CN101421208B - Method for producing propylene - Google Patents

Method for producing propylene Download PDF

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Publication number
CN101421208B
CN101421208B CN2007800130677A CN200780013067A CN101421208B CN 101421208 B CN101421208 B CN 101421208B CN 2007800130677 A CN2007800130677 A CN 2007800130677A CN 200780013067 A CN200780013067 A CN 200780013067A CN 101421208 B CN101421208 B CN 101421208B
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reactor
alkene
reaction
methyl alcohol
carbonatoms
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CN101421208A (en
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山口正志
吉川由美子
武胁隆彦
瀬户山亨
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for producing propylene efficiently from a raw material mixture comprising an olefin having four or more carbon atoms and at least one of methanol and dimethyl ether with high selectivity and in a high yield by inhibiting the production of by-products such as aromatic compounds or paraffins while keeping the reaction rate at a high level. The process comprises diluting a raw material mixture comprising an olefin having four or more carbon atoms and at least one of methanol and dimethyl ether with a diluent (C) (which consists of one or more members selected from among paraffins, aromatic compounds, steam, carbon dioxide, carbon monoxide, nitrogen, argon, and helium)in such a way as to satisfy the requirement (A) that the ratio of the amount by mole of the olefin fed into the reactor to the sum of the amount by mole of methanol fed into the reactor and twice the amount by mole of dimethyl ether fed thereinto is 0.5 to 10 and the requirement (B) that the total concentration of the olefin, methanol and dimethyl ether in the whole component fed into the reactor is 20 to 80% by volume, and subjecting the obtained dilution to catalytic reaction.

Description

The method of manufacture of propylene
Technical field
The present invention relates to a kind of method of manufacture of propylene, is alkene and the raw mix manufacturing that is selected from least a compound in methyl alcohol and the dme more than 4 by containing carbonatoms.
Background technology
As the method for making propylene; Usually adopted the mobile catalytic cracking of the steam cracking or the decompression light oil of petroleum naphtha in the past; In recent years, be the replacement(metathesis)reaction (metathesisreaction) of raw material with ethene and 2-butylene or be that the MTO technology of raw material also attracts tremendous attention with methyl alcohol and/or dme.On the other hand, also known is that the oxygenatedchemicals of alkene and methyl alcohol etc. more than 4 is the method (patent documentation 1) that raw material is made light alkene with carbonatoms.
In the above-mentioned patent documentation 1, embodiment is under the condition of alkene that contains high density and methyl alcohol, to react, but its reason and indeterminate.This is because of know the document that does not have so concrete record according to institutes such as the inventor.
But suppositions such as the inventor are thought: the contriver of patent documentation 1 considers that the carbonatoms that does not add oxygenatedchemicalss such as methyl alcohol is that the contact division of the alkene more than 4 is carried out usually under the condition of high olefin concentration.
The affirmation experiment of reference example 1,2 records of therefore, stating after carrying out.This result can confirm: the concentration of olefin of raw material is low, suppresses to generate by products such as aromatics or paraffinic hydrocarbons, but has the many shortcomings of catalytic amount that speed of response is slow, need.Can infer thus: in the patent documentation 1, under the condition of alkene that contains high density and methyl alcohol, reacting is in order to avoid this shortcoming.
Patent documentation 1: No. the 6888038th, USP
Summary of the invention
The problem that invention will solve
But, by contain carbonatoms be alkene more than 4 when being selected from raw mix at least a in methyl alcohol and the dme and making propylene, if employing high density reaction conditions, then the growing amount of by product such as aromatics or paraffinic hydrocarbons increases thereupon.And the generation of these not preferred by products has not only reduced the yield as the propylene of title product, and has promoted catalyst degradation or made numerous and diverseization etc. of purification step, and reaction process is brought big bad influence.
Problem of the present invention is to provide a kind of method of manufacture of propylene; This method is: in reactor drum; Raw mix is contacted with catalyzer and when making propylene, not only kept speed of response, and suppressed the generation of by products such as aromatics or paraffinic hydrocarbons; Simultaneously can make propylene effectively with high selectivity, said raw mix comprises that carbonatoms is the alkene more than 4 and is selected from least a compound in methyl alcohol and the dme.
