CN103801347A - Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst - Google Patents

Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst Download PDF

Info

Publication number
CN103801347A
CN103801347A CN201210450573.5A CN201210450573A CN103801347A CN 103801347 A CN103801347 A CN 103801347A CN 201210450573 A CN201210450573 A CN 201210450573A CN 103801347 A CN103801347 A CN 103801347A
Authority
CN
China
Prior art keywords
catalyst
disproportionation
carrier
hour
butylene
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.)
Pending
Application number
CN201210450573.5A
Other languages
Chinese (zh)
Inventor
李鹏
田志坚
徐云鹏
曲炜
马怀军
徐仁顺
王炳春
徐竹生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201210450573.5A priority Critical patent/CN103801347A/en
Publication of CN103801347A publication Critical patent/CN103801347A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a catalyst for self-disproportionation of the mixed butene, and a preparation method of the catalyst. The catalyst comprises active ingredients and a carrier, and is characterized in that the carrier of the catalyst is phosphorus and sulfur-modified gama-alumina, the weight of the phosphorus oxide is 0.1%-10% of the weight of the carrier, and the weight of the sulfur oxide is 0.1%-8% of the weight of the carrier. The active ingredients of the catalyst include VIB and VIIB metal oxide, and the total weight loading of the active ingredients is 0.5%-15%. The catalyst obtained by adopting the method can be used for technological process of producing propylene through self-disproportionation reaction of the mixed butene, thus having excellent industrial application values.

