of Cu, Zn, alkali metal, AE metal and RE element. Its preparing process is also disclosed.

Description

A kind of alkynes and diolefin hydrogenate catalyst and preparation and application
Technical field
The present invention relates to a kind of C2 of being used for～C10 cut alkynes and diolefin hydrogenate Catalysts and its preparation method.Be particularly related to a kind of palladium that scribbles the aluminum oxide coating layer that has active component on the inert carrier surface and select hydrogenation catalyst and preparation method thereof.
Technical background
At the petrochemical industry industrial circle, contain 0.3～3% acetylene in the cracking centrifugal station in the ethene cut, this acetylene impurity is the poisonous substance of polyethylene catalysts, influences normally carrying out of ethylene polymerization.For fear of the generation that above-mentioned ethylene rolymerization catalyst intoxicating phenomenon occurs, adopting catalyst to select the method for hydrogenation to make the acetylene conversion in the ethene cut usually is ethene.But selecting hydrogenation to remove in the reaction of acetylene, being adsorbed on acetylene on the catalyst surface, to be easy to deep hydrogenation be ethane, or by hydrogenation dimerization reaction generation 1, unsaturated C4 hydrocarbon such as 3-butadiene, and they continue reaction again, generate C6～C24 high polymer, be commonly called as green oil, green oil sticks on the selective acetylene hydrocarbon hydrogenation catalyst can cause catalysqt deactivation.
Usually, the major catalyst of alkynes and diolefin hydrogenate catalyst is based on precious metal palladium, add different co-catalysts, as silver (US6465391), gold (US6509292), alkali metal and alkaline-earth metal (US6576586) and copper (US66275798), platinum (US6462244), bismuth (US6459008) etc., these co-catalysts are arranged to the crystal structure of adjusting major catalyst and outer-shell electron and are played certain promotion, can also suppress the carrying out of alkynes hydrogenation side reaction simultaneously.
As everyone knows, the carrier material that is used for alkynes and diolefin hydrogenate catalyst comprises aluminium oxide (CN12798126A), reticular fiber structure aluminium oxide (US6388150), silica (US5856262), titanium dioxide, ceria (US4906602), zirconia, CaCO 3, diatomite and honeycomb cordierite (CN1176291), wherein general with alumina support, compare with other carrier, it is simple and direct that alumina support has the preparation method, the characteristics that production cost is low, and the variation of the crystal phase structure of aluminium oxide is more, and the controllability of duct size, pore structure and the specific area of formation carrier is stronger, and the skeleton structure of simultaneous oxidation aluminium combines closely with the activity of such catalysts component.
In the catalytic purification of automobile and exhaust gases of internal combustion engines, obtained certain application being coated with the active oxidation aluminized coating that contains catalytic active component on ceramic honey comb or the metallic carrier.The main effect of this catalyst is that carbon monoxide, hydro carbons and hydro carbons containing oxygen derivative are oxidized to carbon dioxide and water by catalytic combustion.The ceramic honey comb of this combustion catalyst or the passage of metallic carrier are as the flow duct of locomotive waste gas, and they are to have the regulation shape perpendicular to the circle in carrier cross section, square or foam-like passage.Because aluminium oxide itself high-specific surface area, fire-resistant, the resistance and high temperature resistance property that are had are coated in it on ceramic honey comb or the metallic carrier as coating, can disperse well, the supported catalyst active component.It is the double-deck carrier loaded form (US6294140) of major catalyst that this catalyst adopts with platinum, rhodium more, has also occurred the high performance catalyst (US6524992) of individual layer load recently and has adopted base metal chromium, copper, nickel to substitute the combustion catalyst (US5534475) of platinum, rhodium noble metal as major catalyst.
Traditional alkynes and diolefin hydrogenate Preparation of catalysts adopt infusion process more, it mainly is salt solution impregnation solid carrier by major catalyst Pd and co-catalyst silver etc., metal ion enters along the duct of carrier, and the metal ion that has can be moved to the carrier center position.
