CN1373007A - Catalyst for preparing propylene by dismutation reaction and its preparing process and application - Google Patents
Catalyst for preparing propylene by dismutation reaction and its preparing process and application Download PDFInfo
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- CN1373007A CN1373007A CN01104355A CN01104355A CN1373007A CN 1373007 A CN1373007 A CN 1373007A CN 01104355 A CN01104355 A CN 01104355A CN 01104355 A CN01104355 A CN 01104355A CN 1373007 A CN1373007 A CN 1373007A
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- butylene
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- oxide
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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
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Abstract
A catalyst for preparing propylene by dismutation reaction of the gas mixture containing ethylene and butylene is composed of the active components (5-30%) including tungsten oxide, molybdenum oxide and rhenium oxide and the carrier (more than 50 wt.%) which may be molecular sieve of Silicate-2,H, beta, SAPO, ZSM, or MCM type. Said catalyst can be suitable for fixed-bed or fluidized-bed reactor at 0-300 deg.C, 0.01-3/hr and 0.1-2.0 MPa. Its advantages are high selectivity and high conversion.
Description
The present invention relates to a kind of catalyst that contains the gaseous mixture disproportionation preparation of propene of ethene and butylene, the application in the gaseous mixture disproportionation system propylene of ethene and butylene of Preparation of catalysts and catalyst.
Propylene is one of important foundation raw material of development petrochemical industry, also is the petrochemical industry product that demand growth is the fastest in the world, and world's propylene demand from 1,800 ten thousand tons of nearly 5,000 ten thousand tons of increasing to 2000 in 1980, expects 2010 and will reach 75,000,000 tons.It with ethene and butene reaction system propylene one of method that increases propone output, because supply exceed demand for butylene at present, especially the butene-2 shortage is effectively utilized approach, so suit measures to local conditions to adopt this course of reaction can reasonably regulate the product layout of ethene, propylene and butylene.There is part to contain the crude ethylene of methane, ethane and small quantity of hydrogen in addition in the product of heavy oil catalytic pyrolysis, itself and butene reaction are made propylene, both can improve the output of propylene, and can reduce the energy consumption of cryogenic separation again, and this course of reaction is more favourable than propylene disproportionation as can be known by calculation of thermodynamics.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
In addition, United States Patent (USP) (USP:5877365) has reported that C 4 fraction is converted into polyisobutene and propylene process.This process comprises following three steps: (1) butene-1 tautomerizes to butene-2; (2) isobutene polymerisation becomes polyisobutene; (3) butene-2 and ethene disproportionation system propylene.Butene-2 and ethene disproportionation system propylene catalyst system therefor are the oxide carried in a mixed oxide of rhenium (0.01-20wt%), this mixed oxide comprises at least 75% aluminium oxide, other is a sieve and silica-sesquioxide, one or both in the oxide of molecular sieve and 0.01-30% niobium and tantalum.Reaction temperature between 0-200 ℃, the saturated vapor pressure of gaseous mixture when pressure is higher than reaction temperature.
United States Patent (USP) (USP:5120894) has been reported the catalyst of ethene and preparing propylene by butene disproportionation, and this catalyst comprises that Mo.W and Re are compound loaded in aluminium oxide, silica, and alkali metal oxide, the carrier that alkaline earth oxide and ammonium salt are modified etc.But above-mentioned catalyst is used for above-mentioned system propylene disproportionation reaction; Its selectivity is relatively poor.
The purpose of this invention is to provide a kind of gaseous mixture disproportionation preparation of propene that contains ethene and butylene with catalyst and preparation thereof, have high selectivity and high conversion.
The invention provides a kind of gaseous mixture disproportionation preparation of propene catalyst that contains ethene and butylene, it is characterized in that: catalyst consists of ABC/D, and the total weight loading of active constituent is 5-30%, and all the other are carrier;
Wherein, A is the oxide of tungsten, and the weight loading is 0.01-10%,
B is the oxide of molybdenum, and the weight loading is 4-25%,
C is the oxide of rhenium, and the weight loading is 0.01-20%,
D is a mixture carrier, wherein is mainly molecular sieve, and other comprises aluminium oxide, silica, sieve and silica-sesquioxide, at least a in rare earth and the alkaline earth oxide.In addition, described molecular sieve mainly comprises Silicate-2, Y, and H β, SAPO series, ZSM series and MCM series, wherein H β and MCM-22 are best.
Component with B in above-mentioned catalyst of the present invention is molybdenum oxide the best.
In addition, in above-mentioned catalyst, the weight content of molecular sieve accounts for more than 50% of carrier.