Solve the method for problem
The inventor etc. have carried out concentrated research in order to solve above-mentioned problem; And having restudied that traditional propylene when being raw material with oxygenatedchemicalss such as methyl alcohol is created conditions and those skilled in the art's technological general knowledge at present, the result finds: in raw material, contain in the reaction system of oxygenatedchemicalss such as methyl alcohol, dme, even reduce the concentration as alkene, methyl alcohol and the dme of raw material; The reduction of the speed that also almost the do not induce reaction butene conversion of target (promptly as); And, through reducing their concentration, can suppress the not generation of preferred by product such as aromatics or paraffinic significantly; Also can prolong life of catalyst; Consequently need not increase the amount of catalyzer, just can highly selective and make propylene effectively, thus accomplished the present invention.
That is, first main points of the present invention are to provide a kind of method of manufacture of propylene, and this method comprises the steps:
Use the step of following thinner (C) dilution raw mix, satisfying following condition (A) and condition (B), said raw mix comprise carbonatoms be the alkene more than 4 and be selected from methyl alcohol and dme at least a compound;
In reactor drum, making the carbonatoms that contains after the dilution is the step that alkene more than 4 and the raw mix that is selected from least a compound in methyl alcohol and the dme contact with catalyzer,
Condition (A): the carbonatoms that is supplied to reactor drum is the total amount of the amount of the alkene more than 4 with respect to the mole number of the dme of the mole number of the methyl alcohol that is supplied to reactor drum and 2 times, with molar ratio computing, is 0.5～10;
Condition (B): be supplied in all supply compositions of reactor drum, carbonatoms is that the total concn of alkene, methyl alcohol and dme more than 4 is 20 volume %～80 volume %;
Condition (C): be selected from paraffinic, the fragrant same clan, water vapor, carbonic acid gas, carbon monoxide, nitrogen, argon gas and the helium one or more as thinner.
Second main points of the present invention are, a kind of method of manufacture of propylene, and wherein, said catalyzer contains the zeolite as the catalyst activity composition.
The 3rd main points of the present invention are, a kind of method of manufacture of propylene, and wherein, in aforesaid method, said zeolite is one or more the mixture that is selected from MFI, MEL, MOR, MWW, CHA, BEA and FAU.
The 4th main points of the present invention are, a kind of method of manufacture of propylene, and wherein, in aforesaid method, said zeolite is one or more the mixture that is selected from MFI, MEL, MWW and CHA.
Five points of the present invention is, a kind of method of manufacture of propylene, and wherein, in aforesaid method, the gas temperature of said reactor inlet is 400 ℃～600 ℃.
The 6th main points of the present invention are, a kind of method of manufacture of propylene, and wherein, in aforesaid method, said reactor drum is fixed-bed reactor.
The 7th main points of the present invention are, a kind of method of manufacture of propylene wherein, in aforesaid method, is that at least a portion of the alkene more than 4 is recycled to this reactor inlet with the carbonatoms that said reactor outlet gas contained.
The invention effect
According to the present invention; By containing carbonatoms is that alkene more than 4 is when being selected from raw mix at least a in methyl alcohol and the dme and making propylene; Keeping the generation that has suppressed by products such as aromatics or paraffinic hydrocarbons under the prerequisite of speed of response, can come to make effectively propylene with high selectivity and high yield.
Embodiment
Below, explanation is used for the representative embodiment of embodiment of the present invention particularly, but the present invention is only otherwise exceeding its main points just is not limited to following embodiment.
[catalyzer]
At first, describe to the catalyzer that uses in the present invention.
As the catalyzer that in reaction of the present invention, uses, the solid-like material of Br point is just not special to be limited so long as have, and uses present known catalyzer, for example enumerates clay minerals such as kaolin; Make sour impregnations such as sulfuric acid, phosphoric acid, support the material in carriers such as clay mineral; Acid type ion exchange resin; Zeolites; The phosphagel phosphaljel class; The solid acid catalyst of the mesoporous Si-Al molecular sieve of Al-MCM41 etc. etc.
In these solid acid catalysts, preferably have the material of molecular sieve effect, and, the material that preferred acid intensity is not too high.
