CN102527375A - Catalyst used in preparation of propylene by disproportionating mixed C4 olefin and preparation and application thereof - Google Patents

Catalyst used in preparation of propylene by disproportionating mixed C4 olefin and preparation and application thereof Download PDF

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Publication number
CN102527375A
CN102527375A CN2010105889470A CN201010588947A CN102527375A CN 102527375 A CN102527375 A CN 102527375A CN 2010105889470 A CN2010105889470 A CN 2010105889470A CN 201010588947 A CN201010588947 A CN 201010588947A CN 102527375 A CN102527375 A CN 102527375A
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catalyst
boron
carrier
preparation
solution
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李鹏
田志坚
王炳春
马怀军
王磊
曲炜
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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 relates to a catalyst used in preparation of propylene by disproportionating mixed C4 olefin and a preparation and an application thereof. The catalyst consists of an active ingredient and a carrier, wherein the carrier of the catalyst is phosphorus and boron-modified alumina; phosphorus oxide accounts for 0.1-8 percent of the weight of the carrier; boron oxide accounts for 0.1-8 percent of the weight of the carrier; the active ingredient of the catalyst is rhenium oxide; and the total weight loading amount is 1-15 percent. The catalyst prepared with the method can be used in a technical process for producing propylene by undergoing a disproportionating reaction on mixed C4 olefin, and has a good industrial application value.

