CN101190869B - Production increasing method for propylene - Google Patents

Production increasing method for propylene Download PDF

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Publication number
CN101190869B
CN101190869B CN2006101185246A CN200610118524A CN101190869B CN 101190869 B CN101190869 B CN 101190869B CN 2006101185246 A CN2006101185246 A CN 2006101185246A CN 200610118524 A CN200610118524 A CN 200610118524A CN 101190869 B CN101190869 B CN 101190869B
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reaction
catalyzer
reaction zone
butene
propylene
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CN101190869A (en
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谢在库
刘俊涛
王仰东
钟思青
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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 a propylene yield increase method, which mainly solves the problems of the original technique that the material requirements are severe with narrow application scope and that the regeneration cycle is short. The invention adopts bulene and ethylene as materials, and comprises the steps in sequence that: (1) bulene and crystallized aluminosilicate catalyst 1 with molar ratio between silicone and aluminum, SiO2/Al2O3 is at least 10 are blended, a first flow of reaction effluence with molar ratio between 2-butene and 1-butene of 3-5: 1 is produced; (2) the first flow of reaction effluence and catalyst 2 are contacted with each other and generate reaction effluence containing propylene, wherein the catalyst 2 comprises the following components: a (a) SiO2 carrier and (b) tungsten oxide that attached on the SiO2 carrier with weight 0.1 to 20 percent by the carrier. The technical proposal comparatively solves the problem and can be used for the industrial productionof the propylene.

Description

The method of propylene enhancing
Technical field
The present invention relates to a kind of method of propylene enhancing, particularly produce the method for propylene about being rich in butene-1 and butene-2 C-4-fraction catalyzed conversion.
Background technology
Propylene is very important basic Organic Chemicals.Closely for a period of time, owing to be subjected to the influence of polypropylene and alkyl aromatic compound solid demand, the demand of propylene is the gesture of rapid growth, and traditional production of propylene pattern can not satisfy the needs of market to the quick growth of propylene, and therefore replenishing the propylene demand need be by the new technology of other various propylene enhancings.On the other hand, in the world wide, the appreciable C of quantity is arranged 4Olefin feedstock.Be subjected to the influence of factors such as the variation in Chemicals market and transportation cost, it is a kind of approach that utilizes preferably that these raw materials are carried out deep processing on the spot.C wherein 4Conversion of olefines is that propylene is a kind of promising technology.This technology can be utilized the lower C of superfluous relatively added value on the one hand 4Olefin feedstock can obtain broad-spectrum propylene product again on the other hand, and the ethene of by-product makes this technology more attractive simultaneously.
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.This method introduces the modification and the reaction result thereof of dissimilar catalyzer, but the yield of propylene is lower.
Document CN1274342A discloses by catalyzed conversion to contain 20% or higher at least a C 4～C 12The straight chain hydrocarbon of alkene is the method that raw material is produced ethene and propylene, does not contain proton, SiO substantially in the zeolite catalyst that this method is used 2/ Al 2O 3Mol ratio is 200～5000, contain the zeolite of at least a IB family metal, intermediate pore size, the zeolite of preferred ZSM-5 family.Be reflected under 400 to 700 ℃ the temperature, 0.1～10 normal atmosphere and 1～1000 hour -1The weight space velocity condition under carry out.But the high propylene yield of this method only has 25.19%.
The patent WO:0026163 of Equistar company is to contain 60wt%C at least 4, C 5Alkene is raw material, adopts central hole zeolite catalyst, and the kind of its zeolite has, the zeolite of one-dimensional channels as: its apertures such as ZSM-23, AlPO4-11 greater than
Figure B2006101185246D00011
Pore size index is 14～28; Also can be to intersect the zeolite in duct: as its apertures, first duct such as ZSM-57, AlPO4-18 greater than Pore size index is that 14～28, the second duct pore size index is less than 20.This catalyzer can be Na type, H type etc., also can add oxidized metal such as the Pt and the Pd etc. of trace, removes carbon distribution when being beneficial to catalyst regeneration.The general fixed-bed process that adopts.Its temperature of reaction is 200～750 ℃, and reaction pressure is 0.05～1MPa, and air speed WHSV is 0.5～1000 hour -1
Proposed a kind of among the document EP 0109059A1 from C 4～C 12Conversion of olefines is the technology of propylene.Catalyzer uses Si/Al in the document 2O 3Mol ratio is smaller or equal to 300 ZSM-5 molecular sieve, and temperature of reaction is 400～600 ℃, and the alkene air speed was greater than 50 hours -1Investigated the influence of the raw material, temperature of reaction, air speed of various human configuration in this patent in more detail to catalytic cracking reaction.