In the above-mentioned solid acid catalyst; Structure as zeolites with molecular sieve effect or phosphagel phosphaljel class; During with the coded representation of International Zeolite Association (IZA) regulation, for example enumerate AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON etc.Wherein, preferred catalyst tissue (frame wark) density is 18.0T/nm 3Following catalyzer is preferably enumerated MFI, MEL, MOR, MWW, FAU, BEA, CHA as this type material, more preferably enumerates MFI, MEL, MOR, MWW, CHA, preferred especially MFI, MEL, MWW, CHA.
Here, (unit: T/nm of so-called tissue density 3) be meant unit volume (1nm 3) existing T atom in the zeolite (constituting the atom beyond the deoxygenation in the atom of framework of zeolite) number, this value is by the structures shape of zeolite.
And as this solid acid catalyst, more preferably fine pore is that minute aperture, the BET specific surface area of 0.3nm～0.9nm are 200～700m 2/ g, pore volume are crystallinity aluminum silicate, metal silicate, metallic aluminium silicate or the crystallinity phosphagel phosphaljel class etc. of 0.1～0.5 milliliter/g.In addition; Here said fine pore is represented the channel diameter (Crystallographicfree diameter of the channels) of the crystallography of International Zeolite Association (IZA) regulation, is recorded in ATLAS OF ZEOLITEFRAMEWORKTYPES FIFTH RIVISED EDITION2001 (ELSEVIER).Pore (passage) be shaped as circle the time, refer to its diameter; Pore be shaped as ellipse the time, refer to its minor axis.
In addition, in the aluminosilicate, preferred SiO 2/ Al 2O 3Mol ratio is the material more than 10.SiO 2/ Al 2O 3Mol ratio is crossed when hanging down, because the reduction of the weather resistance of catalyzer, so not preferred.SiO 2/ Al 2O 3The upper limit of mol ratio is generally below 10000, and is preferred below 2000.SiO 2/ Al 2O 3Mol ratio too much is higher than on this prescribes a time limit, because the catalyst activity reduction, so be not preferred.Above-mentioned mol ratio can be obtained through ordinary methods such as fluorescent X-ray or chemical analysis.
Aluminium content in the catalyzer can be enough raw material input amount during the preparation catalyzer control, in addition, after preparation, also can wait and reduce aluminium content through steaming.In addition, also can part aluminium be replaced into other element of boron or gallium etc., especially preferably replace with boron.
These catalyzer both can use a kind of separately, also can mix two or more uses.
Above-mentioned catalyst activity composition both can directly be used for reaction as catalyzer, and also can use reaction is that inactive material or tackiness agent carry out being used for reaction after granulation, moulding perhaps mix their.As this being reacted inactive material or tackiness agent, can enumerate aluminum oxide or alumina sol, silicon-dioxide, silica gel, quartz and their mixture etc.
In addition, the composition of above-mentioned catalyst activity composition is a catalyst activity composition itself, and does not comprise that these are inactive material or tackiness agent etc. to reaction.So-called catalyzer of the present invention during for inactive material or tackiness agent etc., is referred to as catalyzer to reaction for inactive material or tackiness agent etc. with above-mentioned catalyst activity composition and these to reaction comprising these; Do not contain these reaction during for inactive material or tackiness agent etc., itself is called catalyzer with the catalyst activity composition.
The difference of the condition of the particle diameter of the catalyzer that uses in the present invention when synthetic and different, but median size is 0.01 μ m～500 μ m usually.When the particle diameter of catalyzer was excessive, the surface-area that demonstrates catalyst activity diminished; When the particle diameter of catalyzer was too small, its operability variation was so any situation all is not preferred.Said median size can be observed to wait and obtained through SEM.
For employed Preparation of catalysts method among the present invention, not special the qualification can prepare according to hydro-thermal synthetic ordinary method usually.In addition, after hydro-thermal is synthetic, also can or modification such as supports and change composition through IX, dealumination treatment, impregnation.
The catalyzer that uses in the present invention is when supply response, if it is just passable to have a material of above-mentioned physical properties or composition, can be the material that utilizes arbitrary method to prepare.
[reaction raw materials]
Then, explain that in the present invention the carbonatoms as reaction raw materials is alkene, methyl alcohol, dme more than 4.