Description

A kind of catalyst and preparation and application from disproportionation for mixed butene
Technical field
The present invention relates to a kind of for mixed butene the catalyst from disproportionation
The invention still further relates to the preparation method of above-mentioned catalyst
The invention still further relates to the application of above-mentioned catalyst.
Background technology
The production of refinery of China accounts for leading with catalytic cracking process, along with the raising of refining capacity, catalytic cracking unit is by a large amount of by-product C 4alkene, due to its bad transportation, generally all burns as fuel, and utilizes olefin dismutation reaction, can be by C relative surplus, that added value is lower 4alkene is converted into the propylene of higher-value.Propylene is one of basic chemical raw materials that on current world Petrochemical Market, demand growth is the fastest, remains at present that supply falls short of demand, and this disproportionation technology can reasonably be reconciled the product layout of propylene and butylene, can produce considerable economic benefit and social benefit.
Can there is following disproportionated reaction and generate propylene in carbon four mixed olefins:
1-butylene+2-butylene=propylene+2-amylene
2(1-butylene)=ethene+3-hexene
Ethene+2-butylene=2(propylene)
The distinguishing feature of this course of reaction is the further disproportionation generation propylene of a small amount of ethene producing, and improves the selective of propylene.In the more nervous area of ethene supply, utilize this course of reaction without ethene directly take mixed butene as reaction raw materials disproportionation propylene processed, thereby reduced production cost.
The key of olefin dismutation reaction is catalyst, and catalyst can be divided into homogeneous catalyst and heterogeneous catalyst, and heterogeneous olefin disproportionation catalyst is generally the compound loaded on inert carrier of W, Mo, Re etc., and inert carrier is generally SiO 2, Al 2o 3, SiO 2-Al 2o 3, Al 2o 3-B 2o 3.
CN1021639C provides the MoO of a kind of sulphur for olefin(e) disproportionation or phosphorus modification 3/ Al 2o 3catalyst.This catalyst is with sulphur or phosphorus compound and alumina support grinding kneading and compacting, by the solution impregnation that contains molybdenum oxide, forms through 120 ° of C oven dry and 560 ° of C roastings.This catalyst is for C 12olefin(e) disproportionation has good activity.
US6,130,181 provide a kind of for C 4the preparation method of the rheium oxide catalyst of olefin dismutation reaction.Aluminium oxide passes through preparation catalyst with the solution containing rhenium compound.Catalyst is for mixed C 4the disproportionated reaction of alkene, under the condition of 60 ° of C, 1.0MPa and 1-butylene/2-butylene mol ratio 1:1, the conversion ratio of 1-butylene is 80%, selectivity of product reaches 90%.But this catalyst alkene total conversion is not high.
US6,586,649 provide a kind of for C 4the preparation method of the tungsten oxide catalyst of olefin dismutation reaction.This catalyst is that tungsten oxide is carried on silica, 300-600 ℃ of reaction condition temperature, a pressure 1-20 atmospheric pressure.
EP0,489,585 have proposed the preparation method of butylene disproportionation catalyst, and catalyst is WO 3/ inert carrier, wherein carrier is SiO 2with MgO or SiO 2with TiO 2what form is cogelled, and the catalyst of preparing by said method can make the activity of ethene and 2-preparing propylene by butene disproportionation increase.But above-mentioned two kinds of tungsten oxide catalyst activity are not high, and reaction temperature is higher.
Summary of the invention
The object of the present invention is to provide a kind of for mixing catalyst and preparation and the application of C 4 olefin disproportionation propylene processed, this catalyst can be applicable to carbon four mixed olefins (carbon four raffinate II after industrial ether) disproportionated reaction produce propylene.Use catalyst provided by the invention can high conversion, the production propylene of high selectivity and high stability.
Provided by the present invention for mixing the catalyst of C 4 olefin disproportionation propylene processed, it is characterized in that: the carrier of catalyst is the gama-alumina of p and s modification, and phosphorous oxide accounts for the 0.1%-10% of vehicle weight, and sulfur oxide accounts for the 0.1%-8% of vehicle weight.The active component of catalyst is VIB and VIIB metal oxide, and its gross weight loading is 0.5%-15%.
Method for preparing catalyst provided by the present invention is:
(a) with solution (0.1-0.7gP/ml) dipping γ-Al that contains P elements 2o 3carrier, at 60-150 ℃ of dry 3-6 hour and in 350-700 ℃ of roasting 1-12 hour;
(b) with solution (0.1-0.7gS/ml) dipping γ-Al that contains element sulphur 2o 3carrier, at 60-150 ℃ of dry 3-6 hour and in 350-700 ℃ of roasting 1-12 hour;
(c) above-mentioned calcining matter is flooded with the solution (0.05-0.3g/ml) containing active metal component, at 60-150 ℃ of dry 3-6 hour and in 350-800 ℃ of roasting 1-12 hour.
Wherein the impregnation sequence of modified component phosphorus, sulphur can be changed, and the order of step (a) and step (b) is exchanged; The phosphorus-containing compound that step a uses is phosphoric acid, metaphosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, and it is sulfuric acid, sulfurous acid, ammonium sulfate or ammonium hydrogen sulfate that step b uses.
Reaction starts procatalyst pretreatment catalyst 1-20h in 400-700 ℃ of inert atmosphere, makes its activation become butylene from disproportionation catalyst.Wherein inert atmosphere is N 2, Ar or He.
Adopt the catalyst of technique scheme of the present invention can use in carbon four mixed olefins self disproportionation reactions, raw material 1-butylene/2-butylene mol ratio is 1:3-3:1, adopt fixed bed reactors, the range of reaction temperature of disproportionated reaction is 10-150 ° of C, reaction pressure scope is 1-10MPa, and the volume space velocity of disproportionated reaction is 0.5-5h -1.Under this reaction condition, effectively raise the selective of the activity of butylene disproportionation reaction and propylene.
The present invention has following distinguishing feature:
(1) catalyst, in the present invention has high activity and high selective, can make disproportionated reaction carry out under gentle condition.
(2), catalyst has higher stability, can repetitive cycling regeneration.
Below by example, the present invention is described in further detail.
The specific embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment.
Embodiment 1
Phosphorus, the preparation of boron modified aluminium oxide supports
The alumina support of preparing as raw material compressing tablet take SB powder (an a kind of industrial diaspore), with phosphoric acid and ammonium sulfate (0.3gP/ml, 0.15gS/ml) it is flooded, particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, make required bearer number and be respectively APS-1, APS-2 and APS-3, wherein the weight percentage of phosphorous oxide is respectively 0.1%, 2% and 5%, and the weight percentage of sulfur oxide is respectively 0.5%, 1% and 3%.Alumina support is flooded with diammonium hydrogen phosphate or ammonium dihydrogen phosphate (0.3gP/ml), particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, make required bearer number and be respectively APS-4 and APS-5, wherein the weight percentage of phosphorous oxide is 2%, and the weight percentage of sulfur oxide is 1%.
Embodiment 2～4
Get different proportioning ammonium perrhenate solution (0.1315gRe for 3 parts of APS-1 carriers 2o 7/ ml) and ammonium molybdate solution (0.0827gMoO 3/ ml) flood, particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, makes required catalyst numbering and is respectively MC-1, MC-2 and MC-3, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%, and the weight percentage of molybdenum oxide is respectively 1%, 2% and 3%.
Embodiment 5～7
Get different proportioning ammonium perrhenate solution (0.1315gRe for 3 parts of APS-2 carriers 2o 7/ ml) and ammonium molybdate solution (0.0827gMoO 3/ ml) flood, particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, make required catalyst numbering and be respectively MC-4, MC-5 and MC-6, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%, and the weight percentage of molybdenum oxide is respectively 1%, 2% and 3%.
Embodiment 8～10
Get different proportioning ammonium perrhenate solution (0.1315gRe for 3 parts of APS-3 carriers 2o 7/ ml) and ammonium molybdate solution (0.0827gMoO 3/ ml) flood, particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, make required catalyst numbering and be respectively MC-7, MC-8 and MC-9, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%, and the weight percentage of molybdenum oxide is respectively 1%, 2% and 3%.
Comparative example 1～2
Get respectively APS-4 and identical proportioning ammonium perrhenate solution (0.1315gRe for APS-5 carrier 2o 7/ ml) flood, the particle after dipping is dried and 550 ° of C roastings 8 hours through 120 ° of C, makes required catalyst numbering and is respectively MC-10 and MC-11, and wherein the weight percentage of rheium oxide is 6%.
Comparative example 3
The alumina support of preparing as raw material compressing tablet take SB powder (an a kind of industrial diaspore), with ammonium metatungstate solution (0.1017gWO 3/ ml) flood, then dry and 550 ° of C roastings make required catalyst for 8 hours and are numbered MC-12 through 120 ° of C, wherein tungsten oxide weight percentage is 6%.
Embodiment 11
Get 10ml catalyst and pack fixed bed reactors into, the internal diameter of reactor is 10mm, and length is 41cm.Reaction procatalyst is at N 2under atmosphere, be warming up to 500 ℃ of pretreatment 2h, then at N 2atmosphere borehole cooling to 80 ℃, enters to mix C 4 olefin (1-butylene/2-butylene=3:1) and carries out disproportionated reaction, and reaction pressure is 1MPa, volume space velocity 1h -1.Stable reaction afterproduct is through on-line chromatograph analysis.The evaluation result of different catalysts is listed in table 1.Under identical reaction condition, by relatively finding out, catalyst MEC-5 has higher feed stock conversion and Propylene Selectivity compared with other catalyst.
The reactivity worth of table 1 different catalysts in carbon four butylene disproportionations
Figure 2012104505735100002DEST_PATH_IMAGE001
Note: Propylene Selectivity is the percentage that propylene carbon atoms molal quantity accounts for all product carbon atoms molal quantitys.