Proposed a kind of among the US5981818 C 4～C 7Conversion of olefines is C 3And C 4The technology of alkene.Catalyzer uses Si/Al in the document 2O 3Mol ratio is 10～200 pentasi1 type molecular sieve catalyst.O.1～0.9 micron the BET specific surface is 300～600 meters squared per gram, and particle diameter is for.Temperature of reaction is 380～500 ℃.Characteristics of above-mentioned patent are to sneak into a certain proportion of water vapour, wherein H in raw material 2O/HC is 0.5～3 (weight %).It is said that adding water vapour can alleviate catalyst carbon deposition, improves the stability of catalyzer.
In the basic patent EP1036133 of Fina company (China's application is CN1284110) disclosed embodiment (embodiment 3), it is 300 ZSM-5 molecular sieve catalyst that catalyzer is selected the sial atomic ratio for use, and reaction raw materials is C4,560 ℃ of feed(raw material)inlet temperature, normal pressure, liquid hourly space velocity 23h -1Under the condition, the once through yield of propylene is no more than 35%.
Technical problems such as the related patent of above-mentioned document all exists the once through yield of propylene lower, and carbon four utilization ratios are low.
Summary of the invention
Technical problem to be solved by this invention is that to overcome the raw material scope of application that exists in the document in the past narrower, and the problem that the regeneration period is short provides a kind of method of new propylene enhancing.It is applied widely that this method has raw material, purpose product yield height, and selectivity is good, 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 method of propylene enhancing is a raw material with butylene and ethene, may further comprise the steps successively:
(1) raw material butylene and silica alumina ratio SiO 2/ Al 2O 3Be at least 1 contact of 10 crystal aluminosilicate catalyzer, it is first strand of reaction effluent of 3～5: 1 that reaction generates butene-2 and butene-1 mol ratio;
(2) first strands of reaction effluents and catalyzer 2 contact reactss generate the reaction effluent that contains propylene; Wherein catalyzer 2 comprises following component:
(a) SiO 2Carrier; With carry thereon
(b) count 0.1～20% Tungsten oxide 99.999 with vehicle weight;
O.1～10 hour wherein, the temperature of reaction of catalyzer 1 is 200～400 ℃, and the reaction weight space velocity is for -1, be O～5MPa in the gauge pressure reaction pressure; The temperature of reaction of catalyzer 2 is 200～400 ℃, and the reaction weight space velocity is 0.1～3 hour -1, be 0～5MPa in the gauge pressure reaction pressure.
The butene feedstock preferred version is butene-1, butene-2 or its mixture in the technique scheme.The weight ratio of ethene and butylene is 0.3～3: 1 in the raw material, and the weight ratio preferable range of ethene and butylene is 0.5～2: 1.
Catalyzer 1 preferred version is selected from ZSM-5 molecular sieve, ZSM-35 molecular sieve, beta-molecular sieve or mordenite molecular sieve in the technique scheme, its silica alumina ratio SiO 2/ Al 2O 3Be at least 10; Catalyzer 1 more preferably scheme optimization from the ZSM-5 molecular sieve, its silica alumina ratio SiO 2/ Al 2O 3Be 50～500.Be 4～10% in the vehicle weight Tungsten oxide 99.999 amount of reusing preferable range in the catalyzer 2.
In the technique scheme, catalyzer 1 preferred operational condition is: temperature of reaction is 200～350 ℃, and the reaction weight space velocity is 1～5 hour -1, be 0.1～3MPa in the gauge pressure reaction pressure.Catalyzer 2 preferred operational conditions are: temperature of reaction is 250～350 ℃, and the reaction weight space velocity is 0.5～3 hour -1, be 1～3MPa in the gauge pressure reaction pressure.
Adopt two reaction zone subregions reactions among the present invention, reaction zone 1 adopts crystal aluminosilicate molecular sieve catalyst 1, and reaction zone 2 adopts tungsten oxide catalysts 2, and wherein reaction zone 1 reaction effluent is directly as the raw material of reaction zone 2.