The present invention also provides the above-mentioned gaseous mixture disproportionation preparation of propene Preparation of catalysts method that contains ethene and butylene, it is characterized in that: the A that adopts respective amount, B and C salt soluble in water is immersed on the mixture carrier successively, makes required catalyst through 200-900 ℃ of roasting.
In above-mentioned preparation method, described A, B and C salt soluble in water is meant its nitrate, chloride or A, B and C acid ammonium.
The catalyst of the invention described above is used for the gaseous mixture disproportionation preparation of propene time spent of ethene and butylene, reaction temperature 0-300 ℃; Weight space velocity: 0.01-3h
-1C in the reactor feed gas
2H
4/ C
4H
8-2 ratios: 0.2～4; Reaction pressure: 0.1-2.0MPa.Wherein contain butene-1 in the butene feedstock gas, butene-2, iso-butane, water, nitrogen, methane, ethane etc., after 5A ° of molecular sieve and the aluminium oxide preliminary treatment, butene-1 is wherein tautomerized to butene-2 through heterogeneous catalyst, then with contain water, nitrogen, the ethylene raw material gas of impurity such as methane, ethane enter together and carry out disproportionation in the reactor that contains above-mentioned disproportionation catalyst.
Below in conjunction with embodiment the present invention is further set forth.
Embodiment 1
Preparation of Catalyst: 10g 50MCM22-30Al
2O
3-20SiO
2Add ammonium tungstate successively, ammonium molybdate and rehenic acid ammonium salt solution, active component W, Mo, the content of Re are respectively 0.01,1 and 0.05g, and 120 ℃ of dryings obtain required catalyst through 400 ℃ of roastings again, and the weight loading of its active component is 10.6%.It is 315m that the BET method records surface area
2/ g.
Embodiment 2
Preparation of Catalyst: 10g 70MCM22-30Al
2O
3Add ammonium tungstate successively, ammonium molybdate and rehenic acid ammonium salt solution, active component W, Mo, the content of Re are respectively 0.01,2.5 and 0.05g, and 120 ℃ of dryings obtain required catalyst through 800 ℃ of roastings again, and the weight loading of its active component is 25.6%.It is 275m that the BET method records surface area
2/ g.
Embodiment 3
Preparation of Catalyst: get the 10g carrier, add 0.1N nitric acid tungsten, nitric acid molybdenum and nitric acid rhenium solution successively, the content of active component W, Mo, Re is respectively 00.2,2.0 and 0.8g, 120 ℃ of dryings, obtain catalyst through 800 ℃ of roastings again, the weight loading of its active component M is 28.5%.It is 281m that the BET method records surface area
2/ g.Used carrier composition is listed in table 4.
Embodiment 4 ethene and butylene disproportionation reaction system propylene
With the catalyst of the 5g embodiment 1 preparation internal diameter of packing into is in the stainless steel fixed bed reactors of 10mm, at N
2Atmosphere in be warmed up to 550 ℃, preliminary treatment 1 hour is then at N
2Atmosphere drop to 125 ℃, the switching reaction condition is N
2/ C
2H
4=1.5; GHSVC
4H
8-1=0.4h
-1T=125 ℃; The C of P=1MPa
2H
4-C
2H
6-N
2Gaseous mixture reacts sample analysis after 20 minutes.It the results are shown in table 1.
In table 1, XC
2H
4The conversion ratio of expression ethene, XC
4H
8-1Expression C
4H
8-1Isomery turns to C
4H
8-2Conversion ratio, XC
4H
8-2Expression C
4H
8-2Conversion ratio, SC
3H
6Expression C
3H
6Selectivity (following identical, no longer explanation).
Table 1 C
2H
4/ C
4H
8The influence of-1 comparison ethene and preparing propylene by butene disproportionation reactivity worth
| ??C 2H 4/C 4H 8-1 | ???XC 2H 4(％) | ???XC 4H 8-1(％) | ??XC 4H 8-2(％) | ??SC 3H 6(％) |
| ????3.0 | ????8.9 | ????75.0 | ????25.1 | ????92.1 |
| ????2.1 | ????11.4 | ????87.3 | ????27.2 | ????90.9 |
| ????1.5 | ????31.7 | ????88.4 | ????48.8 | ????91.5 |
| ????1.3 | ????34.5 | ????93.1 | ????51.2 | ????90.8 |
| ????0.25 | ????36.1 | ????97.2 | ????58.6 | ????92.1 |
Embodiment 5
Press reaction condition N except that reaching with 5g embodiment 2 prepared catalyst
2/ C
2H
4=1.5; C
2H
4/ C
4H
8-1=1.5; GHSV (C
2H
4+ C
4H
8-1)=1h
-1Beyond P=1MPa and the differential responses temperature, carry out ethene and butylene disproportionation reaction system propylene similarly to Example 4.It the results are shown in table 2.