< alkene >
Carbonatoms for as reaction raw materials is the alkene more than 4, not special the qualification.The carbonatoms that for example can use the whole bag of tricks manufacturing of passing through routine that is described below to obtain is the alkene more than 4; Particularly carbonatoms is 4～10 alkene: utilize catalystic pyrolysis or steam splitting process etc. to carry out FT (Fischer-Tropsch process by the alkene (C4 oil raffinate-1, C4 oil raffinate-2 etc.) of oil base feed manufacturing, the hydrogen/Co mixed gas that will utilize coal gasification to obtain as raw material; Fischer-Tropsch) alkene that is synthesized into, the alkene that obtains by the reaction of the oligopolymer of the dimerization reaction that contains ethene, be the dehydriding of the paraffinic hydrocarbons 4 or more or alkene that the oxydehydrogenation method obtains, react alkene that the alkene that obtains, dehydration reaction through alcohol obtains, be the alkene that obtains of the hydrogenation of the diolefin compound more than 4 etc. through carbonatoms through MTO through carbonatoms; At this moment; Both can directly use at random be mixed with other compounds to pass through the carbonatoms that each method of manufacture obtains be the alkene more than 4, also can use the alkene behind the purifying.
< methyl alcohol, dme >
For the manufacturing source of at least a compound in methyl alcohol that is used as reaction raw materials and the dme, not special the qualification.The compound that the alcohols that for example enumerate compound that the mixed gas from the hydrogen/CO of the by product of coal and Sweet natural gas and system iron industry obtains through hydrogenation, derives from life entity (biomass) obtains through modified-reaction, utilize compound that fermentation method obtains, the compound that obtains by organic substances such as recyclable plastic or urban waste etc.At this moment, both can directly use methyl alcohol that at random is mixed with other compounds and the dme that obtains through each method of manufacture, also can use through methyl alcohol and dme behind the purifying.
[operation, condition]
Below, operation, the condition of reacting to the propylene manufacturing of the present invention of using above-mentioned catalyzer and reaction raw materials describe.
< reactor drum >
Carbonatoms of the present invention is that the alkene more than 4 is gas-phase reaction with the reaction that is selected from least a compound in methyl alcohol and the dme.Continous way fixed-bed reactor or continous way flowing bed reactor are selected in the not special restriction of the form of this Gas-phase reactor usually.
In addition, when above-mentioned catalyzer is filled in reactor drum, for the temperature that suppresses catalyst layer is little distribution, can be with silica sand, aluminum oxide, silicon-dioxide, silica-alumina etc. to reacting for recharging after inactive saccharoid and the catalyst mix.At this moment, silica sand etc. is the not special restriction of the usage quantity of inactive saccharoid to reaction.In addition, from considering that with the uniform mixing property aspect of catalyzer this saccharoid preferably has the particle diameter with the catalyzer same degree.
For the heat that disperses to produce by reaction, supply response matrix (reaction raw materials) in reactor drum in batches.
The catalyzer that uses is in the present invention compared with existing catalyzer, and caulking joint is few, the degradation speed of catalyzer is slow, but when moving more than 1 year continuously, need be in operation and carry out the regeneration of catalyzer.
For example, under the situation of selecting fixed-bed reactor, the plural at least reactor drum of preferred setting is in operation and constantly switches reaction and regeneration.As the form of fixed bed reaction, select multi-tubular reactor or heat-insulating type reactor drum.
On the other hand, selecting under the situation of flowing bed reactor, preferred: catalyzer is delivered to regeneration tank continuously, will be in regeneration tank the regenerated catalyzer turn back to continuously in the reactor drum and react.
Here, as the regenerative operation of catalyzer, enumerate regenerated operation through handle the catalyzer that imports from reactor drum with the nitrogen or the water vapor that contain aerobic etc.
< alkene and the supply concentration ratio that is selected from least a compound in methyl alcohol and the dme >
In the present invention; The carbonatoms that is supplied to reactor drum is the total amount of the amount of the alkene more than 4 with respect to the dme mole number of the moles of methanol that is supplied to reactor drum and 2 times; Count more than 0.5, be preferably more than 0.8 with mole, and be below 10, preferred (condition (A)) below 5.
That is, carbonatoms is that the supply molar weight of the alkene more than 4 is M C4, methyl alcohol the supply molar weight be M m, dme molar weight be M DmThe time, M C4Be (M m+ 2M Dm) 0.5～10 times, preferred 0.8～5 times.