Experimental study shows, in the disproportionation reaction process of ethene and butylene, optimal reaction is the ethene of the butene-2 of 1 molecule and 1 molecule generates 2 molecules by the metal carbene ionic mechanism a propylene, therefore optimal disproportionation raw material is a butene-2, but because each isomers boiling point of butylene differs very little, therefore obtaining the higher butene-2 of purity need separate and can obtain through the multitower continuous precision, obviously, separating energy consumption is higher, the running cost height.Raw material with butene-1 and butene-2 arbitrary proportion among the present invention reacts by first isomerization reaction zone, because it is favourable on the thermodynamics to the generation of butene-2, therefore obtain being rich in the raw material of butene-2 through first reaction zone, this raw material enters reaction zone 2 again and carries out disproportionation reaction.Raw material behind first reaction zone, the reasonable mixture ratio of components of butene-2 and butene-1 not only, and alleviated disproportionation catalyst greatly owing to participating in the subsidiary burden that isomerization reaction brings, and help alleviating the load of disproportionation catalyst, prolong life of catalyst.
The weight ratio preferable range of raw material ethene and butylene is 0.3～3: 1 among the present invention, and the weight ratio of ethene and butylene more preferably scope is 0.5～2: 1.The present invention had both taken into account to help improving the purpose product selectivity, had considered the internal circulating load that reduces alkene again.
The catalyzer 1 that reaction zone 1 adopts among the present invention is a molecular sieve catalyst, and its isomerization performance is excellent and appearance carbon ability is stronger, thereby has ensured that catalyzer can have the long regeneration period.
Adopt technical scheme of the present invention, at reaction zone 1 filling silica alumina ratio SiO 2/ Al 2O 3It is 50～500 ZSM-5 molecular sieve catalyst 1; Reactor zone 2 adopts with SiO 2Vehicle weight meter Tungsten oxide 99.999 consumption is 4～10% catalyzer 2; The temperature of reaction of catalyzer 1 is 200～350 ℃, and the reaction weight space velocity is 1～5 hour -1, be 0.1～3MPa in the gauge pressure reaction pressure; The temperature of reaction of catalyzer 2 is 250～350 ℃, and the reaction weight space velocity is 0.5～5 hour -1, be under 1～3MPa condition in the gauge pressure reaction pressure, butene conversion can reach 92%, and the mass fraction of propylene can reach 57%, 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.In addition aequum silica gel is put 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 the required WO of reaction zone 1 reaction 3/ SiO 2Catalyzer 1, WO 3Content is 6% of vehicle weight.
According to silica alumina ratio SiO 2/ Al 2O 3Be that 200 proportional arrangement is siliceous, the slip of aluminium, template and water, stirred 15 hours under the room temperature.Crystallization 10～80 hours under 130～220 ℃ temperature is then washed crystallization liquid afterwards, is promptly obtained the ZSM-5 molecular sieve after the oven dry, roasting.After ZSM-5 molecular sieve adding 87 gram 40% (weight) silica gel mixing with 50 grams, extrusion moulding, and, make the required type ZSM 5 molecular sieve catalyzer 2 of reaction zone 2 reactions after 430 ℃ of roastings 130 ℃ of oven dry.
150 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 10 hours -1, pressure (gauge pressure) 1MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).250 ℃ of reaction zone 2 temperature of reaction, liquid air speed 8 hours -1, reaction pressure (gauge pressure) is 5MPa.The raw material that uses in the experiment is pure butene-1, and ethene and butylene mass ratio are 0.3: 1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 86% based on the butylene mass fraction.Butene conversion is 42% behind reaction zone 2, and the mass fraction of propylene is 48.0%.
[embodiment 2]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 500), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 2%), activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
150 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 8 hours -1, pressure (gauge pressure) 5MPa, reaction zone 1 (loading catalyst 1) reaction effluent enters reaction zone 2 (loading catalyst 2).200 ℃ of reaction zone 2 (loading catalyst 2) temperature of reaction, liquid air speed 5 hours -1, reaction pressure (gauge pressure) is 3MPa.The raw material that uses in the experiment is pure butene-2, and ethene and butylene mass ratio are 0.5: 1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 89% based on the butylene mass fraction.Butene conversion is 57% behind reaction zone 2, and the mass fraction of propylene is 57.3%.
