CN101172926B - Propylene yield increasing method - Google Patents

Propylene yield increasing method Download PDF

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Publication number
CN101172926B
CN101172926B CN2006101178628A CN200610117862A CN101172926B CN 101172926 B CN101172926 B CN 101172926B CN 2006101178628 A CN2006101178628 A CN 2006101178628A CN 200610117862 A CN200610117862 A CN 200610117862A CN 101172926 B CN101172926 B CN 101172926B
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propylene
reaction
catalyst
raw material
butylene
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CN101172926A (en
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刘俊涛
钟思青
孙凤侠
刘国强
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to an production increasing method for propylene. The invention mainly solves the technical problems of large ethylene consumption, limited raw material, complicated pre-processing, limited service range and short regeneration period of catalyst of the prior art. The invention has the technical proposal that ethylene and butylenes are taken as raw materials; the raw materialis contacted with catalyst to generate an effluent which is rich in propylene at the reaction temperature of 350 to 550 EDG C, the reaction pressure of 1.5 to 3.5 MPa through a meter, and the reaction space velocity of 0.1 to 20 hours<-1>, wherein, the weight proportion of the ethylene and the butylenes is 0 to 2:1. The catalyst comprises the components as follow: (a) SiO2 carrier, and (b) tungsten oxide which is carried on the SiO2 carrier and is 0.1 to 20 percent of the weight of the carrier, wherein, the specific surface area of the catalyst carrier is 200 to 700 m<2> g<-1>. The inventionrelatively well solves the technical problems mentioned above, and the invention can be used in the industrial production of the propylene.

