CN101890351B - Eggshell type nickel-based catalyst - Google Patents
Eggshell type nickel-based catalyst Download PDFInfo
- Publication number
- CN101890351B CN101890351B CN200910084548A CN200910084548A CN101890351B CN 101890351 B CN101890351 B CN 101890351B CN 200910084548 A CN200910084548 A CN 200910084548A CN 200910084548 A CN200910084548 A CN 200910084548A CN 101890351 B CN101890351 B CN 101890351B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nickel
- carrier
- weight
- ammoniacal liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an eggshell type nickel-based catalyst and a preparation method and application thereof, belonging to the technical field of nickel-based catalysts and aiming at developing the eggshell type nickel-based catalyst for meeting the demand. The research shows that the eggshell type nickel-based catalyst can be prepared by dissolving nickel salt into ammonia water solution, loading the mixed solution on a catalyst carrier by adopting a spraying or immersing mode, drying, roasting and reducing. The active component of nickel is mostly centralized in an area from the surface of the carrier to the part of 0.7mm below the surface and can remarkably improve the conversion rate and the selectivity of the catalyst. The invention can be applied to the technical fields of hydrogen addition and trace amount of carbon monoxide removal from hydrogen and the like.
Description
Technical field
The present invention relates to a kind of nickel-base catalyst, specifically, relate to a kind of nickel component and be distributed in the eggshell type nickel-based catalyst in the catalyst perimeter.
Background technology
In petrochemical industry; Hydrogenation reaction is used noble metal carrier catalyst and non-noble metal supported catalyst usually; The noble metal catalyst of working load palladium in C-2-fraction and C 3 fraction selective hydrogenation for example, the non-precious metal catalyst of working load nickel usually in gasoline hydrogenation and the benzene hydrogenation.In order to make full use of expensive noble metal and to improve activity of such catalysts and selectivity; Generally noble metal carrier catalyst is prepared into egg-shell catalyst; And along with the continuous development of catalyst preparation technology, people do the eggshell of carried noble metal more and more thinner.
For example, US 5648576 discloses the method that a kind of carbon two or carbon three alkynes gas phases are selectively hydrogenated into corresponding alkene.This method is in the presence of hydrogen, and gas phase treatment contains the material of acetylene or propine allene on the catalyst of sphere or bar shaped.Catalyst system therefor contains palladium and at least a periodic table of elements IB family metal (preferred silver) and aluminium oxide, and wherein the weight ratio of IB family metal and palladium is that 0.05～0.4, at least 80% palladium and at least 80% IB family Metal Distribution are being r by radius
1(mean radius that is equivalent to the catalyst of sphere or extrusion molding) and radius are r
2(r
2At least equal 0.8r
1) sphere or catalyst volume that the face of cylinder limited within.Active component palladium and IB family metal are to adopt infusion process to load on the carrier.
Yet the active component of also not seeing at present about non-precious metal catalyst especially nickel-base catalyst is the report that eggshell type distributes.About the research of nickel-base catalyst, paying close attention to more is that active component nickel is nanoparticle and is distributed on the carrier and the influence to catalyst performance of the reduction act of nickel.For example; Waited comparative analysis quietly suddenly nano nickel catalyst and traditional Raney's nickel catalyst; And the multiple preparation method who has summarized nano nickel catalyst emphatically and application prospect (present Research of catalyzer for hydrogenization of nano nickel and prospect, powder metallurgy industry, 2006 of having looked forward to nano nickel catalyst; The 16th the 1st phase of volume, the 45th～48 page).The performance of catalyst is not only relevant, also relevant with the distribution of nickel in the carrier duct with the effect power of the particle size of active component nickel and nickel and carrier.For example, if reactant molecule is difficult to get into depths, catalyst duct, the utilization rate that is distributed in the nickel at hole depth place so maybe be lower.The product molecule that reaction generates in depths, catalyst duct further reacts as can not in time spreading out, and influences selection of catalysts property on the one hand, will influence life of catalyst on the other hand.Especially internally be diffused as the reaction of control step; Hope that reaction occurs in the position that is beneficial to reactant and product diffusion; General hope occurs in catalyst coating, and the palladium as the eggshell type palladium catalyst is distributed in the eggshell type nickel-based catalyst in the extremely thin top layer.In addition; In the cost of nickel-base catalyst; The large percentage that the cost of active component nickel is shared if the nickel component that is distributed in the depths, duct that utilization rate is not high moves in the zone near catalyst coating, can significantly improve activity of such catalysts and selectivity undoubtedly.Thereby, develop a kind of eggshell type nickel-based catalyst at present and have very large learning value and remarkable economic efficiency.
