CN101410353B - Method for producing propylene - Google Patents

Method for producing propylene Download PDF

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Publication number
CN101410353B
CN101410353B CN2007800113440A CN200780011344A CN101410353B CN 101410353 B CN101410353 B CN 101410353B CN 2007800113440 A CN2007800113440 A CN 2007800113440A CN 200780011344 A CN200780011344 A CN 200780011344A CN 101410353 B CN101410353 B CN 101410353B
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propylene
ethanol
ethene
aluminosilicate
catalyzer
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CN101410353A (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
    • 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
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Disclosed is a method for producing propylene from at least one of ethanol and ethylene with high yield. Specifically disclosed is a method for producing propylene, wherein at least one of ethanol and ethylene is brought into contact with a catalyst in a reaction vessel. This method for producing propylene is characterized in that an aluminosilicate having a pore size of less than 0.5 nm is used as the catalyst. The catalyst is preferably composed of an aluminosilicate having an 8-membered or 9-membered ring, particularly preferably an aluminosilicate having a CHA structure. By producing a polypropylene as an all-purpose resin from propylene, which is produced from bioethanol that is a plant-derived raw material, environmental burden can be reduced.

Description

The manufacture method of propylene
Technical field
The present invention relates in the presence of catalyzer, in reaction vessel at least a in ethanol and the ethene carried out the method that propylene is made in catalysis.
The invention still further relates to making good propylene and make polyacrylic method.
Background technology
As the method for making propylene, usually adopted in the past the mobile catalytic cracking of steam cracking or the decompression light oil of petroleum naphtha, in recent years, the replacement(metathesis)reaction (metathesisreaction) take ethene and 2-butylene as raw material or the MTO technique take methyl alcohol and/or dme as raw material also attract tremendous attention (patent documentation 1).
On the other hand, as the little polymkeric substance of carrying capacity of environment, what receive publicity recently is the polymkeric substance that uses from the raw material of plant, has also occurred several polymkeric substance on the market, but is to be made by main propylene take crude oil as raw material as the polypropylene of widely used resin.Imagination: if can use the raw material (bio-ethanol) from plant to make propylene, the effect of Reducing the burden on the environment is just very large so.
Patent documentation 1: No. the 4148835th, United States Patent (USP)
Summary of the invention
The problem that invention will solve
Put down in writing the alcohol that uses with carbonatoms 1～4 in the claim of patent documentation 1 as raw material, although raw material is not limited to methyl alcohol, concrete disclosed alcohol only has methyl alcohol in this embodiment, not the embodiment of record take ethanol as raw material.
The judgements such as the inventor: use the aluminosilicate ZSM-5 that knows with catalyzer as MTO or (SAPO-34 of シ リ コ ア Le ミ ノ ホ ス Off エ-ト) is as catalyzer as silicoaluminophosphamolecular molecular sieves, when the conversion reaction of carrying out take ethanol as raw material, feed ethanol is dewatered immediately and is generated ethene.And as can be known: in case generated ethene, reaction thereafter is very slow, and the yield of propylene is very low.Relative therewith, during take methyl alcohol as raw material, generated the alkene such as ethene by methyl alcohol, the ethene of generation and material benzenemethanol reaction can efficient generate propylene well, and this is verified in above-mentioned patent documentation 1.
As previously mentioned, imagination: if can use the raw material (bio-ethanol) from plant to make propylene, the effect of Reducing the burden on the environment is just very large so, but at present, fully do not inquire into the method for making propylene take ethanol as raw material, the method for propylene is established take ethanol as raw material and is made with high yield in expectation.
Problem of the present invention is to provide with high yield by at least a method that obtains propylene in ethanol and the ethene.The present invention also provides by making polyacrylic method by the propylene of the method manufacturing.
Solve the method for problem
The inventor etc. have carried out repeatedly deep research in order to solve above-mentioned problem, found that: have the catalyzer of specific physical property by use, can be with at least a the make propylene of very high yield by ethanol and ethene, thus finished the present invention.
Namely, the 1st main points of the present invention are, a kind of manufacture method of propylene, it is at least a method that contacts to make propylene with catalyzer that makes in reactor in ethanol and the ethene, it is characterized in that, above-mentioned catalyzer contains aluminosilicate as the catalyst activity composition, and described aluminosilicate has the aperture of not enough 0.5nm.