Description

The volume increase method of propylene
Technical field
The present invention relates to a kind of volume increase method of propylene, particularly about being rich in the method for butene-1 and butene-2 C-4-fraction and ethylene catalyst reaction system propylene.
Background technology
Propylene is one of important basic raw material, is mainly used in Chemicals such as producing polypropylene, vinyl cyanide, propylene oxide.Wherein polypropylene accounts for the over half of world's propylene demand.In recent years, along with increasing rapidly of derivative demands such as polypropylene, the demand of propylene was all increased year by year.On the other hand, along with the continuous increase of China's ethylene yield and crude capacity, the C4 of ethylene plant and refinery's by-product and the hydro carbons quantity that is rich in alkene more than the C4 roll up.In petroleum resources China in short supply relatively, how to make good use of this part a considerable number of valuable hydro carbons resource, increase its added value, the benefit that improves petroleum chemical enterprise has become urgent day by day task.
For now, mainly contain two technological lines from the C 4 olefin propylene enhancing, be olefins by catalytic cracking and olefin metathesis technology, mainly exist propene yield lower for the olefins by catalytic cracking technology, the more high technical problem of running cost, and the olefin metathesis technology needs consumption of ethylene and raw materials pretreatment complexity generally speaking.The technological merit that the present invention has fully used for reference olefin cracking and olefin metathesis proposes new technical scheme.
Proposed the technology that a kind of disproportionation by butene-1 and butene-2 obtains propylene and amylene among the US6271430, this process using tank reactor, catalyzer are Re 2O 7/ Al 2O 3, temperature of reaction is 0～150 ℃, reaction pressure is 2～200bar.
US5300718 has reported the route by the butene-2 raw material production propylene that contains butene-1 and oxygenatedchemicals.This technology comprises: at first raw material is passed through the alumina removal oxygenatedchemicals; Butene-1 isomery under the magnesia catalyst effect turns to butene-2 in the raw material; Butene-2 and ethene disproportionation generate three steps of propylene.Wherein butene-2 and the employed catalyzer of ethene disproportionation are MgO and WO 3/ SiO 2Mixed bed.
It is carrier that CN1204097C adopts silicon-dioxide, the fixed bed catalyst of load oxide compound, and specific surface area of catalyst is 270～550 meters 2/ gram, 250 ℃～459 ℃ of temperature of reaction, reaction pressure is 0～10MPa, the liquid phase air speed is 0.1～1.0 hour -1Produce propylene under the condition.
CN1618515 adopts and to add niobium in the oxide/silicon dioxide catalyst system or its oxide compound is realized the butylene disproportionation technology, and in the fixed bed reaction system, temperature of reaction is 250～550 ℃, reaction pressure is 0.01～5MPa, and the liquid phase weight space velocity is 0.1～5 hour -1Under the condition, the butylene disproportionation reaction generates propylene.
Disclosing a kind of employing among the document CN1490287A is raw material with carbon containing four or carbon pentaene hydrocarbon mixture, in fixed-bed reactor, adopts 350 ℃～500 ℃ temperature, the pressure of 0.6～1.0MPa and 1～10 hour -1Carry out the method for prepared in reaction ethene and propylene under the condition of weight space velocity.
The technology that above-mentioned document is related, or catalyzer costliness are as the Re that adopts among the patent US6271430 2O 7/ Al 2O 3Catalyzer, or need mass consumption ethene, or exist raw materials pretreatment complexity and catalyst life than technical problems such as weak points.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to need to consume a large amount of ethene in the document, the ingredient requirement harshness, and the pre-treatment complexity, narrow application range, the technical problem that the catalyst regeneration cycle is short provides a kind of method of new production propylene.This method has purpose product yield height, and selectivity is good, and raw materials pretreatment is simple, the advantage that the regeneration period is long.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of volume increase method of propylene is a raw material with ethene and butylene, is 500～550 ℃ in temperature of reaction, in the gauge pressure reaction pressure is 0.1～0.8MPa, and the reaction weight space velocity is 0.5～10 hour -1Under the condition, raw material contacts with catalyzer and generates the logistics that is rich in propylene, and wherein the weight ratio of ethene and butylene is 0～2: 1 in the raw material, and catalyst system therefor comprises following component:
A) SiO 2Carrier; With carry thereon
B) count 0.1～6% Tungsten oxide 99.999 with vehicle weight;
Wherein the specific surface area of support of the catalyst is 200～700 meters 2/ gram.
The weight ratio preferable range of raw material ethene and butylene is 0.02～1: 1 in the technique scheme.
In the technique scheme, catalyzer is in vehicle weight, and Tungsten oxide 99.999 consumption preferable range is 3～6%.
Adopting tungsten oxide catalyst among the present invention, is raw material with the ethene of certain proportion scope and the blending ingredients of butylene, has realized the purpose of butylene catalyzed conversion propylene enhancing under the high temperature lower pressure state.
Lot of experiments shows, adopt tungsten oxide catalyst, in the butylene catalytic conversion process, side reactions such as less generation hydrogen transfer reactions, excessively isomerization reaction, aromatization, mainly follow the metal carbene ionic mechanism and generate propylene, and add a spot of ethene in the raw material butylene, can advance the reaction of butylene and ethene greatly, and reduce the generation of side reaction.
Reaction conditions is chosen higher temperature of reaction among the present invention, on the one hand, utilizes butylene self disproportionation to generate a part of propylene, reduces the consumption of butylene.Simultaneously, the pyroreaction state can still can be realized catalyst life preferably under the situation that reduces the raw materials pretreatment complexity significantly, thereby finally realizes higher propene yield and long catalyst activity sexual cycle.