Table 2 reaction temperature is to the influence of ethene and preparing propylene by butene disproportionation reactivity worth
| Temperature (℃) | ??XC 2H 4(％) | ??XC 4H 8-1(％) | ?XC 4H 8-2(％) | ??SC 3H 6(％) |
| ????0 | ????40.2 | ????76.2 | ????56.6 | ????93.4 |
| ????75 | ????38.1 | ????82.3 | ????52.1 | ????92.8 |
| ????125 | ????31.7 | ????88.4 | ????48.8 | ????91.5 |
| ????150 | ????21.5 | ????91.6 | ????34.9 | ????91.0 |
| ????175 | ????11.1 | ????80.2 | ????20.0 | ????90.3 |
| ????300 | ????9.5 | ????74.2 | ????19.5 | ????89.2 |
Embodiment 6
Remove and press reaction condition N
2/ C
2H
4=1.5; C
2H
4/ C
4H
8-1=1.5; Beyond T=125 ℃ and different pressures and the air speed, carry out ethene and butylene disproportionation reaction system propylene similarly to Example 5.It the results are shown in table 3.
Table 3 reaction velocity and pressure are to the gaseous mixture disproportionation preparation of propene Effect on Performance of ethene and butylene
Embodiment 5
| Pressure (MPa) | Air speed (h -1) | ??XC 2H 4(％) | ??XC 4H 8-1(％) | ?XC 4H 8-2(％) | ???SC 3H 6????(％) |
| ????1 | ????0.01 | ????48.2 | ????93.2 | ????56.6 | ????90.3 |
| ????1 | ????0.3 | ????38.1 | ????90.3 | ????52.1 | ????91.1 |
| ????1 | ????1 | ????31.7 | ????88.4 | ????48.8 | ????91.5 |
| ????1 | ????1.5 | ????28.5 | ????81.6 | ????45.9 | ????92.0 |
| ????1 | ????3 | ????25.3 | ????76.2 | ????36.0 | ????93.1 |
| ????2 | ????1 | ????35.1 | ????89.3 | ????49.9 | ????91.8 |
| ????0.1 | ????1 | ????29.8 | ????85.1 | ????47.2 | ????90.4 |
Except that using the made catalyst 5g of embodiment 3 respectively, carry out the reaction of ethene and preparing propylene by butene disproportionation equally with embodiment.Its catalyst is formed (carrier) and reaction result is listed in table 4.
The different catalyst of forming of table 4 are to ethene and preparing propylene by butene disproportionation reactivity worth
| Catalyst | ????XC 2H 4????(％) | ??XC 4H 8-1(％) | ??XC 4H 8-2(％) | ???SC 3H 6????(％) |
| ??70Silicate-30Al 2O 3-M | ????1.03 | ????80.50 | ????1.36 | ????88.3 |
| ??50SAPO11-30Al 2O 3- ??20MgO-M | ????11.18 | ????84.88 | ????23.02 | ????89.0 |
| ??65SAPO34-30Al 2O 3- ??5La 2O 3-M | ????6.07 | ????89.10 | ????6.98 | ????88.7 |
| ??70SAPO5-30Al 2O 3-M | ????2.09 | ????85.97 | ????3.95 | ????85.1 |
| ??70Y-30Al 2O 3-M | ????0.96 | ????72.80 | ????1.56 | ????84.8 |
| ??65Hβ-25Al 2O 3-10SiO 2??-M | ????64.26 | ????94.65 | ????61.71 | ????90.1 |
| ??70SB-30Al 2O 3-M | ????47.42 | ????91.47 | ????63.71 | ????91.2 |
| ??50ZSM35-30Al 2O 3- ??20SiO 2-Al 2O 3-M | ????68.48 | ????93.45 | ????55.58 | ????92.0 |
| ??50MCM41-20Al 2O 3- ??20La 2O 3-10CeO 2-M | ????57.66 | ????95.58 | ????69.91 | ????93.1 |
| ??50MCM22-30Al 2O 3- ??20SiO 2-M | ????31.7 | ????88.4 | ????48.8 | ????91.5 |
Result by the foregoing description can see, catalyst of the present invention, its preparation method is simple, be used for ethene and butylene disproportionation reaction system propylene and under very wide Reaction conditions range (reactant ratio of components, reaction temperature, pressure and air speed), all demonstrate high selectivity and high conversion, have the good prospect that industry is suitable for.