The 2nd main points of the present invention are, a kind of manufacture method of propylene is characterized in that, in aforesaid method, the catalyst activity composition is the aluminosilicate with eight Yuans rings or nine Yuans rings.
The 3rd main points of the present invention are, a kind of manufacture method of propylene is characterized in that, in aforesaid method, the structure of aluminosilicate is CHA.
The 4th main points of the present invention are, a kind of manufacture method of propylene is characterized in that, in aforesaid method, and the SiO of aluminosilicate 2/ Al 2O 3Mol ratio is more than 5.
The 5th main points of the present invention are, a kind of manufacture method of propylene is characterized in that, in aforesaid method, with the equipment that possesses flowing bed reactor and revivifier, the manufacturing of propylene is carried out on cyclic regeneration catalyzer limit, limit.
The 6th main points of the present invention are, a kind of manufacture method of propylene, it is characterized in that, in aforesaid method, at least a transformation efficiency in ethanol and ethene (being converted into the transformation efficiency of the compound beyond ethanol and the ethene by at least a in ethanol and the ethene) is to react under 20%～80% the condition.
The 7th main points of the present invention are, a kind of manufacture method of propylene is characterized in that, in aforesaid method, at least a portion of the ethene that contains in the reactor outlet gas are recycled in the reactor.
The 8th main points of the present invention are, a kind of manufacture method of propylene is characterized in that, make polypropylene take the propylene of the manufacture method manufacturing by aforesaid propylene as raw material.
The effect of invention
According to the present invention, can be with high yield by at least a manufacturing propylene in ethanol and the ethene.
Therefore, according to the present invention, by by using the propylene of making from the bio-ethanol of the raw material of plant to make widely used resin polypropylene, can seek the reduction of carrying capacity of environment.
Embodiment
Below, specifically describe representational embodiment of the present invention, but the present invention is only otherwise exceed its purport, then is not limited to following mode.
[catalyzer]
＜catalyst activity composition 〉
At first, the catalyzer that uses among the present invention is described.
The catalyzer that uses among the present invention with the aluminosilicate of the not enough 0.5nm in aperture as the catalyst activity composition.Here said aperture represents the channel diameter (Crystallographic free diameter of the channels) of the crystallography of International Zeolite Association (IZA) regulation, is recorded in ATLAS OFZEOLITE FRAMEWORKTYPES FIFTH RIVISED EDITION2001 (ELSEVIER).The not enough 0.5nm in so-called aperture being shaped as in the circular situation of pore (duct), refers to the not enough 0.5nm of its diameter; But in the oval-shaped situation of being shaped as of pore, refer to the not enough 0.5nm of minor axis.
If the aperture of aluminosilicate is more than the 0.5nm, then produce propylene by product (butylene, amylene etc.) in addition and become many unfavorable conditions, can not be with high yield by at least a propylene of making in ethanol and the ethene.Although can be also indefinite by being made the details of the mechanism of action of propylene with the aluminosilicate of the not enough 0.5nm in aperture by at least a in ethanol and the ethene with high yield, but think: owing to strong acid point having occurred, can make ethanol or ethene sensitization, in addition, by little aperture, can optionally generate propylene.Namely infer: when being the little pore of the not enough 0.5nm of diameter, although can be from this pore out as the propylene of target compound, rest in the pore owing to molecule is excessive as the butylene of by product or amylene etc.Think the selection rate of improving propylene owing to such mechanism.
In addition, the lower limit in the aperture of aluminosilicate is not particularly limited.
As the structure of such aluminosilicate, usually preferably contain eight Yuans rings or nine Yuans structure of rings, more preferably only by eight structures that consisted of by ring.
As the aluminosilicate that is only consisted of by eight Yuans rings, during with the coded representation of International Zeolite Association (IZA) regulation, such as enumerating AFX, CAS, CHA, DDR, ERI, ESV, GIS, GOO, ITE, JBW, KFI, LEV, LTA, MER, MON, MTF, PAU, PHI, RHO, RTE, RTH etc.Aluminosilicate with these structures can be synthetic based on known information, for example, discloses have the CHA structure synthesis method of aluminosilicate of (channel diameter of the crystallography of IZA regulation is 0.38nm) among the US4544538A.