To discovering of selective acetylene hydrocarbon hydrogenation course of reaction, the selective hydrogenation reaction major part concentrates on the Pd in catalyst coating duct, and then utilization rate is very low to be in the hydrogenation reaction of Pd of depths, duct.Because even acetylene molecule can enter the depths, duct, also cause reactions such as acetylene secondary hydrogenation, oligomerisation easily, block the duct, reduce reactivity and selectivity.
Selective acetylene hydrocarbon hydrogenation catalyst contains precious metals pd, Ag and Au etc. mostly, because the part noble metal is distributed in carrier inside, reduced due activity of catalyst coating and selectivity, therefore need the extra precious metal ion that adds, thereby the activity that guarantees catalyst coating has been formed.
Summary of the invention
An object of the present invention is to provide a kind of catalyst that is used for C2～C10 cut alkynes and diolefin hydrogenate that has aluminum oxide coating layer, wherein major catalyst Pd and co-catalyst only are distributed in the aluminum oxide coating layer of catalyst coating, and the thickness of aluminum oxide coating layer has only 10～300 microns.
Another object of the present invention has provided the method for preparing catalyst of the present invention, has reduced the consumption of major catalyst Pd and co-catalyst Ag etc.
In order to achieve the above object, the inventor has carried out intensive research.In conjunction with to combustion catalyst discover that inert carrier generally only plays the effect of matrix, its specific area is almost nil, intensity is high, and chemistry, physical property are stable.Activated alumina is coated in the surface as coating, can not slacken the combination of coating and inert carrier because of the change of external condition, and the catalytic active component that is present in the aluminum oxide coating layer can not migrate in the inert carrier yet, guaranteed the total amount of the active component of carrier surface.Because the thickness of aluminum oxide coating layer has only 10～300 microns, major catalyst Pd and co-catalyst can both be participated in the selective hydrogenation reaction of alkynes and alkadienes completely, improved the hydrogenation efficiency of catalyst activity component, than the traditional catalyst major catalyst still is that the consumption of co-catalyst all decreases, thereby reduces production costs.
The invention provides a kind of C2 of being used for～C10 cut alkynes and diolefin hydrogenate catalyst, described catalyst comprises inert carrier, aluminum oxide coating layer, catalyst activity component, the catalyst activity component is present in the aluminum oxide coating layer, the catalyst activity component comprises major catalyst palladium and co-catalyst silver, bismuth, and at least a copper, zinc, alkali metal, alkaline-earth metal, rare earth element, wherein:
Inert carrier is selected from carborundum, talcum powder, seat clay, and that its shape is selected from is granular, spherical, profile of tooth, annular, tooth sphere, sheet or strip, and its specific surface is less than 10m 2/ g;
Aluminum oxide coating layer is coated on the inert carrier outer surface, and thickness is 10～500 microns, and its specific area is at 1～200m 2/ g;
In the catalyst activity component, the percentage by weight of major catalyst palladium and inert carrier (following percentage is all the percentage by weight with inert carrier) counts 0.001～1.0%.
Particularly, preferred carborundum of inert carrier or talcum powder, its shape is preferably granular, spherical, annular, tooth is spherical, strip, and its specific surface is preferably less than 5m 2/ g.Aluminum oxide coating layer is coated on the inert carrier outer surface, and thickness is preferably 10～300 microns, and its specific area is preferably 5～120m 2/ g.
The major catalyst palladium content that is present in the aluminum oxide coating layer is preferably 0.01～0.05%.
Being present in the co-catalyst in the aluminum oxide coating layer and the percentage by weight of inert carrier is 0.002～14%.The co-catalyst silver content that is present in the aluminum oxide coating layer is preferably 0.001～8%, and the co-catalyst bi content that is present in the aluminum oxide coating layer is preferably 0.001～5%.
Described alkali metal can be potassium, sodium, rubidium, caesium, and alkaline-earth metal can be calcium, magnesium, strontium, barium, and rare earth element can be lanthanum, neodymium, cerium.
C2～C10 cut alkynes and the diolefin hydrogenate catalyst of being used for of the present invention, can be applied to remove in the C2 cut of cracking separative element in the petrochemical industry and remove propine and allene reaction in acetylene reaction (comprising front-end hydrogenation flow process, back end hydrogenation flow process), the C3 cut, and the high-carbon chain hydrocarbon (removes alkynes and alkadienes reaction among the C4～C10).