Adopting technical scheme of the present invention, is 6～8% at catalyzer in vehicle weight Tungsten oxide 99.999 consumption, and the weight ratio of raw material ethene and butylene is 0.02～1: 1, and temperature of reaction is 400～500 ℃, and the reaction weight space velocity is 0.5～10 hour -1, be under 0.1～0.8MPa condition in the gauge pressure reaction pressure, butene conversion can reach more than 60%, and propene yield can reach 65% simultaneously, has obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Accurately take by weighing the aequum ammonium metawolframate respectively, add 200 ml deionized water, be stirred to dissolving fully.Other takes by weighing aequum silica gel and puts into 1000 milliliters of round-bottomed flasks, silica gel before use in air through 550 ℃ of roastings 3 hours.Then above-mentioned ammonium metatungstate solution is poured in the round-bottomed flask that silica gel is housed, in rotary evaporation liquid, put into 120 ℃ of oven dry of baking oven after boiling off moisture and spend the night for 60 ℃.The above-mentioned sample that makes is placed 550 ℃ of roastings of retort furnace 4～12 hours, make WO 3Content is 12% catalyzer of vehicle weight.
It is 24 millimeters fixed-bed reactor that the tungsten oxide catalyst that makes 6 grams are put into internal diameter, logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, the raw material that uses in the experiment is pure butene-1, and temperature of reaction is 480 ℃, is 0.37 hour at weight space velocity -1, pressure (gauge pressure) is under the 0.5MPa condition, and reaction result is: yield of ethene is 3.55%, and propene yield is 23.3%, and the transformation efficiency of butylene is 68.81%.
[embodiment 2～7]
The WO that makes according to each step of embodiment 1 3Content is 3% catalyzer, and it is 24 millimeters fixed-bed reactor that the tungsten oxide catalyst that makes 6 grams are put into internal diameter, and logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, and the raw material that uses in the experiment is pure butene-1.Air speed 2 hours -1, under the pressure 0.1MPa condition, the reaction result such as the table 1 of condition of different temperatures:
Table 1 butene-1 is the influence of raw material differing temps
The embodiment sequence number 2? 3? 4? 5? 6? 7?
Temperature (℃) 350? 400? 450? 500? 530? 550?
Yield of ethene, % 7.27? 6.02? 4.16? 3.95? 4.57? 5.01?
Propene yield, % 10.51? 15.60? 20.61? 23.29? 24.04? 24.14?
Butene conversion, % 59.00? 66.13? 71.07? 70.70? 72.26? 73.99?
The propylene selectivity, % 17.81? 23.60? 29.00? 33.17? 33.28? 32.62?
Ethylene selectivity, % 12.32? 9.11? 5.86? 5.63? 6.32? 6.78?
[0030][embodiment 8～13]
The WO that makes according to each step of embodiment 1 3Content is 6% catalyzer of vehicle weight, and it is 24 millimeters fixed-bed reactor that tungsten oxide catalyst 6 grams that make are put into internal diameter, and logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, and the raw material that uses in the experiment is pure butene-2.450 ℃ of temperature, under gauge pressure pressure 0.1MPa condition, the reaction result such as the table 2 of different air speed conditions:
Table 2 butene-2 is the influence of the different air speeds of raw material
The embodiment sequence number 8? 9? 10? 11? 12? 13?
Air speed, hour -1 25.8? 10.3? 6.6? 2.7? 1.7? 0.37?
Yield of ethene, % 0.2? 0.2? 0.3? 0.6? 0.9? 1.6?
Propene yield, % 9.4? 9.6? 11.2? 14.8? 17.4? 20.3?
Butene conversion, % 28.0? 28.3? 32.7? 42.2? 49.2? 57.6?
The propylene selectivity, % 33.7? 33.9? 34.3? 35.2? 35.3? 35.3?
Ethylene selectivity, % 0.5? 0.6? 0.7? 1.1? 1.6? 2.4?
[embodiment 14～19]
The WO that makes according to each step of embodiment 1 3Content is 4% catalyzer of vehicle weight, it is 24 millimeters fixed-bed reactor that the tungsten oxide catalyst that makes 6 grams are put into internal diameter, and logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, and experiment is 450 ℃ of temperature, pressure (gauge pressure) 0.1MPa, air speed is 3 hours -1Under the condition, in differing ethylene and the butylene amount than reaction result down and product composition as table 3:
Table 3 differing ethylene and butylene weight ratio are to the influence of reaction result and product composition
The embodiment sequence number 14? 15? 16? 17? 18? 19?
Ethene and butylene weight ratio 0.14? 0.25? 0.37? 0.50? 0.63? 0.77?
Temperature 450? 450? 450? 450? 450? 450?
Methane 0.02? 0.02? 0.02? 0.02? 0.02? 0.02?
Ethane 0.06? 0.06? 0.07? 0.06? 0.06? 0.06?
Ethene 5.87? 9.28? 13.75? 17.79? 23.67? 31.34?
Propane 0.12? 0.09? 0.07? 0.05? 0.04? 0.03?
Propylene 32.51? 36.97? 39.94? 39.47? 40.70? 36.97?
Trimethylmethane 0.25? 0.22? 0.20? 0.18? 0.18? 0.15?
Normal butane 0.29? 0.23? 0.20? 0.17? 0.16? 0.14?
Neopentane 0.01? 0.01? 0.01? 0.01? 0.01? 0.01?
Butylene 34.84? 30.72? 27.25? 24? 23.37? 21.2?
Carbon is more than five 26.04? 22.40? 18.49? 18.25? 11.79? 10.09?
Butene conversion 60.42? 61.60? 63.17? 64.18? 62.92? 54.88?
Propene yield 36.12? 41.07? 53.97? 58.04? 65.65? 66.02?
[0038][embodiment 20]
The WO that makes according to each step of embodiment 1 3Content is 8% catalyzer of vehicle weight, it is 24 millimeters fixed-bed reactor that the tungsten oxide catalyst that makes 6 grams are put into internal diameter, logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, the raw material that uses in the experiment is 3.4: 1 as the mol ratio of butene-2 and butene-1, in temperature of reaction is 350 ℃, air speed 0.8 hour -1, under pressure (gauge pressure) the 0.8MPa condition, butene conversion is 50%, propene yield 24.41%.
[embodiment 21]
The WO that makes according to each step of embodiment 1 3Content is 18% catalyzer of vehicle weight, it is 24 millimeters fixed-bed reactor that the tungsten oxide catalyst that makes 6 grams are put into internal diameter, logical nitrogen is cooled to temperature of reaction 550 ℃ of activation after 2 hours before the experiment, the raw material that uses in the experiment is 6.4: 1 as the mol ratio of butene-2 and butene-1, in temperature of reaction is 350 ℃, air speed 15 hours -1, pressure (gauge pressure) is under the 0.1MPa condition, butene conversion is 43%, propene yield 21.34%.