Claims (8)
1. gaseous mixture disproportionation preparation of propene catalyst that contains ethene and butylene, it is characterized in that: catalyst consists of ABC/D, and the total weight loading of active constituent is 5-30%, and all the other are carrier;
Wherein, A is the oxide of tungsten, and the weight loading is 0.01-10%,
B is the oxide of molybdenum, and the weight loading is 4-25%,
C is the oxide of rhenium, and the weight loading is 0.01-20%,
D is a mixture carrier, wherein is mainly molecular sieve, and other comprises aluminium oxide, silica, sieve and silica-sesquioxide, at least a in rare earth and the alkaline earth oxide.
2. by the gaseous mixture disproportionation preparation of propene catalyst of described ethene of claim 1 and butylene, it is characterized in that: the component of B is a molybdenum oxide.
3. by the gaseous mixture disproportionation preparation of propene catalyst of described ethene of claim 1 and butylene, it is characterized in that molecular sieve is Silicate-2, Y, H β, SAPO series, ZSM series or MCM series molecular sieve.
4. by the gaseous mixture disproportionation preparation of propene catalyst of described ethene of claim 3 and butylene, it is characterized in that molecular sieve is H beta-molecular sieve or MCM series molecular sieve.
5. by the gaseous mixture disproportionation preparation of propene catalyst of claim 1,2 or 3 described ethene and butylene, it is characterized in that the weight content of molecular sieve accounts for more than 50% of carrier.
6. gaseous mixture disproportionation preparation of propene Preparation of catalysts method by the described ethene of claim 1 and butylene, it is characterized in that: the A that adopts respective amount, B and C salt soluble in water is immersed on the mixture carrier successively, makes required catalyst through 200-900 ℃ of roasting.
7. by the described preparation method of claim 6, it is characterized in that described salt soluble in water is the ammonium salt of nitrate, chloride or the A of A, B and C, B or C acid.
8. gaseous mixture disproportionation preparation of propene that is used for ethene and butylene by the described catalyst of claim 1.
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314486C (en) * | 2003-11-19 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst for disproportionation of butylene to produce propylene |
| US7550638B2 (en) * | 2005-11-16 | 2009-06-23 | Equistar Chemicals, Lp | Integrated cracking and metathesis process |
| CN101020134B (en) * | 2006-02-15 | 2010-09-08 | 中国石油化工股份有限公司 | W-base catalyst and its preparation and application |
| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
| CN101768040B (en) * | 2009-01-07 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
| CN103272581A (en) * | 2013-05-06 | 2013-09-04 | 中国科学院宁波材料技术与工程研究所 | Catalyst for preparing propylene by disproportionation of ethylene and butane and preparation method of catalyst |
| CN103772108A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing propylene by fluidized bed olefin disproportionation |
| CN103769084A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing hexene through olefin metathesis |
| CN104888763A (en) * | 2015-05-08 | 2015-09-09 | 宁波富德能源有限公司 | Catalyst for preparing propylene by disproportionation of ethylene and butylene |
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| CN100430354C (en) * | 2005-08-15 | 2008-11-05 | 中国石油化工股份有限公司 | Method for producing propylene through dismutation of olefin |
| CN100586908C (en) * | 2006-08-11 | 2010-02-03 | 中国石油化工股份有限公司 | Production method for propylene |
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2001
- 2001-02-28 CN CN01104355A patent/CN1120047C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314486C (en) * | 2003-11-19 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst for disproportionation of butylene to produce propylene |
| US7550638B2 (en) * | 2005-11-16 | 2009-06-23 | Equistar Chemicals, Lp | Integrated cracking and metathesis process |
| CN101310000B (en) * | 2005-11-16 | 2012-05-23 | 伊奎斯塔化学有限公司 | Integrated cracking and metathesis process |
| CN101020134B (en) * | 2006-02-15 | 2010-09-08 | 中国石油化工股份有限公司 | W-base catalyst and its preparation and application |
| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
| CN101768040B (en) * | 2009-01-07 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
| CN103772108A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing propylene by fluidized bed olefin disproportionation |
| CN103769084A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for preparing hexene through olefin metathesis |
| CN103772108B (en) * | 2012-10-25 | 2015-08-12 | 中国石油化工股份有限公司 | The method of fluidized bed olefin disproportionation propylene |
| CN103769084B (en) * | 2012-10-25 | 2015-12-16 | 中国石油化工股份有限公司 | The catalyst of olefin(e) disproportionation hexene |
| CN103272581A (en) * | 2013-05-06 | 2013-09-04 | 中国科学院宁波材料技术与工程研究所 | Catalyst for preparing propylene by disproportionation of ethylene and butane and preparation method of catalyst |
| CN104888763A (en) * | 2015-05-08 | 2015-09-09 | 宁波富德能源有限公司 | Catalyst for preparing propylene by disproportionation of ethylene and butylene |
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