Preparation of catalysts method of the present invention: by with containing 1～30 weight % alumina gel solution, add acid-conditioning solution and under pH=2～6 conditions, flood inert carrier, at 60～300 ℃ after 3-30 hour drying, be cooled to room temperature 300～1200 ℃ of calcinings after 4～20 hours, obtain having the inert carrier of aluminum oxide coating layer, soak altogether with the solution that contains palladium solution and contain co-catalyst component then or step impregnation in the aluminum oxide coating layer on inert carrier surface, 100～300 ℃ after 5～24 hours dryings, made in 4～20 hours 350～650 ℃ of calcinings.
Catalyst of the present invention can also adopt another kind of preparation method: by with the solution that contains palladium solution, contains co-catalyst component with contain that 1～30 weight % alumina gel solution is even and mix after, add acid-conditioning solution and under pH=2～6 conditions, flood inert carrier, 60～300 ℃ after 5-30 hour drying, made in 4～20 hours 300～1200 ℃ of calcinings.
Particularly, the colloid of described aluminium oxide is that the aqueous solution with high purity aluminium oxide makes; The acid that adds is selected from nitric acid, acetic acid, citric acid, hydrochloric acid; Contain palladium solution and be selected from palladium bichloride, palladium nitrate, palladium solution; The solution of argentiferous is selected from silver nitrate, silver perchlorate solution in the co-catalyst; Bismuth-containing solution is selected from bismuth nitrate, bismuth chloride solution.
C2～C10 cut alkynes and the diolefin hydrogenate catalyst of being used for of the present invention, because the thickness of aluminum oxide coating layer has only 10～300 microns, major catalyst Pd and co-catalyst can both be participated in the selective hydrogenation reaction of alkynes and alkadienes completely, improved the hydrogenation efficiency of catalyst activity component, than conventional catalyst catalyst major catalyst still is that the consumption of co-catalyst all decreases, thereby reduces production costs.
The specific embodiment
The invention is further illustrated by the following examples, to deepen the understanding of the present invention.Invention itself is not subjected to the restriction of these embodiment.Content among each embodiment is the percentage by weight with inert carrier.
Embodiment 1
To contain 5gAl 2O 320% Al 2O 3Colloidal solution is used HNO 3Adjust pH=3.5, take by weighing the 100gSiC annular carrier and impregnated in the colloidal solution for preparing, at 120 ℃ of dry 24h, it is stand-by to be cooled to room temperature then behind 300 ℃ of calcining 8h.The PdCl that will contain 0.02g Pd 2Solution contains the AgNO of 0.1g Ag 3Solution contains the Bi (NO of 0.1g Bi 3) 2Solution contains the Ca (NO of 0.01g Ca 3) 2The carrier that step impregnation is stand-by, behind a kind of element of every dipping all should 150 ℃ through the 24h drying, at last 600 ℃ the calcining 8h obtain catalyst A, wherein Pd content is 0.03%, Ag content is 0.1%, Bi content is 0.1%, Ca content is 0.01%.
Embodiment 2
Containing 10g Al 2O 35% Al 2O 3In the colloidal solution, add HNO 3Adjust pH=2.5, take by weighing 100g SiC annular carrier dipping, at 200 ℃ of dry 8h, it is stand-by to be cooled to room temperature behind 300 ℃ of calcining 15h.Stand-by carrier be impregnated in earlier in the nitrate solution that contains 0.01g Ag, 0.05g Bi, 0.02g La, at 200 ℃ of dry 8h, and then with this carrier impregnation in the chloride salt solution that contains 0.05g Pd, 0.005g Ca, 0.005g Sr and 0.02g K, at 200 ℃ of dry 8h, 300 ℃ of calcining 15h obtain catalyst B, wherein Pd content is 0.05%, Ag content is 0.01%, Bi content is 0.05%, Ca content is 0.005%, K content is 0.02%, and Sr content is 0.005%, and La content is 0.02%.