Summary of the invention
The present invention is in order to satisfy at present to developing the demand of eggshell type nickel-based catalyst; Carried out intensive research; Through discovering; Through regulating active component nickel distribution situation on catalyst carrier, make the active component nickel major part concentrate on carrier surface in the zone of half degree of depth of central shaft, can significantly improve the conversion ratio and the selectivity of catalyst.
The present invention realizes that the technical scheme of above-mentioned purpose is:
Eggshell type nickel-based catalyst of the present invention is made up of carrier and the active component nickel that loads on the carrier; Weight and weight percent meter with catalyst; The nickel content of said catalyst is that the nickel more than 5%～60%, 90% is distributed in carrier surface to the caltalyst of degree of depth 0.7mm.
Preferably, the nickel more than 95% is distributed in carrier surface to the caltalyst of degree of depth 0.7mm.
Preferably, with the weight and the weight percent meter of catalyst, said catalyst contains 10%～40% nickel.
Preferably, said method for preparing catalyst is: with the soluble salts of active components dissolving, solvent is the mixture of ammoniacal liquor and water, and the weight ratio of ammoniacal liquor and water is 1: 0～0.5, with the spray solution or the impregnated carrier of gained, and drying, decomposition and reduction then.
Preferably, said carrier is a two or more mixture in aluminium oxide, silica, active carbon, titanium dioxide or molecular sieve or these carriers.
The present invention provides a kind of method for preparing eggshell type nickel-based catalyst, and this method is simple to operation, and preparation process is few, and repeatability is reliable, and the field that prepared Ni-based loaded catalyst is used for many hydrogenation property has higher activity and selectivity.
Specifically the preparation scheme is, with the soluble salts of active components dissolving, solvent is the mixture of ammoniacal liquor and water, and the weight ratio of ammoniacal liquor and water is 1: 0～0.5, with the spray solution or the impregnated carrier of gained, and drying, decomposition and reduction then.Said ammoniacal liquor is commercially available concentrated ammonia liquor, and the mass percent concentration of ammoniacal liquor is generally 25%～28%, with NH
3Meter.When the ratio of water was 0, solvent was independent ammoniacal liquor, not dilute with water.
Preferably, the catalyst carrier that load is had nickel salt is in 100 ℃～150 ℃ oven dry.
Preferably, the reduction temperature of described catalyst is 200 ℃～500 ℃, and the time is 3～8h.
The nickel salt that catalyst of the present invention uses can be any soluble nickel salt, comprises nickel nitrate, nickelous carbonate, basic nickel carbonate, nickel acetate, citric acid nickel, nickelous sulfate etc. for example.
Catalyst of the present invention also can comprise other active component and/or auxiliary agent.For example introduce Acidity of Aikalinity and nickel and the carrier interactions of alkaline components, improve catalyst activity and optionally effect thereby play to improve catalyst.For example introduce molybdenum and/or tungsten component,, make the nickel particle thinner and more even to disperse the nickel component better.
The present invention provides the multiple application of eggshell type nickel-based catalyst.
Catalyst of the present invention also can be used for various hydrogenation reactions.Eggshell type nickel-based catalyst for example of the present invention can be used for pyrolysis gasoline hydrogenation, can be used for the prepared from benzene and hydrogen cyclohexane, and it is C 5 hydrogenated etc. to can be used for carbon four.In various hydrogenation processes, can select suitable hydrogenation technique condition according to the technical conditions and the experience of this area.Catalyst of the present invention does not have specific (special) requirements.
Catalyst of the present invention can be used for removing the carbon monoxide in the hydrogen.Contain carbon monoxide in the hydrogen, can use the catalyst poisoning of this hydrogen usually or reduce activity, thereby need the carbon monoxide in the hydrogen be changed into the methane that usually catalyst is not had influence.The reactor of the hydrogen that for example, will contain micro CO through catalyst of the present invention is housed is being methane with co hydrogenation wherein.
The nickel component of existing nickel-base catalyst is distributed on the whole carrier, and in catalyst of the present invention, most of nickel component is distributed in the housing of carrier, and the centronucleus part does not have the nickel component basically, and this distribution mode helps various catalytic reactions undoubtedly.Reactant arrives active sites easily, and especially internally diffusion reaction is more favourable, and the product that reaction generates can leave active sites quickly, thereby helps improving activity of such catalysts, also helps improving selection of catalysts property.Research shows that catalyst of the present invention has higher conversion ratio and selectivity to synthetic fatty amine.Method for preparing catalyst of the present invention is simple to operation, and repeatability is high.