Description

Be used for catalyst and the preparation and the application of mixed c 4 preparing propylene through olefin disproportionation
Technical field
The present invention relates to a kind of be used for mixed c 4 preparing propylene through olefin disproportionation catalyst and preparation and application.
Background technology
The production of China refinery accounts for leading with catalytic cracking process, along with the raising of refining capacity, catalytic cracking unit is with a large amount of C of by-product 4Alkene owing to its bad transportation, generally all acts as a fuel and burns, and utilize olefin dismutation reaction, can be with superfluous, that added value is lower relatively C 4Alkene is converted into the propylene of higher-value.Propylene is one of basic chemical raw materials that demand growth is the fastest on the petrochemical industry market, the present world, 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 and social benefit.
Following disproportionated reaction can take place and generate propylene in carbon four mixed olefins:
1-butylene+2-butylene=propylene+2-amylene
2 (1-butylene)=ethene+3-hexenes
Ethene+2-butylene=2 (propylene)
The distinguishing feature of this course of reaction be the small amount of ethylene that produces further disproportionation generate propylene, the selectivity of raising propylene.In the relatively more nervous area of ethene supply, utilize this course of reaction directly to be reaction raw materials disproportionation system propylene without ethene, thereby reduced production cost with the mixed butene.
The key of olefin dismutation reaction is a 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
US6,130,181 provide a kind of C of being used for 4The rheium oxide Preparation of catalysts method of olefin dismutation reaction.Aluminium oxide passes through the immersion process for preparing catalyst with the solution that contains rhenium compound.Catalyst is used for mixed C 4The disproportionated reaction of alkene, the conversion ratio of 1-butylene is 80% under the condition of 60 ° of C, 1.0MPa and 1-butylene/2-butylene mol ratio 1:1, selectivity of product reaches 90%.But this catalyst alkene total conversion is not high.
US6,586,649 provide a kind of C of being used for 4The preparation method of the tungsten oxide catalyst of olefin dismutation reaction.This catalyst is that tungsten oxide is carried on the silica, 300 ~ 600 ℃ of reaction condition temperature, 1 ~ 20 atmospheric pressure of pressure.
EP0,489,585 have proposed butylene disproportionation Preparation of catalysts method, and catalyst is WO 3/ inert carrier, wherein carrier is SiO 2With MgO or SiO 2With TiO 2What form is cogelled, can make the activity increase of ethene and 2-preparing propylene by butene disproportionation through the catalyst of method for preparing.But above-mentioned two kinds of tungsten oxide catalyst activity are not high, and reaction temperature is higher.
So far, do not find to be used for the process of mixed c 4 preparing propylene by olefin dismutation reaction as yet with phosphorus and boron modified aluminas load rheium oxide active constituent catalyst.
Summary of the invention
The object of the present invention is to provide a kind of catalyst and preparation and application that is used for the mixed c 4 preparing propylene through olefin disproportionation, this catalyst can be applicable to carbon four mixed olefins (carbon four raffinate II behind the industrial ether) disproportionated reaction and produces propylene.Use catalyst provided by the invention can high conversion, the production propylene of high selectivity and high stability.
The catalyst that is used for the mixed c 4 preparing propylene through olefin disproportionation provided by the present invention; It is characterized in that: the carrier of catalyst is the aluminium oxide of phosphorus and boron modification; Phosphorous oxide accounts for 0.1% ~ 5% of vehicle weight; Boron oxide accounts for 0.1% ~ 5% of vehicle weight, and the activity of such catalysts component is a rheium oxide, and its gross weight loading is 3% ~ 12%.
Method for preparing catalyst provided by the present invention is:
(a) with the solution (concentration 0.1 ~ 0.7g P that contains P elements 2O 5/ ml) dipping γ-Al 2O 3Carrier is 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 700 ℃ of roastings 1 ~ 12 hour;
(b) with the solution (concentration 0.1 ~ 0.7g B that contains boron element 2O 3/ ml) dipping γ-Al 2O 3Carrier is 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 700 ℃ of roastings 1 ~ 12 hour;
(c) to the solution (concentration 0.05 ~ 0.4g Re of above-mentioned calcining matter with the rhenium-containing element 2O 7/ ml) flood, 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 800 ℃ of roastings 1 ~ 12 hour.
Wherein the impregnation sequence of modified component phosphorus, boron can be changed, and promptly the order of step (a) and step (b) is exchanged; The phosphorus-containing compound that step a uses is boric acid as phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, the boron-containing compound that step b uses; The rhenium compound that contains that step c uses is ammonium perrhenate or perrhenic acid.
The activation in 350 ~ 750 ° of C temperature ranges under nitrogen atmosphere of reaction beginning procatalyst, soak time is 1 ~ 10 hour.
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 generally 10 ~ 150 ° of C, and the reaction pressure scope is generally 1 ~ 10MPa, and the volume space velocity of disproportionated reaction is 1 ~ 10h -1Under this reaction condition, effectively raise the selectivity of butylene disproportionation reactive activity and propylene.
The present invention has following distinguishing feature:
(1), the catalyst among the present invention has high activity and high selectivity, can make disproportionated reaction under the condition of gentleness, carry out.
(2), catalyst has advantages of higher stability, can the repetitive cycling regeneration.
Through instance the present invention is described in further detail below.
The specific embodiment
Below in conjunction with embodiment the present invention is done further elaboration, but the present invention is not produced any restriction.
Embodiment 1
Phosphorus, the preparation of boron modified aluminium oxide supports
With SB powder (an a kind of industrial diaspore) is the alumina support of raw material compressing tablet preparation, with phosphoric acid and BAS (concentration 0.25g P 2O 5/ ml and 0.35g B 2O 3/ ml) it is flooded; Particle behind the dipping was through 120 ° of C oven dry and 550 ° of C roastings 8 hours; Make required bearer number and be respectively APB-1, APB-2 and APB-3; Wherein the weight percentage of phosphorous oxide is respectively 0.1%, 2% and 5%, and the weight percentage of boron oxide is respectively 0.5%, 2% and 5%.With diammonium hydrogen phosphate or ammonium dihydrogen phosphate (concentration 0.25g P 2O 5/ ml) alumina support is flooded; Particle behind the dipping was through 120 ° of C oven dry and 550 ° of C roastings 8 hours; Make required bearer number and be respectively APB-4 and APB-5, wherein the weight percentage of phosphorous oxide is 2%, and the weight percentage of boron oxide is 2%.
Embodiment 2～4
Get 3 parts of APB-1 carriers with ammonium perrhenate solution (concentration 0.1427g Re 2O 7/ ml) flooding, particle behind the dipping makes required catalyst numbering and is respectively MEC-1 through 120 ° of C oven dry and 550 ° of C roastings 8 hours, MEC-2 and MEC-3, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%.
Embodiment 5～7
Getting 3 parts of APB-2 carriers floods with above-mentioned ammonium perrhenate solution; Particle behind the dipping was through 120 ° of C oven dry and 550 ° of C roastings 8 hours; Make required catalyst numbering and be respectively MEC-4, MEC-5 and MEC-6, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%.
Embodiment 8～10
Getting 3 parts of APB-3 carriers floods with above-mentioned ammonium perrhenate solution; Particle behind the dipping was through 120 ° of C oven dry and 550 ° of C roastings 8 hours; Make required catalyst numbering and be respectively MEC-7, MEC-8 and MEC-9, wherein the weight percentage of rheium oxide is respectively 3%, 6% and 12%.
Comparative example 1～2
Getting APB-4 and APB-5 carrier respectively floods with above-mentioned ammonium perrhenate solution; Particle behind the dipping was through 120 ° of C oven dry and 550 ° of C roastings 8 hours; Make required catalyst numbering and be respectively MEC-10 and MEC-11, wherein the weight percentage of rheium oxide is 6%.
Comparative example 3
With SB powder (an a kind of industrial diaspore) is the alumina support of raw material compressing tablet preparation; Flood with ammonium perrhenate solution; 120 ° of C oven dry of warp and 550 ° of C roastings made required catalyst in 8 hours and are numbered MEC-12 then, and wherein the rheium oxide weight percentage is 6%.
Embodiment 11
Get the 10ml catalyst fixed bed reactors of packing into, the internal diameter of reactor is 10mm, and length is 41cm.The reaction procatalyst is at N 2Under the atmosphere, be warming up to 500 ℃ of preliminary treatment 2h, then at N 2Cool to 80 ℃ under the atmosphere, (1-butylene/2-butylene=3:1) carry out disproportionated reaction, reaction pressure is 1MPa, volume space velocity 1h to advance mixed c 4 alkene -1The stable reaction afterproduct is through the on-line chromatograph analysis.The evaluation result of different catalysts is listed in table 1.Under identical reaction condition, can find out that through comparing catalyst MEC-5 compares with other catalyst has higher feed stock conversion and propylene selectivity.
Figure 2010105889470100002DEST_PATH_IMAGE001