[embodiment 3]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 60), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 8%), reaction zone 1 all is arranged in the same reactor with reaction zone 2, catalyzer 1 is seated in reactor inlet, catalyzer 2 is seated in reactor exit.Activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
350 ℃ of reactor reaction temperature, pressure (gauge pressure) 1MPa, catalyzer 1 air speed is 5 hours relatively -1, catalyzer 2 air speeds are air speed 3 hours relatively -1The raw material that uses in the experiment is pure butene-2, and ethene and butylene mass ratio are 1: 1, and ethene directly enters reaction zone 2 through reaction zone 1, and butene conversion is 70%, and the mass fraction of propylene is 53.0%.
[embodiment 4]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 60), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 8%), reaction zone 1 all is arranged in the same reactor with reaction zone 2, catalyzer 1 mixes with catalyzer 2 and is seated in the reactor.
330 ℃ of reactor reaction temperature, pressure (gauge pressure) 3MPa, catalyzer 1 air speed is 8 hours relatively -1, catalyzer 2 air speeds are air speed 1 hour relatively -1Raw material butene-2 that uses in the experiment and butene-1 mol ratio are 0.5: 1, and ethene and butylene mass ratio are 0.67: 1, and butene conversion is 66.7%, and the mass fraction of propylene is 55.3%.
[embodiment 5]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 10), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 18%), activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
400 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 1 hour -1, pressure (gauge pressure) 0.5MPa, reaction zone 1 (loading catalyst 1) reaction effluent enters reaction zone 2 (loading catalyst 2).380 ℃ of reaction zone 2 temperature of reaction, liquid air speed 10 hours -1, reaction pressure (gauge pressure) is 0.5MPa.The raw material that uses in the experiment is pure butene-2, ethene and butylene mass ratio are 1.5/1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 74.1% based on the butylene mass fraction, butene conversion is 78% behind reaction zone 2, and the mass fraction of propylene is 46.8%.
[embodiment 6]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 400), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 18%), activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
400 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 1 hour -1, pressure (gauge pressure) 0.5MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).300 ℃ of reaction zone 2 temperature of reaction, liquid air speed 1 hour -1, reaction pressure (gauge pressure) is 3MPa.The raw material that uses in the experiment is pure butene-2, ethene and butylene mass ratio are 2.0: 1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 74.1% based on the butylene mass fraction, butene conversion is 84% behind reaction zone 2, and the mass fraction of propylene is 42.2%.
[embodiment 7]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 350), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 18%), activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
400 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 1 hour -1, pressure (gauge pressure) 0.5MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).300 ℃ of reaction zone 2 temperature of reaction, liquid air speed 1 hour -1, reaction pressure (gauge pressure) is 3MPa.The raw material that uses in the experiment is pure butene-2, ethene and butylene mass ratio are 2.5: 1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 74.1% based on the butylene mass fraction, butene conversion is 87% behind reaction zone 2, and the mass fraction of propylene is 37.2%.
[embodiment 8]
Reaction zone 1 used type ZSM 5 molecular sieve catalyzer 1 (the silica alumina ratio SiO that makes according to each step of embodiment 1 2/ Al 2O 3Be 100), reaction zone 2 used oxide catalyst 2 (WO 3Content be vehicle weight 18%), activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
400 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 1 hour -1, pressure (gauge pressure) 0.5MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).450 ℃ of reaction zone 2 temperature of reaction, liquid air speed 1 hour -1, reaction pressure (gauge pressure) is 0.5MPa.The raw material that uses in the experiment is pure butene-2, ethene and butylene mass ratio are 3.0: 1, and ethene directly enters reaction zone 2 without reaction zone 1, and reaction zone 1 butene-2 is 74.1% based on the butylene mass fraction, butene conversion is 87.2% behind reaction zone 2, and the mass fraction of propylene is 32.6%.
[embodiment 9]
The reaction zone 2 used oxide catalyst 2 (WO that make according to each step of embodiment 1 3Content be vehicle weight 8%), changing reaction zone 1 used molecular sieve catalyst 1 is beta-molecular sieve, silica alumina ratio SiO 2/ Al 2O 3Be 700, activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
280 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 10 hours -1, pressure (gauge pressure) 0.2MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).300 ℃ of reaction zone 2 temperature of reaction, liquid air speed 1 hour -1, reaction pressure (gauge pressure) is 2.5MPa.The raw material that uses in the experiment is pure butene-1, ethene and butylene mass ratio are 1.5: 1, and ethene enters reaction zone 2 again through reaction zone 1, and reaction zone 1 butene-2 is 81.0% based on the butylene mass fraction, butene conversion is 80.2% behind reaction zone 2, and the mass fraction of propylene is 43.0%.