The specific embodiment
Further explain Catalysts and its preparation method of the present invention with the mode of embodiment below, but the present invention is not limited to this.
Embodiment 1
Six water nickel nitrates are dissolved in process maceration extract in the ammoniacal liquor; Used ammoniacal liquor is mixed with weight ratio by commercially available 25%～28% ammoniacal liquor and water at 1: 0.5; Adopt equivalent impregnation method dipping spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 250m
2/ g, pore volume are 0.44ml/g, and drying is 4 hours under 120 ℃, 420 ℃ of following roastings 4 hours, reduce 8 hours down at 350 ℃ with hydrogen then, make catalyst A, in the weight of catalyst, contain the nickel of 10 weight %.The catalyst spheres particle is cut in half, can be clear that, the nickel component is distributed in carrier surface to the caltalyst of degree of depth 0.7mm, in the spherical nucleus of the degree of depth greater than 0.7mm, can't see the nickel component basically.
Embodiment 2
Six water nickel nitrates are dissolved in process maceration extract in the ammoniacal liquor; Used ammoniacal liquor is mixed with weight ratio by commercially available 25%～28% ammoniacal liquor and water at 1: 0.3; Adopt equivalent impregnation method dipping spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 274m
2/ g, pore volume are 0.45ml/g, and be first following dry 4 hours at 60 ℃; Descended dry 4 hours at 120 ℃ then,, and then flood equally one time again 420 ℃ of following roastings 4 hours; Drying, roasting was reduced 8 hours down at 375 ℃ with hydrogen; Make catalyst B,, contain the nickel of 20 weight % in the weight of catalyst.The catalyst spheres particle is cut in half, can be clear that, the nickel component is distributed in carrier surface to the caltalyst of degree of depth 0.7mm, in the spherical nucleus of the degree of depth greater than 0.7mm, can't see the nickel component basically.
Embodiment 3
Six water nickel nitrates are dissolved in process maceration extract in the ammoniacal liquor; Used ammoniacal liquor is mixed with weight ratio by commercially available 25%～28% ammoniacal liquor and water at 1: 0.1; Adopt spray method to spray the spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 264m
2/ g, pore volume are 0.45ml/g, earlier 60 ℃ dry 4 hours down, then 120 ℃ dry 4 hours down; 420 ℃ of following roastings 4 hours, repeat said process then again, reduced 8 hours down at 375 ℃ with hydrogen at last; Make catalyst C,, contain the nickel of 22 weight % in the weight of catalyst.The catalyst spheres particle is cut in half, can be clear that, the nickel component is distributed in carrier surface to the caltalyst of degree of depth 0.7mm, in the spherical nucleus of the degree of depth greater than 0.7mm, can't see the nickel component.
Embodiment 4
Six water nickel nitrates are dissolved in process maceration extract in the ammoniacal liquor; Used ammoniacal liquor is mixed with weight ratio by commercially available 25%～28% ammoniacal liquor and water at 1: 0.2; Adopt spray method to spray the spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 264m
2/ g, pore volume are 0.45ml/g, and drying is 4 hours under 120 ℃, again 420 ℃ of following roastings 4 hours, reduce 8 hours down at 375 ℃ with hydrogen, make catalyst D, in the weight of catalyst, contain the nickel of 12 weight %.The catalyst spheres particle is cut in half, can be clear that, the nickel component is distributed in carrier surface to the caltalyst of degree of depth 0.7mm, in the spherical nucleus of the degree of depth greater than 0.7mm, can't see the nickel component.
Embodiment 5
Six water nickel nitrates are dissolved in process maceration extract in the ammoniacal liquor, used ammoniacal liquor is commercially available 25%～28% ammoniacal liquor, adopts equivalent impregnation method dipping spherical alumina carrier, and alumina support is produced by the Beijing Chemical Research Institute, and specific area is 158m
2/ g, pore volume are 0.8ml/g, and be first following dry 4 hours at 60 ℃; Then 120 ℃ dry 4 hours down, again 420 ℃ of following roastings 4 hours, repeat above-mentioned dipping, drying and roasting process three times then; Reduced 8 hours down at 390 ℃ with hydrogen; Make catalyst E,, contain the nickel of 38 weight % in the weight of catalyst.The catalyst spheres particle is cut in half, can be clear that, the nickel component is distributed in carrier surface to the caltalyst of degree of depth 0.7mm, in the spherical nucleus of the degree of depth greater than 0.7mm, can't see the nickel component basically.