Wherein, preferred skeleton (frame wark) density is 18.0T/nm 3Following aluminosilicate, preferred aluminosilicate can be enumerated AFX, CHA, DDR, ERI, LEV, RHO.CHA most preferably.
Here said skeletal density (unit: T/nm 3) refer to unit volume (1nm 3) zeolite in the number of the T atom (consisting of the atom beyond the deoxygenation in the atom of zeolite framework) that exists, this value is by the structures shape of zeolite.
SiO as the aluminosilicate of catalyst activity composition 2/ Al 2O 3Mol ratio is preferably more than 5, more preferably more than 10.If SiO 2/ Al 2O 3Mol ratio is excessively low, and then the weather resistance of catalyzer reduces, thereby not preferred.SiO 2/ Al 2O 3The upper limit of mol ratio is generally below 1000.SiO 2/ Al 2O 3Mol ratio is higher than on this too much prescribes a time limit, and catalyst activity reduces, thereby not preferred.Above-mentioned mol ratio can be obtained by usual methods such as fluorescent X-ray or chemical analysis.
Above-mentioned catalyst activity composition both can directly be used for reaction as catalyzer, also can use and carry out granulation, moulding or they are mixed rear for reaction reacting inactive material or tackiness agent.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 catalyst activity composition itself, and does not comprise that these are to reacting inactive material or tackiness agent etc.So-called catalyzer of the present invention comprising these when reacting inactive material or tackiness agent etc., is collectively referred to as catalyzer with above-mentioned catalyst activity composition and these to reacting inactive material or tackiness agent etc.; Do not contain these when reacting inactive material or tackiness agent etc., the catalyst activity composition itself is called catalyzer.
The condition of the particle diameter of catalyzer when synthetic is different, and 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, operability was poor, and any situation all is not preferred.This median size can be observed to wait by SEM and be obtained.
The preparation method of＜catalyzer 〉
The preparation method of the catalyzer that uses among the present invention is not particularly limited, usually can be according to the known method preparation that is called as Hydrothermal Synthesis.In addition, behind Hydrothermal Synthesis, can also be by ion-exchange, dealumination treatment, soak into or the modification such as support and change composition.
The catalyzer that the present invention uses as long as have above-mentioned physical property and composition, then can be the material that adopts the either method preparation in supplying to reaction the time.
[reaction raw materials]
Then, ethanol as reaction raw materials, ethene etc. are described in the present invention.
＜ethanol 〉
Ethanol as reaction raw materials is not particularly limited.Such as using arbitrarily the ethanol that utilizes known the whole bag of tricks to obtain as described below: the ethanol that utilizes ethanol that the hydration reaction of ethene makes, made by synthesis gas, the ethanol that will make as raw material and by fermentation from the polyose of plant etc.At this moment, both can directly use the ethanol of the state that is mixed with arbitrarily the compound (particularly water) that in various manufacture method, produces, also can use the ethanol after making with extra care.
＜ethene 〉
Ethene as reaction raw materials is not particularly limited.Such as using arbitrarily the ethene that utilizes known the whole bag of tricks to obtain as described below: the ethene that utilizes catalystic pyrolysis or steam splitting process etc. to be made by the oil base feed, hydrogen/the Co mixed gas that utilizes coal gasification to obtain is carried out FT (Fischer-Tropsch process, the ethene that Fischer-Tropsch) is synthesized into as raw material, utilize the dehydriding of ethane or the ethene that the oxydehydrogenation method obtains, the ethene that obtains is reacted in replacement(metathesis)reaction and homology materialization (homologation) by propylene, react the ethene that obtains by MTO, ethene that dehydration reaction by ethanol obtains etc.At this moment, both can directly use the ethene of the state that is mixed with arbitrarily the ethene compound in addition that in various manufacture method, produces, also can use the ethene after making with extra care.
In addition, when utilizing method of the present invention to make propylene, the ethene recycling that contains in the reactor outlet gas can also be used.