This supply concentration ratio is crossed low or too high, reacts all slack-off, is not preferred, and particularly this supply concentration ratio is crossed when hanging down, and the consumption of raw material olefin reduces, so not preferred.
That is, in the present invention, it is characterized in that, through being the alkene more than 4 and being selected from least a compound in methyl alcohol and the dme that with suitable concentration ratio supply carbonatoms the substrate concn afterreaction speed of after reduction, stating significantly improves.
In addition, with carbonatoms be alkene more than 4 when being selected from that at least a compound is supplied to reactor drum in methyl alcohol and the dme, both can supply with them respectively, also can be pre-mixed a part or whole after resupply.
<substrate concn >
In the present invention, it is that the total concn (substrate concn) of alkene, methyl alcohol and dme more than 4 is 20 volume %～80 volume % that all that are supplied to reactor drum are supplied with carbonatoms in compositions, preferred 30 volume %～70 volume % (condition (B)).
When this substrate concn is too high, significantly generate aromatics or paraffinic, have the tendency of the selection rate reduction of propylene.On the contrary, this substrate concn is crossed when hanging down, because speed of response is slack-off, so need a large amount of catalyzer, and also the purifying cost of product or the cost of erection of conversion unit increase, and are uneconomic.
Through in above-mentioned preferred substrate concn scope, reacting, under suitable catalytic amount, can suppress to generate not preferred by product, and make propylene with low cost.
Therefore, in order to obtain such substrate concn, in the present invention, with thinner (thinner (C)) the diluting reaction matrix of following record.
< thinner >
In reactor drum; Except that carbonatoms be more than 4 alkene, be selected from methyl alcohol and the dme at least a compound; Can also contain reaction for inactive gas, promptly said reaction comprised paraffinic, the fragrant same clan, water vapor, carbonic acid gas, carbon monoxide, nitrogen, argon gas, helium and their mixture for inactive gas.In addition, in these thinners, the paraffinic or the fragrant same clan also can participate in reaction sometimes according to reaction conditions, but because reacting weight is few, therefore are defined as thinner.
As this type thinner, both can directly use the impurity that contains in the reaction raw materials, also can the thinner that prepare in addition be mixed use with reaction raw materials.
In addition, thinner both can mix with reaction raw materials before getting into reactor drum, also can be supplied to reactor drum respectively with reaction raw materials.
< space velocity >
Here said " space velocity " is meant; Reaction raw materials is that carbonatoms is the flow of alkene through the catalyzer (catalyst activity composition) of unit weight more than 4, and said here " weight of catalyzer " is the weight of the catalyst activity composition of the non-active ingredient that uses in the granulation that is not included in catalyzer, the moulding or tackiness agent.In addition, flow is meant that carbonatoms is the flow (weight/time) of the alkene more than 4.
Space velocity is preferably 0.1Hr -1～500Hr -1Between, 1.0Hr more preferably -1～100Hr -1Between.When space velocity was too high, the alkene of raw material was with to be selected from methyl alcohol and the dme at least a conversion of compounds rate low, and can not get sufficient propylene selection rate.In addition, cross when low when space velocity, in order to obtain certain turnout, needed catalyzer quantitative change is many, when reactor drum is excessive, generates preferred by product such as aromatics or paraffinic hydrocarbons, and the propylene selection rate reduces, so not preferred.
< temperature of reaction >
As the lower limit of temperature of reaction, the gas temperature of reactor inlet is about more than 300 ℃ usually, and is preferred more than 400 ℃; As the upper limit of temperature of reaction, be generally below 700 ℃, preferred below 600 ℃.Reaction temperature is spent when hanging down, and speed of response is low, and a large amount of residual tendencies of unreacting material are arranged, and in addition, the yield of propylene also reduces.On the other hand, when temperature of reaction was too high, the yield of propylene significantly reduced.
< reaction pressure >
The upper limit of reaction pressure is preferably below the 2MPa (absolute pressure, down together) usually, is preferably below the 1MPa, more preferably below the 0.7MPa.In addition, the not special restriction of the lower limit of reaction pressure, but be generally more than the 1kPa, be preferably more than the 50kPa.When reaction pressure was too high, paraffinic or aromatics etc. the not growing amount of preferred by product increased, and the yield of propylene has the tendency of reduction.Reaction pressure is crossed when hanging down, and speed of response has slack-off tendency.