Comparative example 1
Six water nickel nitrates are dissolved in process the aqueous solution in the water, adopt equivalent impregnation method dipping spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 250m
2/ g, pore volume are 0.44ml/g, and drying is 4 hours under 120 ℃, again 420 ℃ of following roastings 4 hours, reduce 8 hours down at 350 ℃ with hydrogen, make catalyst F, in the weight of catalyst, contain the nickel of 10 weight %.The catalyst spheres particle is cut in half, can be clear that, the nickel component is evenly distributed in the catalyst whole particle basically.
Comparative example 2
Method according to US2008118642A1 prepares catalyst G.Six water nickel nitrates are dissolved in process the aqueous solution in the water, adopt spray method dipping spherical alumina carrier, alumina support is produced by the Beijing Chemical Research Institute, and specific area is 250m
2/ g, pore volume are 0.44ml/g, and drying is 4 hours under 120 ℃, again 420 ℃ of following roastings 4 hours, reduce 8 hours down at 350 ℃ with hydrogen, make catalyst G, in the weight of catalyst, contain the nickel of 10 weight %.The catalyst spheres particle is cut in half, can see that the nickel component is distributed in carrier surface basically to the caltalyst of degree of depth 0.7mm.
Embodiment 6
Present embodiment is hydrogenated to example fully with cracking c_5 and explains the application of catalyst of the present invention in field of hydrogenation, but application of the present invention is not limited to this.
Employed cracking c_5 material is provided by Yanshan Petrochemical company, and its composition is listed in table 1.
Catalyst B being packed in the fixed bed reactors, the cracking c_5 material is mixed the back and stream gets into bed from the bed lower end with hydrogen, is that 60 ℃, hydrogen to oil volume ratio are 60, the volume hourly space velocity is the catalytic performance of evaluate catalysts under 2h-1 and the 3MPa in inlet temperature.Composition with material behind gas chromatographic analysis raw material and the hydrogenation.Result of the test shows that behind the hydrogenation, monoolefine content is 0.3 weight % in carbon five materials, does not detect diolefin, thereby catalyst B of the present invention can be hydrogenated into alkane fully with the cracking c_5 raw material.
Table 1
Embodiment 7
Present embodiment is explained catalyst of the present invention application in the micro CO in removing hydrogen.
Respectively with catalyst A, F and the G fixed-bed tube reactor of packing into of preparation, under 400 ℃ of temperature and pressure 3.0MPa, with hydrogen reducing 6 hours, the hydrogen volume air speed was 2500h
-1, be cooled to 170 ℃ of reaction temperatures, feed unstripped gas, this unstripped gas contains 95% H
2, 0.4% carbon monoxide and the methane of surplus, the feed gas volume air speed is 10000h
-1, carrying out evaluation test, the content of carbon monoxide is listed in table 2 with evaluation result in the assay products.
Table 2
| Catalyst | Outlet CO content, ppm |
| A | ＜1ppm |
| F | 85ppm |
| G | 38ppm |
Can find out from the result of the test of table 2, under identical process conditions, although the nickel content of catalyst is identical,, catalyst A of the present invention has advantages of high catalytic activity.Difference only is that the distribution mode of nickel component is different with regulate different of preparation procedure parameter and crystal grain that produce is different, so catalyst activity and optionally distinguish and derive from own character of catalyst and preparation method thereof.
Claims (3)
1. an eggshell type nickel-based catalyst is characterized in that, said catalyst is made up of carrier and the active component nickel that loads on the carrier; With the weight and the weight percent meter of catalyst, the nickel content of said catalyst is that the nickel more than 5%～60%, 95% is distributed in carrier surface to the caltalyst of degree of depth 0.7mm; Said method for preparing catalyst is: six water nickel nitrates are dissolved; Solvent is the mixture of ammoniacal liquor and water, and the weight ratio of ammoniacal liquor and water is 1: 0～0.5, with the spray solution or the impregnated carrier of gained; Dry down at 100 ℃～150 ℃ then; 420 ℃ of following decomposition, at 200 ℃～500 ℃ following reduction 3～8h, the mass percent concentration of said ammoniacal liquor is 25%～28% again.
2. nickel-base catalyst as claimed in claim 1 is characterized in that, with the weight and the weight percent meter of catalyst, said catalyst contains 10%～40% nickel.