[embodiment 10]
The reaction zone 2 used oxide catalyst 2 (WO that make according to each step of embodiment 1 3Content be vehicle weight 8%), changing reaction zone 1 used molecular sieve catalyst 1 is mordenite molecular sieve, silica alumina ratio SiO 2/ Al 2O 3Be 30, activation 3 hours under 550 ℃, nitrogen atmosphere before catalyzer 2 reaction.
220 ℃ of reaction zone 1 (loading catalyst 1) temperature of reaction, air speed 10 hours -1, pressure (gauge pressure) 0.2MPa, reaction zone 1 reaction effluent enter reaction zone 2 (loading catalyst 2).320 ℃ of reaction zone 2 temperature of reaction, liquid air speed 1 hour -1, reaction pressure (gauge pressure) is 4.0MPa.The raw material that uses in the experiment is pure butene-1, ethene and butylene mass ratio are 5: 1, and ethene enters reaction zone 2 again through reaction zone 1, and reaction zone 1 butene-2 is 84.0% based on the butylene mass fraction, butene conversion is 93.% behind reaction zone 2, and the mass fraction of propylene is 23.0%.

Claims (8)

1. the method for a propylene enhancing is a raw material with butylene and ethene, may further comprise the steps successively:
(1) raw material butylene and silica alumina ratio SiO 2/ Al 2O 3Be at least 1 contact of 10 crystal aluminosilicate catalyzer, it is first strand of reaction effluent of 3～5: 1 that reaction generates butene-2 and butene-1 mol ratio;
(2) first strands of reaction effluents and catalyzer 2 contact reactss generate the reaction effluent that contains propylene; Wherein catalyzer 2 comprises following component:
(a) SiO 2Carrier; With carry thereon
(b) count 0.1～20% Tungsten oxide 99.999 with vehicle weight;
Wherein, the temperature of reaction of catalyzer 1 is 200～400 ℃, and the reaction weight space velocity is 0.1～10 hour -1, be 0～5MPa in the gauge pressure reaction pressure; The temperature of reaction of catalyzer 2 is 200～400 ℃, and the reaction weight space velocity is 0.1～3 hour -1, be 0～5MPa in the gauge pressure reaction pressure.
2. according to the method for the described propylene enhancing of claim 1, it is characterized in that butene feedstock is butene-1, butene-2 or its mixture; The weight ratio of ethene and butylene is 0.3～3: 1 in the raw material.
3. according to the method for the described propylene enhancing of claim 2, it is characterized in that the weight ratio of ethene and butylene is 0.5～2: 1 in the raw material.
4. according to the method for the described propylene enhancing of claim 1, it is characterized in that crystal aluminosilicate catalyzer 1 is selected from ZSM-5 molecular sieve, ZSM-35 molecular sieve, beta-molecular sieve or mordenite molecular sieve, its silica alumina ratio SiO 2/ Al 2O 3Be at least 10.
5. according to the method for the described propylene enhancing of claim 4, it is characterized in that catalyzer 1 is selected from the ZSM-5 molecular sieve, its silica alumina ratio SiO 2/ Al 2O 3Be 50～500.
6. according to the method for the described propylene enhancing of claim 1, it is characterized in that in the catalyzer 2 in vehicle weight Tungsten oxide 99.999 consumption being 4～10%.
7. according to the method for the described propylene enhancing of claim 1, the temperature of reaction that it is characterized in that catalyzer 1 is 200～350 ℃, and the reaction weight space velocity is 1～5 hour -1, be 0.1～3MPa in the gauge pressure reaction pressure.
8. according to the method for the described propylene enhancing of claim 1, the temperature of reaction that it is characterized in that catalyzer 2 is 250～350 ℃, and the reaction weight space velocity is 0.5～3 hour -1, be 1～3MPa in the gauge pressure reaction pressure.
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US8324440B2 (en) 2010-02-05 2012-12-04 Uop Llc Support properties of silica supported catalysts and their use in olefin metathesis
US8935891B2 (en) 2011-06-09 2015-01-20 Uop Llc Olefin metathesis catalyst containing tungsten fluorine bonds

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