< reaction product >
As reactor outlet gas (reactor effluent), obtain containing the mixed gas of propylene, unreacting material, by product and thinner as reaction product.Density of propylene in this mixed gas is generally 5～95 weight %.
It is the alkene more than 4 that unreacting material is generally carbonatoms.Contain at least a in methyl alcohol and the dme according to reaction conditions, but preferred at least a transformation efficiency in methyl alcohol and dme is to react under 100% the reaction conditions.Thus, make reaction product and unreacting material separate easily.
As by product, can enumerate ethene, carbonatoms is olefines, paraffinic, aromatics and water more than 4.
< separation of product >
To be directed into as the mixed gas that contains propylene, unreacting material, by product and thinner of reactor outlet gas and knownly separate, in the purifier apparatus, can reclaim according to each composition, purifying, the processing that utilizes again, discharge as reaction product.
As this separate, a kind of mode of purification process, use the method that comprises the step that is described below, the gas of cooling, compression reactor outlet is removed the step of condensed most of moisture; After removing moisture, still contain the hydrocarbon fluid of part moisture with dryings such as molecular sieves, then, through the step of each alkene of distillation purifying and paraffinic hydrocarbons.In aforesaid method, can the hydrocarbon fluid after the compression be supplied to a distillation tower, but also a plurality of compressors can be set, roughing out is hydrocarbon that is prone to condensation and the hydrocarbon that is difficult for condensation, they is supplied to each distillation tower distills.
For the part or all of composition except that propylene (alkene, paraffinic hydrocarbons etc.), preferably behind above-mentioned separation, purifying, mix with reaction raw materials, utilize again, or directly be supplied to reactor drum and utilize again.In addition, in by product, reaction for can be used as thinner, inactive composition is utilized again.
Embodiment
Below enumerate embodiment the present invention more specifically is described, but the present invention does not receive any qualification of following examples.
In addition, the catalyzer that uses in following embodiment, comparative example and the reference example is according to the method preparation that is described below.
[preparation catalyzer]
< preparation example 1 >
26.6g bromination four n-propyl ammoniums (TPABr) and 4.8g sodium hydroxide are dissolved in the 280g water successively, then, add 75g colloid silica (SiO at leisure 2=40 weight %, Al<0.1 weight %) and the mixed solution of 35g water,, fully stir, obtain aqueous gel.Then, this gel is put in the autoclave of 1000ml, depressed certainly, under 170 ℃, carried out hydro-thermal synthetic 72 hours with the 300rpm stirring velocity.Product is through pressure filtration, and the separate solid composition fully after the washing, descended dry 24 hours at 100 ℃.Dried catalyzer was fired 6 hours under airiness, 550 ℃, obtained the aluminosilicate of Na type.
The aluminosilicate of this Na type of 2.0g is suspended in 40 milliliters of the aqueous ammonium nitrate solutions of 1M, stirred 2 hours down at 80 ℃.Through separate solid composition the liquid of suction filtration after handling, fully after the washing, make it once more to be suspended in 40 milliliters of the aqueous ammonium nitrate solutions of 1M, and stirred 2 hours down at 80 ℃.Through suction filtration the liquid after handling is separated, the solids component that separation is obtained carries out abundant wet concentration, and is following dry 24 hours at 100 ℃ then.Dried catalyzer was fired 4 hours under airiness, under 500 ℃, prepared the aluminosilicate (being called " catalyst A ") of H type.
Confirmed that through XRD (X-ray diffraction) structure of the zeolite of this catalyst A is the MFI type.
The result of the composition through this catalyst A of chemical analysis standard measure, SiO 2/ Al 2O 3=1100 (mol ratios).
< preparation example 2 >
With 26.6g bromination four n-propyl ammoniums (TPABr), 12.4g boric acid, 1.25g an ammonium nitrate 9H 2O and 4.8g sodium hydroxide are dissolved in the 280g water successively, then, add 75g colloid silica (SiO at leisure 2=40 weight %, the about 0.06 weight % of Al=) and the mixed solution of 35g water, fully stir, obtain aqueous gel.Then, this gel is dropped in the autoclave of 1000ml, depressing certainly, under 170 ℃, carried out hydro-thermal synthetic 72 hours with the 300rpm stirring velocity.Treatment step afterwards is identical with preparation example 1, obtains the boroaluminosilicate (being called " catalyst B ") of H type thus.