＜other raw material 〉
In the present invention, except above-mentioned ethanol or ethene, can also there be the alkene of carbonatoms more than 4 in the reaction raw materials.As the alkene of carbonatoms more than 4, be not particularly limited, for example when making propylene by manufacture method of the present invention, the alkene recycling that contains in the reactor outlet gas can be used.Because the part of the alkene of carbonatoms more than 4 is converted to propylene, therefore by with the recycling of the alkene in the reactor outlet gas, can improve the total recovery of propylene.
In addition, can also there be oxygenatedchemicals except ethanol.As the oxygenatedchemicals except ethanol, for example can enumerate methyl alcohol or dme.
[operation, condition]
Below, operation, the condition of the propylene manufacturing reaction of the present invention of using above-mentioned catalyzer and reaction raw materials are described.
(1) reaction method
(reactor)
In the present invention, the form of the reactor of use is not particularly limited, and usually selects fixed-bed reactor or the flowing bed reactor of continous way.The preferred flow bed bioreactor.
In addition, when above-mentioned catalyzer is filled in flowing bed reactor, for the temperature distribution with catalyst layer is suppressed at very littlely, quartz sand, aluminum oxide, silicon-dioxide, silica-alumina etc. can be filled after reacting inactive saccharoid and catalyst mix.At this moment, quartz sand etc. is not particularly limited the usage quantity of reacting inactive saccharoid.In addition, from considering with the even Combination aspect of catalyzer, this saccharoid preferably with the particle diameter of catalyzer same degree.
The heating that produces in order to disperse to be accompanied by reaction, can be in the reactor supply response matrix (reaction raw materials) in batches.
During the selective flow bed bioreactor, preferred: the revivifier of catalyzer is set at reactor, and the catalyzer that will extract out from reactor is delivered to revivifier continuously, the catalyzer of in revivifier regenerating continuously turned back in reactor on one side react on one side.
Here, as the revivifier of catalyzer, can enumerate by with the revivifier that contains the nitrogen of aerobic or water vapour etc. and process the catalyst regeneration that will import from reactor.
[substrate concn]
Supply with ethanol and at least a concentration in the ethene (being substrate concn) in compositions about all that are supplied to reactor, be not particularly limited, but ethanol and ethene sum be preferably all supply with in compositions below 90 % by mole.More preferably 5 % by mole～70 % by mole.If this substrate concn is too high, then the generation of aromatics or paraffinic becomes significantly, and the yield of propylene has the tendency of reduction.If substrate concn is excessively low, then speed of response is slack-off, therefore needs a large amount of catalyzer, and reactor has the tendency that too becomes large.
Therefore, in order to obtain such substrate concn, as required, preferably use the thinner of following record with at least a dilution in ethanol and the ethene.
(thinner)
At least a in the reactor in ethanol and ethene, can also exist hydro carbons, aromatics class and their mixture etc. of helium, argon, nitrogen, carbon monoxide, carbonic acid gas, hydrogen, water, paraffinic, methane etc. to reacting inactive gas, wherein, preferred coexistence has water (water vapour).
As such thinner, both can directly use the impurity that contains in the reaction raw materials, also can with the thinner for preparing in addition with re-use after reaction raw materials mixes.
In addition, thinner both can mix with reaction raw materials before entering reactor, also can be supplied to respectively reactor with reaction raw materials.
(2) reaction conditions
(space velocity)
Here said space velocity, refer to the flow as at least a weight with respect to catalyzer (catalyst activity composition) in the ethanol of reaction raw materials and the ethene, said catalyst weight 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 here.In addition, flow is total (that is being its total amount when, using ethanol and ethene) flow (weight/time) at least a in ethanol and the ethene.
The preferred 0.01Hr of space velocity -1～500Hr -1Between, more preferably 0.1Hr -1～100Hr -1Between.When space velocity was too high, it is many that the ethene in the reactor outlet gas becomes, the propene yield step-down, thereby not preferred.In addition, space velocity is crossed when hanging down, and generates the preferred by products such as paraffinic, and propene yield reduces, thereby not preferred.
(temperature of reaction)
As the lower limit of temperature of reaction, usually be about more than 200 ℃, be preferably more than 300 ℃; As the upper limit of temperature of reaction, be generally below 700 ℃, be preferably 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, lower same) usually, is preferably below the 1MPa, more preferably below the 0.7MPa.In addition, the lower limit of reaction pressure is not particularly limited, but is generally more than the 1kPa, is preferably more than the 50kPa.When reaction pressure was too high, the growing amount of the not preferred by product of paraffinic etc. 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.