Claims (9)

1. catalyst that is used for the mixed c 4 preparing propylene through olefin disproportionation; This catalyst is made up of active component and carrier; It is characterized in that: the carrier of catalyst is the aluminium oxide of phosphorus and boron modification, and phosphorous oxide accounts for 0.1% ~ 8% of vehicle weight, and boron oxide accounts for 0.1% ~ 8% of vehicle weight; The activity of such catalysts component is a rheium oxide, and its gross weight loading is 1% ~ 15%.
2. according to the said catalyst of claim 1, it is characterized in that: the modified material phosphorous oxide accounts for 0.1 ~ 5% of vehicle weight, and boron oxide accounts for 0.1% ~ 5% of vehicle weight.
3. according to the said catalyst of claim 1, it is characterized in that: active component rheium oxide weight content is 3 ~ 12%.
4. the said Preparation of catalysts method of each claim among the claim 1-3 is characterized in that:
(a) with containing P elements concentration 0.1 ~ 0.7g P 2O 5The solution impregnation γ of/ml-Al 2O 3Carrier is 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 700 ℃ of roastings 1 ~ 12 hour;
(b) with containing boron element concentration 0.1 ~ 0.7g B 2O 3The solution impregnation γ of/ml-Al 2O 3Carrier is 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 700 ℃ of roastings 1 ~ 12 hour;
(c) to above-mentioned calcining matter with rhenium-containing concentration of element 0.05 ~ 0.4g Re 2O 7The solution of/ml floods, 60 ~ 150 ℃ of dryings 3 ~ 6 hours and in 350 ~ 800 ℃ of roastings 1 ~ 12 hour.
5. according to the described preparation method of claim 4, it is characterized in that: wherein the impregnation sequence of modified component phosphorus, boron can be changed, and promptly the order of step (a) and step (b) is exchanged.
6. according to the described preparation method of claim 4, it is characterized in that: step a contains the phosphorus-containing compound that uses in the solution of P elements and is phosphoric acid, ammonium dihydrogen phosphate (ADP) or diammonium hydrogen phosphate, and step b contains the boride that uses in the solution of boron element and is boric acid.
7. according to the described preparation method of claim 4, it is characterized in that: the rhenium compound that contains of the rhenium-containing unit cellulose solution that uses in the solution of step c rhenium-containing element is ammonium perrhenate or perrhenic acid.
Among the claim 1-3 the said catalyst applications of each claim in the reaction of mixed c 4 preparing propylene through olefin disproportionation.
9. according to the described application of claim 8, it is characterized in that: range of reaction temperature is 10 ~ 150 ° of C, and the reaction pressure scope is 1 ~ 10MPa.
CN2010105889470A 2010-12-15 2010-12-15 Catalyst used in preparation of propylene by disproportionating mixed C4 olefin and preparation and application thereof Pending CN102527375A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN103721729A (en) * 2013-12-17 2014-04-16 中国科学院长春应用化学研究所 Solid acid catalyst and preparation method thereof, and preparation method of diolefin compound

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7145050B2 (en) * 2001-08-28 2006-12-05 Symrise Gmbh & Co. Kg Modified supported metathesis catalysts
CN101676246A (en) * 2008-09-18 2010-03-24 中国石油天然气股份有限公司 Method for producing high-value olefin by low carbon olefin disproportionation reaction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7145050B2 (en) * 2001-08-28 2006-12-05 Symrise Gmbh & Co. Kg Modified supported metathesis catalysts
CN101676246A (en) * 2008-09-18 2010-03-24 中国石油天然气股份有限公司 Method for producing high-value olefin by low carbon olefin disproportionation reaction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XU XIAODING, ET AL.: "Re207/A1203 B203 Metathesis Catalysts", 《J. CHEM. SOC.,FARADAY TRANS. I》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103721729A (en) * 2013-12-17 2014-04-16 中国科学院长春应用化学研究所 Solid acid catalyst and preparation method thereof, and preparation method of diolefin compound
CN103721729B (en) * 2013-12-17 2016-06-01 中国科学院长春应用化学研究所 The preparation method of a kind of solid acid catalyst, its preparation method and double olefin compound

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Application publication date: 20120704