Confirmed that through XRD (X-ray diffraction) structure of the zeolite of this catalyst B is the MFI type.
Behind the composition through quantitative this catalyst B of chemical analysis, SiO 2/ Al 2O 3=324 (mol ratios), SiO 2/ B 2O 3=94 (mol ratios).
[manufacturing of propylene]
Below show the embodiment and the comparative example that use above-mentioned catalyst A, B to make propylene.
< embodiment 1 >
Use catalyst A to make propylene.
Use atmospheric fixed bed circulation reaction unit in the reaction, the mixture of above-mentioned catalyst A of 25mg and 0.5g silica sand is filled in the quartz system reaction tubes of internal diameter 6mm.The gas that will be prepared into iso-butylene (20 volume %), methyl alcohol (10 volume %) and nitrogen (70 volume %) is through vaporizer and be supplied to this reactor drum.Temperature of reaction (reactor inlet gas temperature) is 550 ℃.Back 70 minutes of reaction beginning has been analyzed product with gas chromatograph.
Table 1 shows reaction conditions and reaction result.
Butene conversion is 51.2%, methanol conversion is 100%, the selection rate of propylene is 52.7%.On the other hand, total selection rate of aromatics and paraffinic hydrocarbons is 1.8%, belongs to low-down level.
< embodiment 2 >
The concentration of iso-butylene and methyl alcohol is respectively 2 times of concentration of iso-butylene and methyl alcohol among the embodiment 1 in making raw gas concentration, under the reaction conditions identical with embodiment 1, reacts.Table 1 shows reaction conditions and reaction result.Butene conversion is 64.7%, methanol conversion is 100%, the selection rate of propylene is 54.9%.Total selection rate of aromatics and paraffinic hydrocarbons is 6.4%, though than embodiment more than 1, also be low-down level.
< embodiment 3 >
The concentration of iso-butylene and methyl alcohol is respectively 2.33 times of concentration of iso-butylene and methyl alcohol among the embodiment 1 in making raw gas concentration, under the reaction conditions identical with embodiment 1, reacts.Table 1 shows reaction conditions and reaction result.Table 1 shows reaction conditions and reaction result.Butene conversion is 64.9%, methanol conversion is 100%, the selection rate of propylene is 52.7%.Total selection rate of aromatics and paraffinic hydrocarbons is 9.1%, though than embodiment 1, more than 2, also belong to low-down level.
< comparative example 1 >
The concentration of iso-butylene and methyl alcohol is respectively 3 times of concentration of iso-butylene and methyl alcohol among the embodiment 1 in making raw gas concentration, under the reaction conditions identical with embodiment 1, reacts.Table 1 shows reaction conditions and reaction result.Table 1 shows reaction conditions and reaction result.Butene conversion is 65.1%, methanol conversion is 100%, the selection rate of propylene is 47.4%.Total selection rate of aromatics and paraffinic hydrocarbons is 15.3%, compares with embodiment 1～3, significantly increases, and the selection rate of propylene can not meet the demands.
< embodiment 4 >
Use catalyst B to replace catalyst A, with the gas that is prepared into iso-butylene 15 volume %, methyl alcohol 15 volume % and nitrogen 70 volume % through vaporizer and be supplied to this reactor drum, except that above-mentioned, with embodiment 1 the same the reaction.Table 1 shows reaction conditions and reaction result.Butene conversion is 50.0%, methanol conversion is 100%, the selection rate of propylene is 52.7%.On the other hand, total selection rate of aromatics and paraffinic hydrocarbons is 2.1%, belongs to low-down level.
< embodiment 5 >
The concentration of iso-butylene and methyl alcohol is respectively 2 times of concentration of iso-butylene and methyl alcohol among the embodiment 1 in making raw gas concentration, under the reaction conditions identical with embodiment 4, reacts.Table 1 shows reaction conditions and reaction result.Butene conversion is 59.0%, methanol conversion is 100%, the selection rate of propylene is 54.7%.Total selection rate of aromatics and paraffinic hydrocarbons is 5.7%, though than embodiment more than 4, also belong to low-down level.