(transformation efficiency)
In the present invention, preferably in ethanol and ethene at least a transformation efficiency (by at least a transformation efficiency that is converted into the compound except ethanol and ethene in ethanol and the ethene) be to react under 20%～80% the condition.
During this transformation efficiency less than 20%, unreacted ethanol or ethene are many, and propene yield is low, thereby not preferred.On the other hand, when this transformation efficiency surpassed 80%, the by product of not expecting of paraffinic etc. increased, and propene yield reduces, thereby not preferred.Transformation efficiency more preferably 20%～70%.
When reacting with flowing bed reactor, by adjusting the residence time of catalyzer in reactor and the residence time in revivifier, can be with preferred transformation efficiency running.
(3) resultant of reaction
As reactor outlet gas (reactor effluent), obtain containing the mixed gas of propylene, ethene, by product and thinner as resultant of reaction.Density of propylene in this mixed gas is generally 1～95 % by weight, is preferably 2～80 % by weight.
According to reaction conditions, contain ethanol in this mixed gas, do not react but preferably in reactor outlet gas, do not contain fully under the reaction conditions of ethanol.Thus, easy separating reaction resultant and unreacting material.
Usually contain ethene in this mixed gas, preferably at least a portion of the ethene in this mixed gas is recycled in the reactor and recycles as reaction raw materials.
In addition, as by product, can enumerate olefines, paraffinic, aromatics and the water of carbonatoms more than 4.
(4) separation of resultant
Mixed gas as the propylene that contains resultant of reaction, ethene, by product and the thinner of reactor outlet gas material can be imported to knownly separate, in the purifier apparatus, according to each composition reclaim, the processing of purifying, recycling, discharge.
Part or all of composition except propylene (alkene, paraffinic hydrocarbons etc.), particularly ethene preferably mix or directly supply to reactor with reaction raw materials behind above-mentioned separation, purifying and recycles.In addition, in the by product, can be used as thinner and recycle reacting inactive composition.
[polyacrylic manufacturing]
Polyacrylic manufacture method of the present invention is to use according to the propylene of the manufacture method manufacturing of the propylene of the invention described above to make polyacrylic method.
This polyacrylic manufacture method is not particularly limited, can be according to usual method at propylene polymerization with making propylene carry out polyreaction in the presence of the catalyzer.
Embodiment
Below, enumerate embodiment and be described more specifically the present invention, but the present invention is not subjected to any restriction of following examples.
＜embodiment 1 〉
Catalyzer is the proton type aluminosilicate with CHA structure, uses SiO 2/ Al 2O 3The aluminosilicate of=36 (mol ratios) as raw material, carries out the manufacturing of propylene with ethanol as catalyzer according to the present invention.In the aperture of this aluminosilicate, minor axis, major diameter are 0.38nm.
In reaction, use atmospheric fixed bed circulation reaction unit, the mixture of the above-mentioned catalyzer of 100mg and 400mg quartz sand is filled in the crystal reaction tube of internal diameter 6mm.Make ethanol and nitrogen by vaporizer take the space velocity of ethanol as 0.3Hr -1Being supplied in the reactor, is 90 volume % so that ethanol is 10 volume % and nitrogen, reacts under 400 ℃, 0.1MPa.The reaction beginning is carried out the analysis of resultant after rear 3.5 hours with gas chromatograph.
Table 1 shows reaction result.
In addition, become ethene owing to ethanol enters to dewater immediately behind the reactor, so transformation efficiency is ethanol/conversion of ethylene, calculates with { mole number of the ethanol of (mole number of the ethene of the mole number-reactor outlet of the ethanol of supply)/supply with }.In addition, the selection rate of each resultant is with the carbon % by mole calculating of the composition except ethene in the reactor outlet gas, and propene yield is that the product with ethanol/conversion of ethylene and propylene selection rate calculates.
As shown in table 1, obtain following result: transformation efficiency is 51.6%, when the propylene selection rate is 81.3%, and both are all very high, and propene yield is 41.9%.Therefore as can be known: in the present embodiment, if with the recycling of the ethene in the reactor outlet gas, then the total recovery of propylene can be for more than 80%.