3. nickel-base catalyst as claimed in claim 1 is characterized in that, said carrier is a two or more mixture in aluminium oxide, silica, active carbon, titanium dioxide or molecular sieve or these carriers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084548A CN101890351B (en) | 2009-05-21 | 2009-05-21 | Eggshell type nickel-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910084548A CN101890351B (en) | 2009-05-21 | 2009-05-21 | Eggshell type nickel-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101890351A CN101890351A (en) | 2010-11-24 |
| CN101890351B true CN101890351B (en) | 2012-10-24 |
Family
ID=43099791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910084548A Active CN101890351B (en) | 2009-05-21 | 2009-05-21 | Eggshell type nickel-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101890351B (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728361A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof |
| CN102391067A (en) * | 2011-07-21 | 2012-03-28 | 吉林市道特化工科技有限责任公司 | Method for synthesizing isopropyl alcohol by hydrogenating acetone |
| WO2014088538A1 (en) * | 2012-12-03 | 2014-06-12 | United Technologies Corporation | Core-shell catalyst and method for palladium-based core particle |
| CN104971784A (en) * | 2015-07-07 | 2015-10-14 | 厦门大学 | Preparation method of supported metal catalysts |
| CN106563447B (en) * | 2016-10-20 | 2019-09-13 | 中国石油化工股份有限公司 | A kind of preparation method for the catalyst adding hydrogen for bisphenol-A |
| CN109794284B (en) * | 2017-11-17 | 2020-06-09 | 中国科学院大连化学物理研究所 | Molecular sieve material with metal enriched surface, preparation method and application thereof |
| CN109908892A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of ultra-pure hydrogen purifying sorbent material and application |
| CN111229216B (en) * | 2018-11-29 | 2022-08-05 | 万华化学集团股份有限公司 | Eggshell type silver catalyst and preparation method and application thereof |
| FR3099391B1 (en) | 2019-07-31 | 2021-10-29 | Ifp Energies Now | CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES DISTRIBUTED AS A CRUST |
| FR3099388B1 (en) | 2019-07-31 | 2021-07-16 | Ifp Energies Now | CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES DISTRIBUTED IN CRUST AND A NICKEL COPPER ALLOY |
| FR3099386B1 (en) | 2019-07-31 | 2021-07-16 | Ifp Energies Now | CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL DISTRIBUTED IN CRUST AND A NICKEL COPPER ALLOY |
| FR3099389B1 (en) | 2019-07-31 | 2021-07-16 | Ifp Energies Now | CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL SULFUR DISTRIBUTED IN CRUST |
| FR3099387B1 (en) | 2019-07-31 | 2021-10-29 | Ifp Energies Now | CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL DISTRIBUTED IN CRUST |
| CN112691672A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Eggshell catalyst and preparation method and application thereof |
| FR3110865A1 (en) | 2020-05-29 | 2021-12-03 | IFP Energies Nouvelles | PROCESS FOR PREPARING A CATALYST COMPRISING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES DISTRIBUTED INTO A CRUST AND A NICKEL COPPER ALLOY |
| FR3110862A1 (en) | 2020-05-29 | 2021-12-03 | IFP Energies Nouvelles | PROCESS FOR PREPARING A CATALYST CONTAINING AN ACTIVE PHASE OF NICKEL IN THE FORM OF SMALL PARTICLES DISTRIBUTED INTO A CRUST |
| FR3110866B1 (en) | 2020-05-29 | 2022-07-01 | Ifp Energies Now | METHOD FOR PREPARING A CATALYST COMPRISING AN ACTIVE NICKEL PHASE DISTRIBUTED IN A CRUST |
| FR3110864B1 (en) | 2020-05-29 | 2022-07-01 | Ifp Energies Now | METHOD FOR PREPARING A CATALYST COMPRISING AN ACTIVE NICKEL PHASE DISTRIBUTED IN CRUST AND A NICKEL-COPPER ALLOY |
| FR3110863A1 (en) | 2020-05-29 | 2021-12-03 | IFP Energies Nouvelles | PROCESS FOR PREPARATION OF A CATALYST INCLUDING AN ACTIVE PHASE OF NICKEL DISTRIBUTED IN CRUST OBTAINED FROM MELTED SALTS AND A NICKEL COPPER ALLOY |
| FR3110867B1 (en) | 2020-05-29 | 2022-07-01 | Ifp Energies Now | METHOD FOR PREPARING A CATALYST COMPRISING AN ACTIVE NICKEL PHASE DISTRIBUTED IN A CRUST OBTAINED FROM MOLTEN SALTS |
| CN111974405A (en) * | 2020-08-10 | 2020-11-24 | 华东理工大学 | CO selective methanation method |
| FR3125439A1 (en) | 2021-07-22 | 2023-01-27 | IFP Energies Nouvelles | METHOD FOR PREPARING A CATALYST COMPRISING AN ACTIVE PHASE OF NICKEL DISTRIBUTED IN THE CRUST VIA IMPREGNATION OF HEXANOL |