Embodiment 3
Containing 6g Al 2O 330% Al 2O 3In the colloidal solution, use HNO 3Adjust pH=4.2, take by weighing 100g talcum powder annular carrier and impregnated in the solution for preparing, at 100 ℃ of dry 13.5h, it is stand-by to be cooled to room temperature then behind 780 ℃ of calcining 20h.Pd (the NO that will contain 0.01gPd again 3) 2, contain the AgNO of 0.5g Ag 3, contain the Bi (NO of 0.5g Bi 3) 2, contain the Cu (NO of 0.05g Cu 3) 2, contain the NaNO of 0.05g Na 3Be made into mixed solution, stand-by carrier impregnation in mixed solution, at 135 ℃ of dry 30h, is obtained catalyst C then behind 550 ℃ of calcining 20h.Wherein Pd content is 0.01%, and Ag content is 0.5%, and Bi content is 0.5%, and Cu content is 0.05%, and Na content is 0.05%.
Embodiment 4
Containing 3g Al 2O 325%Al 2O 3In the colloidal solution, add the CsCl that contains 0.05g Cs 2, mixed solution is made in dissolving, adjust pH=5.5 with HCl after, dipping 100g granular refractory soil, at 240 ℃ of dry 18h, it is stand-by to be cooled to room temperature then behind 1000 ℃ of calcining 20h.Pd (the NO that will contain 0.02g Pd again 3) 2, contain the AgNO of 0.02g Ag 3, contain the Bi (NO of 0.01g Bi 3) 2Be made into mixed solution, stand-by carrier impregnation in mixed solution, at 140 ℃ of dry 20h, is obtained catalyst D then behind 600 ℃ of calcining 20h.Wherein Pd content is 0.02%, and Ag content is 0.02%, and Bi content is 0.01%, and Cs content is 0.05%.
Embodiment 5
Containing 5.5g Al 2O 331% Al 2O 3In the colloidal solution, adjust pH=3.7 with acetic acid, take by weighing 100g SiC bead-type substrate and impregnated in the solution for preparing, at 210 ℃ of dry 5.5h, it is stand-by to be cooled to room temperature behind the 18h 430 ℃ of calcinings then.Stand-by carrier be impregnated in the nitrate solution that contains 0.005g Ag and contain 0.03g Bi earlier, behind 120 ℃ of dry 20h, containing the CuCl of 0.01gCu again 2Middle dipping behind 120 ℃ of dry 20h, impregnated in the PdCl that contains 0.06g Pd 2Solution again at 120 ℃ of dry 20h, obtains catalyst E behind 650 ℃ of calcining 10h.Wherein Pd content is 0.06%, and Ag content is 0.005%, and Bi content is 0.03%, and Cu content is 0.01%.
Embodiment 6
Containing 8g Al 2O 315% Al 2O 3In the colloidal solution, adjust pH=2.1 with citric acid, take by weighing 100g talcum powder bead-type substrate and impregnated in the solution for preparing, at 220 ℃ of dry 14h, it is stand-by to be cooled to room temperature behind the 15h 900 ℃ of calcinings then.Stand-by carrier be impregnated in the PdCl that contains 0.005g Pd earlier 2Solution behind 120 ℃ of dry 20h, impregnated in the nitrate solution that contains 0.01g Ag and contain 0.04g Bi again, behind 120 ℃ of dry 20h, obtains catalyst F behind 430 ℃ of calcining 13h.Wherein Pd content is 0.005%, and Ag content is 0.01%, and Bi content is 0.04%.
Embodiment 7
Containing 6g Al 2O 310%Al 2O 3In the colloidal solution, add the KCl contain 0.01g K, mixed solution is made in dissolving, adjust pH=2.3 with HCl after, dipping 100g SiC ball type carrier, at 340 ℃ of dry 18h, it is stand-by to be cooled to room temperature then behind 780 ℃ of calcining 13h.Stand-by carrier be impregnated in the Pd (NO that contains 0.04gPd earlier 3) 2Solution behind 120 ℃ of dry 20h, impregnated in the nitrate solution that contains 0.1gAg and contain 0.01gBi again, behind 120 ℃ of dry 20h, obtains catalyst G behind 430 ℃ of calcining 13h.Wherein Pd content is 0.04%, and Ag content is 0.1%, and Bi content is 0.01%, and K content is 0.01%.