＜embodiment 2 〉
React under similarly to Example 1 catalyzer and reaction conditions, difference is: the space velocity of ethanol is 0.6Hr -1, alcohol concn is that 30 volume %, nitrogen are 70 volume %.The reaction beginning is carried out the analysis of resultant after rear 4.5 hours with gas chromatograph.
Table 2 shows reaction result.
As shown in table 2, obtain following result: transformation efficiency is 65.1%, when the propylene selection rate is 63.0%, and both are all very high, and propene yield is 41.1%.
＜embodiment 3 〉
React under similarly to Example 1 catalyzer and reaction conditions, difference is: it is that 30 volume %, nitrogen concentration are that the space velocity of 70 volume %, ethene is 0.4Hr that raw material is become ethene, ethylene concentration by ethanol -1The reaction beginning is carried out the analysis of resultant after rear 3.3 hours with gas chromatograph.Table 2 shows reaction result.
As shown in table 2, obtain following result: transformation efficiency is 73.7%, the propylene selection rate is 54.6%, and both are all very high, and propene yield is 40.3%.
＜embodiment 4 〉
React under reaction conditions similarly to Example 3, difference is: as catalyzer, use the proton type aluminosilicate with LEV structure, wherein SiO 2/ Al 2O 3=30 (mol ratios), and to have minor axis be that 0.36nm, major diameter are the pore of 0.48nm.The reaction beginning is carried out the analysis of resultant after rear 1.0 hours with gas chromatograph.
Table 2 shows reaction result.
As shown in table 2, obtain following result: transformation efficiency is 71.2%, the propylene selection rate is 57.4%, and both are all very high, and propene yield is 40.9%.
＜comparative example 1 〉
React under reaction conditions similarly to Example 1, difference is: as catalyzer, use the proton type aluminosilicate (H-ZSM5) with MFI structure, wherein SiO 2/ Al 2O 3=311 (mol ratios), and to have minor axis be that 0.51nm, major diameter are that pore and the minor axis of 0.55nm is that 0.53nm, major diameter are the pore of 0.56nm.The reaction beginning is carried out the analysis of resultant after rear 2.0 hours with gas chromatograph.Table 1 shows reaction result.
As shown in Table 1: transformation efficiency is 34.4%, the propylene selection rate is 32.2%, and propene yield is 11.1%, does not obtain enough yields.
＜comparative example 2 〉
Except using the proton type silicoaluminophosphamolecular molecular sieves (SAPO-34) with CHA structure that synthesizes according to No. 4440871 specification sheetss of United States Patent (USP) as the catalyzer, under reaction conditions similarly to Example 1, react.The reaction beginning is carried out the analysis of resultant after rear 3.3 hours with gas chromatograph.Table 1 shows reaction result.In addition, this silicoaluminophosphamolecular molecular sieves is to have the material that minor axis, major diameter are the pore of 0.38nm.
As shown in Table 1: transformation efficiency is 5.7%, the propylene selection rate is 88.5%, and propene yield is 5.0%, does not obtain sufficient yield.
＜comparative example 3 〉
Except using proton type aluminosilicate, the SiO with FAU structure 2/ Al 2O 3=7 (mol ratios), minor axis, major diameter are the material of fine pore of 0.74nm as beyond the catalyzer, react under reaction conditions similarly to Example 3.The reaction beginning is carried out the analysis of resultant after rear 5.7 hours with gas chromatograph.Table 2 shows reaction result.
By table 2 can be 14.6% with: transformation efficiency, when the propylene selection rate is 10.5%, propene yield is 1.5%, does not obtain sufficient yield.