Claims (3)

1. the volume increase method of a propylene is a raw material with ethene and butylene, is 500～550 ℃ in temperature of reaction, is 0.1～0.8MPa in the gauge pressure reaction pressure, and the reaction weight space velocity is 0.5～10 hour -1Under the condition, raw material contacts with catalyzer and generates the logistics that is rich in propylene, and wherein the weight ratio of ethene and butylene is 0～2: 1 in the raw material, and catalyst system therefor comprises following component:
A) SiO 2Carrier; With carry thereon
B) count 0.1～6% Tungsten oxide 99.999 with vehicle weight;
Wherein the specific surface area of support of the catalyst is 200～700 meters 2/ gram.
2. according to the volume increase method of the described propylene of claim 1, it is characterized in that the weight ratio of ethene and butylene is 0.02～1: 1 in the raw material.
3. according to the volume increase method of the described propylene of claim 1, it is characterized in that catalyzer is 3～6% in vehicle weight Tungsten oxide 99.999 weight.
CN2006101178628A 2006-11-02 2006-11-02 Propylene yield increasing method Active CN101172926B (en)

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Publication number Priority date Publication date Assignee Title
CN102276406B (en) * 2010-06-11 2014-07-23 中国石油化工股份有限公司 Method for increasing yield of propylene
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
CN104549226B (en) * 2013-10-28 2017-05-10 中国石油化工股份有限公司 Catalyst used for olefin disproportionation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020002317A1 (en) * 2000-03-17 2002-01-03 Peter Schwab Flexible preparation of propene and hexene
WO2006052688A2 (en) * 2004-11-08 2006-05-18 Abb Lummus Global Inc. Catalyst and process for the metathesis of ethylene and butene to produce propylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020002317A1 (en) * 2000-03-17 2002-01-03 Peter Schwab Flexible preparation of propene and hexene
WO2006052688A2 (en) * 2004-11-08 2006-05-18 Abb Lummus Global Inc. Catalyst and process for the metathesis of ethylene and butene to produce propylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
US 20020002317 A1,说明书第1页第[0001]段到第[0008]段.

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