Embodiment 8
Al 2O 3The coating preparation process impregnated in stand-by carrier earlier Pd (the NO that contains 0.025g Pd with embodiment 7 3) 2Solution behind 120 ℃ of dry 20h, impregnated in the nitrate solution that contains 0.15g Ag and contain 0.009g Bi again, after the same dried condition, obtains catalyst H behind 430 ℃ of calcining 13h.Wherein Pd content is 0.025%, and Ag content is 0.5%, and Bi content is 0.009%, and K content is 0.01%.
The catalyst of selecting the foregoing description to prepare carries out the acetylene hydrogenation reaction experiment, and reaction condition is as follows:
The 1ml catalyst is packed in the tubular reactor, and beds is filled the porcelain ring up and down.Use nitrogen replacement, again after reduction, from top to bottom pass through reactor after simulation prepared from the unstripped gas of deethanization cat head and a certain amount of hydrogen.Hydrogen alkynes ratio is 1.5, inlet concentration of acetylene 0.11mol%, air speed 15000hr -1
Catalyst A～H is carried out catalyst selection hydrogenation examination under the different temperatures, the highest conversion of alkyne and the corresponding selection such as the table 1 of each catalyst.
The performance assessment criteria of each catalyst of table 1
Figure C200510117439D00121

Claims (16)

1. one kind is used for C2～C10 cut alkynes and diolefin hydrogenate catalyst, form by inert carrier, aluminum oxide coating layer, catalyst activity component, the catalyst activity component is present in the aluminum oxide coating layer, the catalyst activity component consists of: the major catalyst palladium, with co-catalyst silver and bismuth and at least a copper, zinc, alkali metal, alkaline-earth metal, rare earth element, wherein:
Inert carrier is a carborundum, and that its shape is selected from is granular, spherical, profile of tooth, annular, tooth sphere, sheet or strip, and its specific surface is less than 10m 2/ g;
Aluminum oxide coating layer is coated on the inert carrier outer surface, and thickness is 10～500 microns, and its specific area is 1～200m 2/ g;
The percentage by weight of major catalyst palladium and inert carrier is 0.001～1.0%.
2. hydrogenation catalyst according to claim 1 is characterized in that inert carrier is a carborundum, that its shape is selected from is granular, spherical, annular, tooth is spherical and strip in a kind of, its specific surface is less than 5m 2/ g.
3. hydrogenation catalyst according to claim 1 is characterized in that aluminum oxide coating layer thickness is 10～300 microns, and its specific area is 5～120m 2/ g.
4. hydrogenation catalyst according to claim 1, it is characterized in that being present in the major catalyst palladium in the aluminum oxide coating layer and the percentage by weight of inert carrier is 0.01～0.05%.
5. hydrogenation catalyst according to claim 1, it is characterized in that being present in the co-catalyst in the aluminum oxide coating layer and the percentage by weight of inert carrier is 0.002～14%.
6. hydrogenation catalyst according to claim 5, the silver-colored percentage by weight with inert carrier of co-catalyst that it is characterized in that being present in the aluminum oxide coating layer is 0.001～8%.
7. according to claim 5 or 6 described hydrogenation catalysts, it is characterized in that being present in the co-catalyst bismuth in the aluminum oxide coating layer and the percentage by weight of inert carrier is 0.001～5%.
8. according to the described hydrogenation catalyst preparation method of one of claim 1～7, step is as follows:
(1), adds under acid-conditioning solution pH=2～6 conditions and flood inert carrier with containing 1～30 weight % alumina gel solution;
(2) carrier that step 1) is obtained 300～1200 ℃ of calcinings 4～20 hours, was cooled to room temperature again after 60～300 ℃ of dry 3-30 hours, obtained having the inert carrier of aluminum oxide coating layer;
(3) soak altogether with the solution that contains palladium solution, contains co-catalyst component or step impregnation at the aluminum oxide coating layer on inert carrier surface;
(4) behind the dipping, after 100～300 ℃ of dry 5-24 hours, made in 4～20 hours 350～650 ℃ of calcinings.