Claims (9)

1. the catalyst from disproportionation for mixed butene, this catalyst is made up of active component and carrier, it is characterized in that:
The carrier of catalyst is the gama-alumina of p and s modification, and phosphorous oxide accounts for the 0.1%-10% of vehicle weight, and sulfur oxide accounts for the 0.1%-8% of vehicle weight;
The active component of catalyst is VIB and VIIB metal oxide, and its gross weight loading is 0.5%-15%.
2. according to catalyst described in claim 1, it is characterized in that: described carrier gama-alumina, specific area is 150-400m 2/ g, average pore size is 6-20nm, pore volume is 0.5-1.2ml/g.
3. according to catalyst described in claim 1, it is characterized in that: described VIB and VIIB metal component comprise one or two or more kinds in Re, Mo, W.
4. a preparation method for catalyst described in any one claim in claim 1-3, is characterized in that:
(a) with solution (0.1-0.7gP/ml) dipping γ-Al that contains P elements 2o 3carrier, at 60-150 ℃ of dry 3-6 hour and in 350-700 ℃ of roasting 1-12 hour; Again with solution (0.1-0.7gS/ml) impregnated carrier that contains element sulphur, 60-150 ℃ of dry 3-6 hour and after 350-700 ℃ of roasting 1-12 hour calcining matter;
(b) above-mentioned calcining matter is flooded with the solution (0.05-0.3g/ml) containing active metal component, at 60-150 ℃ of dry 3-6 hour and in 350-800 ℃ of roasting 1-12 hour.
5. according to preparation method claimed in claim 4, it is characterized in that:
The phosphorus-containing compound using in step a is phosphoric acid, metaphosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate; The sulfur-containing compound using is sulfuric acid, sulfurous acid, ammonium sulfate or ammonium hydrogen sulfate.
6. in a claim 1-3, described in any one claim, catalyst is applied in the reaction that mixes C 4 olefin disproportionation propylene processed.
7. according to application claimed in claim 6, it is characterized in that: in claim 1-3, described in any one, catalyst uses with front, pretreatment catalyst 1-20h in 400-700 ℃ of inert atmosphere makes its activation become butylene from disproportionation catalyst.
8. according to application claimed in claim 7, it is characterized in that: inert atmosphere is N 2, Ar or He.
9. according to application claimed in claim 6, it is characterized in that: raw material 1-butylene/2-butylene mol ratio is 1:3-3:1, and butylene from the reaction condition of disproportionation is: reaction temperature 10-150 ℃, reaction pressure 1-10MPa, weight space velocity 0.5-5h -1.
CN201210450573.5A 2012-11-12 2012-11-12 Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst Pending CN103801347A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210450573.5A CN103801347A (en) 2012-11-12 2012-11-12 Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210450573.5A CN103801347A (en) 2012-11-12 2012-11-12 Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst

Publications (1)

Publication Number Publication Date
CN103801347A true CN103801347A (en) 2014-05-21

Family

ID=50699019

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210450573.5A Pending CN103801347A (en) 2012-11-12 2012-11-12 Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst

Country Status (1)

Country Link
CN (1) CN103801347A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106607067A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Olefin disproportionation catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634539A (en) * 1968-06-10 1972-01-11 Shell Oil Co Olefin disproportionation
US4368141A (en) * 1981-06-24 1983-01-11 Phillips Petroleum Company Olefin disproportionation and catalyst therefor
CN1033246A (en) * 1987-11-18 1989-06-07 国际壳牌研究有限公司 The catalyst system and the using method thereof that are used for olefin(e) disproportionation
CN1465435A (en) * 2002-06-21 2004-01-07 中国科学院大连化学物理研究所 Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof
CN102335631A (en) * 2010-07-16 2012-02-01 中国石油天然气股份有限公司 Mesoporous catalyst for low-carbon olefin disproportionation and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634539A (en) * 1968-06-10 1972-01-11 Shell Oil Co Olefin disproportionation
US4368141A (en) * 1981-06-24 1983-01-11 Phillips Petroleum Company Olefin disproportionation and catalyst therefor
CN1033246A (en) * 1987-11-18 1989-06-07 国际壳牌研究有限公司 The catalyst system and the using method thereof that are used for olefin(e) disproportionation
CN1465435A (en) * 2002-06-21 2004-01-07 中国科学院大连化学物理研究所 Catalyst for preparing propene at low temp. from ethylene and butylene, proparation process and use thereof
CN102335631A (en) * 2010-07-16 2012-02-01 中国石油天然气股份有限公司 Mesoporous catalyst for low-carbon olefin disproportionation and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106607067A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Olefin disproportionation catalyst
CN106607067B (en) * 2015-10-21 2019-06-11 中国石油化工股份有限公司 Olefin disproportionation catalyst

Similar Documents

Publication Publication Date Title
JPH0569582B2 (en)
CN105268459B (en) A kind of catalyst for dehydrogenation of low-carbon paraffin of sulfur-bearing and preparation method thereof
CN107029779B (en) A kind of multi-stage porous hydrocracking catalyst and its application containing Y type molecular sieve
CN106902867B (en) Beta zeolite catalyst for preparing BTEX (benzene, toluene, ethylbenzene and xylene) mixture from polyaromatic hydrocarbon and preparation method thereof
CN101905163A (en) Coal tar hydrorefining catalyst and preparation method thereof
CN105233848A (en) Ni, W and P loaded hydrofining catalyst with three-peak type pore size distribution for anthracene oil, and preparation method and application
CN106552640A (en) Reformer feed catalyst for pre-hydrogenation and preparation method thereof
CN103801347A (en) Catalyst for self-disproportionation of mixed butene, and preparation method and applications of catalyst
CN106268931B (en) A kind of hydrocracking catalyst and its application containing composite molecular screen
CN108262063A (en) Hydrogenation catalyst and preparation method thereof
CN105457672B (en) The method of hydrocracking catalyst and preparation method thereof and hydrocracking reaction
CN101767013B (en) Fluid catalyst for preparing acrylonitrile by ammonia oxidation process
CN106179388A (en) A kind of preparation method of hydrotreating catalyst
RU2603776C1 (en) Method of hydrocracking hydrocarbon material
CN103785483B (en) A kind of method of hydrogenation catalyst and preparation method and lightweight oil hydrofining
JPH0573466B2 (en)
CN103785484B (en) A kind of hydrogenation catalyst and preparation method and the hydrorefined method of light oil
CN103100392A (en) Hydrocracking catalyst and preparation method thereof
CN102861591B (en) Hydrogenation catalyst containing boron and preparation method thereof
CN102309990A (en) Hydrocracking catalyst and preparation method thereof
CN106031880B (en) A kind of multi-stage porous hydrocracking catalyst and its application
CN106179383A (en) The preparation method of hydrotreating catalyst
CN103254927B (en) Treatment method for catalytic reformation and prehydrogenation of gasoline
CN102527375A (en) Catalyst used in preparation of propylene by disproportionating mixed C4 olefin and preparation and application thereof
CN104557399A (en) Method for preparing propylene from pentene and ethylene by disproportionation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20140521

RJ01 Rejection of invention patent application after publication