< embodiment 6 >
The concentration of iso-butylene and methyl alcohol is respectively 2.33 times of concentration of iso-butylene and methyl alcohol among the embodiment 4 in making raw gas concentration, under the reaction conditions identical with embodiment 1, reacts.Table 1 shows reaction conditions and reaction result.Butene conversion is 59.2%, methanol conversion is 100%, the selection rate of propylene is 52.1%.Total selection rate of aromatics and paraffinic hydrocarbons is 8.4%, though than embodiment 4, more than 5, also be low-down level.
< comparative example 2 >
The concentration of iso-butylene and methyl alcohol is respectively 3 times of concentration of iso-butylene and methyl alcohol among the embodiment 1 in making raw gas concentration, under the reaction conditions identical with embodiment 4, reacts.Table 1 shows reaction conditions and reaction result.Butene conversion is 59.5%, methanol conversion is 100%, the selection rate of propylene is 47.6%.Total selection rate of aromatics and paraffinic hydrocarbons is 14.8%, compares with embodiment 4～6, significantly increase, but the selection rate of propylene still is unappeasable level.
< reference example 1,2 >
Do not increase the supply flow rate of nitrogen except not adding material benzenemethanol, under the reaction conditions identical, react with embodiment 1,2.Table 1 shows reaction conditions and reaction result.Among the embodiment 1 and 2, even material concentration is 1/2, transformation efficiency does not have big variation yet; And in reference example 1 and 2, be 1/2 through making material concentration, transformation efficiency reduces greatly.
Figure G2007800130677D00131
With reference to detailed Description Of The Invention or specific embodiment the present invention is described, as long as but be no more than in theme of the present invention and the scope, those skilled in the art can carry out various changes or modification.
The application is based on the invention of the Japanese patent application of submitting on April 14th, 2006 (the special 2006-112254 of hope), and its content incorporates this literary composition as reference.
Industrial applicibility
The present invention provide a kind of in reactor drum through make contain carbonatoms be more than 4 alkene be selected from methyl alcohol and dme at least a raw mix contact with catalyzer when making propylene; Keeping under the prerequisite of speed of response the generation of by products such as suppressing aromatics or paraffinic hydrocarbons, high selectivity and make the method for propylene effectively.

Claims (7)

1. the method for manufacture of a propylene, this method comprises the steps:
Use the step of following thinner (C) dilution raw mix, satisfying following condition (A) and condition (B), said raw mix comprise carbonatoms be the alkene more than 4 and be selected from methyl alcohol and dme at least a compound;
In reactor drum, making the carbonatoms that contains after the dilution is the step that alkene more than 4 and the raw mix that is selected from least a compound in methyl alcohol and the dme contact with catalyzer,
Condition (A): the carbonatoms that is supplied to reactor drum is the total amount of the amount of the alkene more than 4 with respect to the mole number of the dme of the mole number of the methyl alcohol that is supplied to reactor drum and 2 times, with molar ratio computing, is 0.5～10;
Condition (B): be supplied in all supply compositions of reactor drum, carbonatoms is that the total concn of alkene, methyl alcohol and dme more than 4 is 20 volume %～80 volume %;
Condition (C): be selected from paraffinic, the fragrant same clan, water vapor, carbonic acid gas, carbon monoxide, nitrogen, argon gas and the helium one or more as thinner.
2. the method for manufacture of the described propylene of claim 1, wherein, said catalyzer contains the zeolite as the catalyst activity composition.
3. the method for manufacture of the described propylene of claim 2, wherein, said zeolite is one or more the mixture that is selected among MFI, MEL, MOR, MWW, CHA, BEA and the FAU.
4. the method for manufacture of the described propylene of claim 3, wherein, said zeolite is one or more the mixture that is selected among MFI, MEL, MWW and the CHA.
5. the method for manufacture of each described propylene in the claim 1～4, wherein, the gas temperature of said reactor inlet is 400 ℃～600 ℃.
6. the method for manufacture of each described propylene in the claim 1～5, wherein, said reactor drum is fixed-bed reactor.
7. the method for manufacture of each described propylene in the claim 1～6 wherein, is that at least a portion of the hydrocarbon more than 4 is recycled to this reactor inlet with the carbonatoms that is contained in the said reactor outlet gas.
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