9, method for preparing catalyst according to claim 8 is characterized in that in described step 1), and the colloidal solution that contains 1～30 weight % aluminium oxide is that the aqueous solution by high purity aluminium oxide makes, and the acid of adding is selected from nitric acid, acetic acid, citric acid, hydrochloric acid.
10, method for preparing catalyst according to claim 8 is characterized in that the described solute that contains palladium solution is selected from palladium bichloride, palladium nitrate, palladium; The solute of the solution of argentiferous is selected from silver nitrate, silver perchlorate in the co-catalyst; The solute of bismuth-containing solution is selected from bismuth nitrate, bismuth chloride.
11, according to the described hydrogenation catalyst preparation method of one of claim 1～7, step is as follows:
(1) with the solution that contains at least a element in palladium and the co-catalyst component with contain 1～30 weight % alumina gel solution and evenly mix after, flood inert carrier under adding acid-conditioning solution pH=2～6 conditions;
(2) carrier 300～1200 ℃ of calcinings 4～20 hours, was cooled to room temperature more then after 60～300 ℃ of dry 5-30 hours;
(3) more remaining cocatalyst component is made into salting liquid and continues impregnated carrier, after 5～24 hours, made in 4～20 hours 350～650 ℃ of calcinings again 100～300 ℃ of dryings.
12, method for preparing catalyst according to claim 11, it is characterized in that in described step 1), the colloidal solution that contains 1～30 weight % aluminium oxide is that the aqueous solution by high purity aluminium oxide makes, and the acid of adding is selected from nitric acid, acetic acid, citric acid, hydrochloric acid.
13, method for preparing catalyst according to claim 11 is characterized in that the described solute that contains palladium solution is selected from palladium bichloride, palladium nitrate, palladium; The solute of the solution of argentiferous is selected from silver nitrate, silver perchlorate in the co-catalyst; The solute of bismuth-containing solution is selected from bismuth nitrate, bismuth chloride.
14, the described catalyst of one of claim 1～7 is applied to remove acetylene in the C2 cut of cracking separative element.
15, the described catalyst of one of claim 1～7 is applied to remove in the C3 cut of cracking separative element propine and allene.
16, the described catalyst of one of claim 1～7 is applied to remove among the high-carbon chain hydrocarbon C4～C10 of cracking separative element alkynes and alkadienes.
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CN101433841B (en) * 2007-12-13 2010-04-14 中国石油天然气股份有限公司 Selectively hydrogenating catalyst and preparation method thereof
CN102188969B (en) * 2010-03-16 2014-05-28 中国石油化工股份有限公司 Selective hydrogenation catalyst of cracked gasoline and preparation method of selective hydrogenation catalyst
CN102240548A (en) * 2010-05-14 2011-11-16 中国石油化工股份有限公司 Catalyst for C4 fraction selective hydrogenation and removal of alkyne, and preparation method thereof
CN102240565B (en) * 2010-05-14 2013-08-14 中国石油化工股份有限公司 Method for preparing hydrogenation catalyst
CN102464543B (en) * 2010-11-12 2014-12-17 中国石油化工股份有限公司 Application of alkyne selective hydrogenation catalyst
CN102125839B (en) * 2011-01-21 2014-06-04 北京三聚环保新材料股份有限公司 Alkyne hydrogenation catalyst and preparation method thereof
CN102688783A (en) * 2011-03-25 2012-09-26 中国石油化工股份有限公司 Alkyne selective hydrogenation catalyst carrier and preparation method and catalyst thereof
CN103801293B (en) * 2012-11-05 2016-06-29 中国石油化工股份有限公司 A kind of hydrogenation catalyst and preparation method thereof and application
CN111229275A (en) * 2018-11-28 2020-06-05 中国科学院大连化学物理研究所 Catalyst for preparing olefin by selective hydrogenation of alkyne and application thereof
CN109647387B (en) * 2018-12-26 2022-04-22 万华化学集团股份有限公司 Method and catalyst for recovering diphenol by catalytic hydrocracking of phenol-containing tar

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