[table 1]
Embodiment 1 Comparative example 1 Comparative example 2
The kind of catalyzer Aluminosilicate Aluminosilicate Silicoaluminophosphamolecular molecular sieves
The structure of catalyzer Eight Yuans rings of CHA Ten Yuans rings of MFI Eight Yuans rings of CHA
Major diameter * the minor axis of pore (nm) 0.38×0.38 0.55×0.51 0.38×0.38
Raw material Ethanol Ethanol Ethanol
Alcohol concn (volume %) 10 10 10
Ethanol feed rate (mmol/hrg-cat) 6.25 6.25 6.25
Ethanol WHSV (hr -1) 0.29 0.29 0.29
Ethanol/conversion of ethylene 51.6％ 34.4％ 5.7％
The propylene selection rate 81.3％ 32.2％ 88.5％
The butylene selection rate 5.8％ 36.3％ 4.8％
C5 +Alkene (※) selection rate 0.8％ 23.0％ 0.0％
The paraffinic selection rate 12.1％ 1.9％ 6.7％
The aromatics selection rate 0.0％ 6.6％ 0.0％
Propene yield 41.9％ 11.1％ 5.0％
The alkene of ※ carbonatoms more than 5
[table 2]
Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 3
The kind of catalyzer Aluminosilicate Aluminosilicate Aluminosilicate Aluminosilicate
The structure of catalyzer Eight Yuans rings of CHA Eight Yuans rings of CHA Eight Yuans rings of LEV The FAU 12-membered ring
Major diameter * the minor axis of pore (nm) 0.38×0.38 0.38×0.38 0.48×0.36 0.74×0.74
Raw material Ethanol Ethene Ethene Ethene
Ethanol/ethylene concentration (volume %) 30 30 30 30
Ethanol/ethene feed rate (mmol/hrg-cat) 13 13 13 13
Ethanol/ethene WHSV (hr -1) 0.60 0.37 0.37 0.37
Ethanol/conversion of ethylene 65.1％ 73.7％ 71.2％ 14.6％
The propylene selection rate 63.0％ 54.6％ 57.4％ 10.5％
The butylene selection rate 15.1％ 19.8％ 10.3％ 14.5％
C5 +Alkene (※) selection rate 15.2％ 17.8％ 18.5％ 1.3％
The paraffinic selection rate 6.2％ 6.9％ 10.5％ 73.7％
The aromatics selection rate 0.5％ 0.9％ 3.3％ 0.0％
Propene yield 41.1％ 40.3％ 40.9％ 1.5％
The alkene of ※ carbonatoms more than 5
Describe the present invention with reference to detailed or specific embodiment, but only it will be recognized by those skilled in the art that otherwise exceeding the spirit and scope of the present invention just can implement various changes or correction.
The application is based on the Japanese patent application (Patent 2006-094538) of filing an application on March 30th, 2006, and its content is incorporated among the application as reference.
Industrial applicibility
The invention provides a kind of with high yield by the method for at least a production propylene in ethanol and the ethene and by making polyacrylic method by the propylene of the method manufacturing.The present invention can seek the reduction of carrying capacity of environment by by using the propylene of making from the bio-ethanol of the raw material of plant to make polypropylene as widely used resin.

Claims (8)

1. the manufacture method of a propylene, it is at least a method that contacts to make propylene with catalyzer that makes in reactor in ethanol and the ethene, wherein, above-mentioned catalyzer contains aluminosilicate as the catalyst activity composition, and described aluminosilicate has the aperture of not enough 0.5nm.
2. the manufacture method of propylene claimed in claim 1, wherein, the catalyst activity composition is the aluminosilicate with eight Yuans rings or nine Yuans rings.
3. the manufacture method of propylene claimed in claim 2, wherein, the structure of aluminosilicate is CHA.
4. the manufacture method of each described propylene in the claim 1～3, wherein, the SiO of aluminosilicate 2/ Al 2O 3Mol ratio is more than 5.
5. the manufacture method of each described propylene in the claim 1～4 wherein, is utilized the equipment that possesses flowing bed reactor and revivifier, and the manufacturing of propylene is carried out on cyclic regeneration catalyzer limit, limit.
6. the manufacture method of each described propylene in the claim 1～5, wherein, at least a transformation efficiency in ethanol and ethene is to react under 20%～80% the condition, and described transformation efficiency is for being converted into the transformation efficiency of the compound beyond ethanol and the ethene by at least a in ethanol and the ethene.
7. the manufacture method of each described propylene in the claim 1～6 wherein, is recycled at least a portion of the ethene that contains in the reactor outlet gas in the reactor.
8. polyacrylic manufacture method, the method has following operation:
Make the operation of propylene by each described method in the claim 1～7; And
The propylene of making in the above-mentioned operation is made polyacrylic operation as raw material.
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