| FR3125440A1 (en) | 2021-07-22 | 2023-01-27 | IFP Energies Nouvelles | METHOD FOR PREPARING A CATALYST COMPRISING AN ACTIVE PHASE OF NICKEL DISTRIBUTED IN THE CRUST VIA IMPREGNATION OF HEPTANOL |
| CN115678596B (en) * | 2022-10-12 | 2024-08-27 | 中国石油大学(华东) | Method for selectively hydrogenating and removing diolefins from light hydrocarbons |
| CN115672333B (en) * | 2022-10-12 | 2024-07-12 | 中国石油大学(华东) | Ni-series eggshell catalyst, preparation method and method for selectively hydrodeolefinating reformate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266085A (en) * | 2000-02-03 | 2000-09-13 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101116822A (en) * | 2007-08-30 | 2008-02-06 | 汉能科技有限公司 | Non-uniform combustion catalyst and method for preparing the same |
-
2009
- 2009-05-21 CN CN200910084548A patent/CN101890351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266085A (en) * | 2000-02-03 | 2000-09-13 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101116822A (en) * | 2007-08-30 | 2008-02-06 | 汉能科技有限公司 | Non-uniform combustion catalyst and method for preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| 邱业君.甲烷部分氧化制合成气镍基催化剂的研究.《中国博士学位论文全文数据库 工程科技I辑（月刊）》.2009,(第4期),第27页第1-2段以及第33页表2-3. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101890351A (en) | 2010-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101890351B (en) | Eggshell type nickel-based catalyst | |
| CN104151129B (en) | The method of selective hydrogenation of alpha-methyl-styrene | |
| CN105921148A (en) | Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof | |
| CN111408370A (en) | Supported PtZn intermetallic alloy catalyst and preparation method and application thereof | |
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN104689830B (en) | A kind of catalyst for alkynes and diolefin hydrogenate in mixed olefins | |
| CN104907098B (en) | The co-based fischer-tropsch composite catalyst of metal polyacid, it is prepared and evaluation method | |
| CN101157029A (en) | A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method | |
| CN101898131A (en) | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof | |
| CN104971717A (en) | Pt-modified ZnO/Al2O3 catalyst and preparation method and application thereof | |
| CN110026230A (en) | A kind of dehydrogenating low-carbon alkane prepares catalyst and its application of corresponding alkene | |
| CN109701552A (en) | A kind of palladium-copper system support type sub-nanometer catalyst and preparation method thereof | |
| CN109806885A (en) | A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection | |
| CN110523433A (en) | A kind of nickel-base catalyst and the preparation method and application thereof | |
| CN112264078A (en) | Modified boron nitride supported metal catalyst and preparation method and application thereof | |
| CN102553634A (en) | Catalyst for Fischer-Tropsch synthesis and application thereof | |
| CN114192180A (en) | Modified boron nitride loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof | |
| CN105498759A (en) | High-performance catalyst for preparation of benzene by cyclotrimerization of acetylene as well as preparation method and application thereof | |
| CN110152735B (en) | Carbon dioxide reduction catalyst, preparation method and reduction reaction method | |
| CN104399469A (en) | Catalyst for catalyzing maleic anhydride and hydrogenating to prepare butanedioic anhydride under low temperature and low pressure and preparation method of catalyst | |
| CN113694921B (en) | Nano-diamond/graphene composite carrier loaded atomic-scale dispersed iridium cluster catalyst and preparation method and application thereof | |
| CN107970933A (en) | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating | |
| CN112295580B (en) | Sodium carbonate supported palladium-copper nano catalyst and application thereof in preparation of olefin by catalytic hydrogenation of alkyne | |
| CN107970929B (en) | A kind of alkynes and alkadienes liquid phase selective hydrogenation catalyst, preparation method and application | |
| CN104449835A (en) | Cracking C9 and C9+ hydrocarbon hydrogenation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |