CN109071378A - The manufacturing method of light alkene - Google Patents
The manufacturing method of light alkene Download PDFInfo
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- CN109071378A CN109071378A CN201680084499.6A CN201680084499A CN109071378A CN 109071378 A CN109071378 A CN 109071378A CN 201680084499 A CN201680084499 A CN 201680084499A CN 109071378 A CN109071378 A CN 109071378A
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- zeolite
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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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
-
- 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 present invention provides a kind of manufacturing method of light alkene, it has and makes the raw material containing at least one of group for being made of methanol and dimethyl ether is selected from, the Contact operation contacted in reactor with the shaped body catalyst containing zeolite, total amount of the raw material relative to the raw material, at least one of the group being made of methanol and dimethyl ether 10 mass % or more are selected from containing this, this contains the zeolite in the shaped body catalyst of zeolite and meets following (1)~(4): (1) zeolite is intermediate pore size zeolite, (2) zeolite contains substantially no proton, (3) zeolite contains silver, (4) the silica alumina molar ratio (SiO of the zeolite2/Al2O3Molar ratio) it is 800 or more and 2000 or less.
Description
Technical field
The present invention relates to the manufacturing methods of light alkene.
Background technique
In recent years, among the method for the manufacture light alkenes such as ethylene and propylene, propylene is manufactured by methanol and/or dimethyl ether
Method attract attention (referring for example to patent document 1).In addition, also proposed by the method (example of ethylene and methanol manufacture propylene
As referring to patent document 3).As catalyst used in these methods, zeolite catalyst is proposed, is specifically proposed
SAPO-34 type and ZSM-5 type both.
Such as the manufacture of the catalyst and the catalyst that make methanol be converted into light alkene is disclosed in patent document 1
Method and application method.Among the disclosure, the zeolite catalyst of SAPO-34 type is special catalyst.
In addition, being disclosed in patent document 2 for utilizing includes the reactor of moving bed reactor, the confession that will generate oxygen
The continuous processing of propylene is selectively converted to raw material.Specifically, disclosing by the inclusion of molecular sieve, having and generate oxygen
At least part of object is converted into the ability of C3 alkene and two elementary works by C2 and C4 olefin interconversion inversion of phases for the ability of C3 alkene
Energy catalyst granules, the method for making the raw material be converted into propylene.It also discloses as the two meta functions catalyst, using with phase
When in ZSM-5 structure, be equivalent to SAPO-34 structure zeolite.
In turn, it is disclosed in patent document 3 and to manufacture propylene using ethylene and methanol and/or dimethyl ether as raw material
In method, provide the recycling amount of unreacting ethylene less, the low novel process of installation cost, service charge.It is recorded in the patent document
Embodiment used in catalyst be H-ZSM-5 type zeolite that silica alumina molar ratio is 1100.
In addition, the yield for improving propylene, the aromatic compound for taking out high additive value are disclosed in patent document 4 in turn
Object, the method for obtaining the high-quality gasoline without containing aromatic compound.The patent document record method be characterized in that,
Dimethyl ether reaction is set to obtain the reaction mixture containing light alkene class and gasoline hydrocarbon on catalyst in reactor, it will
It is separated into C5 alkene mixture, the gasoline mixture of C5 or more and water phase using the first separator, by the gasoline of C5 or more
Mixture is supplied to the second separator, by the most aromatic compound contained in mixture separate and recover, will residual at
At least part divided is recycled to reactor as recycling stream.Used catalyst is preferably ZSM-5 type.
In turn, in addition, being disclosed in patent document 5 comprising containing substantially no proton and containing silver-colored intermediate pore size boiling
The catalyst of stone.It is disclosed in the patent document by the method for hydrocarbon manufacture ethylene and propylene containing C4~C12 alkene.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2008-544941 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2008-504273 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2008-106056 bulletin
Patent document 4: No. 2009/0124841 bulletin of US publication
Patent document 5: No. 2000/10948 pamphlet of International Publication
Summary of the invention
Problems to be solved by the invention
But it is industrially manufactured using above-mentioned zeolite catalyst in the prior art, by methanol and/or dimethyl ether low
In the case where grade alkene, at least there is a problem of following.
Firstly, the zeolite catalyst of SAPO-34 type, due to its fine pore is small, the deterioration of the activity caused by coking is aobvious
It writes.Therefore, in order to manufacture light alkene in circulating fluidized bed system, the circulation of great catalyst is needed.In addition, due to coke
The activity deterioration of catalyst caused by change is significant, therefore it is further low to obtain to cannot achieve the obtained olefines of recycling
Grade alkene.These features are very unfavorable in industrial implementation.
On the other hand, using the zeolite catalyst of ZSM-5 type using methanol and/or dimethyl ether as the rudimentary alkene of raw material
Aromatic series in the manufacturing method of hydrocarbon, in the case where activity appropriate and hyperactivity cannot be controlled in, as by-product
The selection rate for closing object increases, and the selection rate of propylene reduces.At the same time, there is also the catalyst degradations caused by coking to add
Fast problem.Here, for the used catalyst for deteriorating activity due to coking, it can be empty by carrying out the coke
Gas burns to regenerate.But the vapor generated in the regeneration can promote the dealuminzation of zeolite skeleton, therefore cause in the regeneration not
The activity deterioration for the catalyst that can restore.In addition, the more more then more significant progress of the deterioration caused by the dealuminzation of amount of coke.
In addition, must need largely to urge to convert methanol and/or dimethyl ether completely in the case that activity is too low
Agent.Therefore, it in the case where manufacturing light alkene using the zeolite catalyst of ZSM-5 type, for active purpose is controlled, needs
To implement pre-treatment to not used catalyst (after preparation, not yet for the catalyst of Contact operation) to which activity is most suitable
Change.
But in the case where processing before the zeolite catalyst to ZSM-5 type is implemented is to by its active most appropriate, by
It is very narrow in the active OK range, thus using well known pre-treatment carry out catalyst activity most appropriate when, adjusted
The whole active reproducibility to OK range lacks.Therefore it in order to industrially implement, needs to find to be easy and reproducibility is good
The method for carrying out well realizing yield and active most appropriate using the pre-treatment of catalyst.
Therefore, the object of the present invention is to provide the rudimentary alkene for the light alkene that can obtain high yield steadily in the long term
The manufacturing method of hydrocarbon.
The solution to the problem
The inventors of the present invention further investigate to solve above-mentioned prior art problem, as a result, it has been found that, by using tool
By make the raw material selected from least one of the group being made of methanol and dimethyl ether containing prescribed limit amount, with defined boiling
The manufacturing method of the light alkene for the Contact operation that stone catalyst contacts in reactor can obtain in high yield steadily in the long term
Light alkene, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of manufacturing method of light alkene, having makes containing in the group being made of methanol and dimethyl ether
At least one raw material, the Contact operation that is contacted in reactor with the shaped body catalyst containing zeolite,
Total amount of the raw material relative to the raw material, containing it is described in the group being made of methanol and dimethyl ether extremely
Few one kind 10 mass % or more,
Zeolite in the shaped body catalyst containing zeolite meets following (1)~(4):
(1) zeolite is intermediate pore size zeolite,
(2) zeolite contains substantially no proton,
(3) zeolite contains silver,
(4) the silica alumina molar ratio (SiO of the zeolite2/Al2O3Molar ratio) it is 800 or more and 2000 or less.
[2] manufacturing method of the light alkene according to [1], wherein in the shaped body catalyst containing zeolite
Zeolite also contain alkali metal.
[3] manufacturing method of the light alkene according to [1] or [2], wherein for the formed body containing zeolite
Catalyst is heated in the presence of vapor and oxygen, at 500 DEG C or more.
[4] manufacturing method of the light alkene according to any one of [1]~[3], wherein it is described containing zeolite at
The cationic occupation rate of the silver relative to cationic site of zeolite in shaped body catalyst is 10% or more and 70% or less.
[5] manufacturing method of the light alkene according to any one of [1]~[4], wherein it is described containing zeolite at
Shaped body catalyst also contains silica.
[6] manufacturing method of the light alkene according to any one of [1]~[5], wherein the reactor is fluidisation
The reactor of bed or fixed-bed type.
[7] manufacturing method of the light alkene according to any one of [1]~[6], wherein the raw material also contains alkene
Hydro carbons.
The effect of invention
The manufacturing method of light alkene according to the present invention can manufacture the light alkene of high yield steadily in the long term.
Specific embodiment
It is described in detail below for embodiments of the present invention (hereinafter referred to as " present embodiment ").Below reality
Applying mode is for illustrating illustration of the invention, and the present invention is not limited to the following embodiments and the accompanying drawings.The present invention is without departing from its master
Various modifications are able to carry out in the range of purport.
[manufacturing method of light alkene]
The manufacturing method of the light alkene of present embodiment has and makes containing being selected from the group that is made of methanol and dimethyl ether
At least one of raw material, inscribed in reactor with the shaped body catalyst (being also only called " catalyst " below) containing zeolite
The Contact operation of touching.In addition, total amount (100 mass %) of the raw material relative to the raw material, is selected from containing being somebody's turn to do by methanol and diformazan
At least one of the group of base ether composition 10 mass % or more.And then it is somebody's turn to do the zeolite in the shaped body catalyst containing zeolite and meets
Following (1)~(4):
(1) zeolite is intermediate pore size zeolite,
(2) zeolite contains substantially no proton,
(3) zeolite contains silver,
(4) the silica alumina molar ratio (SiO of the zeolite2/Al2O3Molar ratio) it is 800 or more and 2000 or less.
Here, light alkene refers to that carbon number (is referred to as by the alkene of carbon number 2~5 sometimes below in this specification
"C").Additionally, it is preferred that light alkene be propylene.
[Contact operation]
The Contact operation of present embodiment is to make raw material, contact in reactor with the shaped body catalyst containing zeolite
Process.In addition, raw material can also contain olefines in Contact operation.In turn, in Contact operation, from obtaining higher yield
Light alkene from the viewpoint of, alkene that raw material is preferably also generated containing the manufacturing method by the light alkene of present embodiment
At least part of hydro carbons.
<raw material>
The raw material of present embodiment at least contains selected from least one of the group that is made of methanol and dimethyl ether, can be with
Also contain olefines.Raw material contains relative to the total amount (100 mass %) of the raw material selected from being made of methanol and dimethyl ether
At least one of group 10 mass % or more, 25 mass % or more are preferably comprised.The methanol that contains in raw material and dimethyl ether
Total amount is 100 mass % hereinafter, containing in the case where olefines, and preferably the total amount is 90 mass % or less.
In this specification, " total amount of raw material " is the quality containing methanol, dimethyl ether and olefines, change in addition to this
Close object even if belong to raw material, without containing in the total amount of raw material.Thus without containing in the case where olefines, certain raw material contains choosing
100 mass % of at least one of the group of free methanol and dimethyl ether composition.
The olefines of present embodiment is preferably the olefines of the olefines of carbon number 2~8, more preferable carbon number 2~6.These
Olefines is supplied preferably as the raw material for being mixed in methanol and dimethyl ether.Alternatively, it is also possible to by the boiling with present embodiment
Product composition obtained from the contact of stone catalyst, using known distillation purifying process, by desired light alkene class
Separation and recovery recycles a part of olefines in addition to this or total amount.It should be noted that so-called in this specification
" olefines " includes also loop chain alkane, also may include diene, alkynes class other than straight-chain, branched and cyclic olefin.
In present embodiment, by recycling at least part of olefines generated, this implementation can effectively be obtained by existing
The tendency of the light alkene of the purpose of mode.
In reaction product, other than light alkene, there is also the olefines of 6 or more carbon number and a small amount of aromatic hydrocarbons.
Here, desired light alkene is separated and recovered by reaction product, by the olefines of the carbon number 2~8 contained in residual component
It is reused in reactor, thus there is the tendency for the yield that can be further improved desired light alkene.
In addition, there is the water from left away water in reacting environment due to using methanol and/or dimethyl ether as raw material
Steam.The zeolite contained in known usually previous catalyst dealuminzation, deterioration due to high-temperature vapor, but utilize this implementation
When the catalyst of mode, even if being not easy to produce the deterioration of zeolite in the case where vapor coexists.The contact work of present embodiment as a result,
In sequence, with can need not separating vapor using the catalyst of present embodiment.
For (allowing desired light alkene separation and recovery, the recycling ratio of residual component sharp again as raw material
Quality ratio), the total amount (100 mass %) relative to raw material is preferably 10 mass % or more and 95 mass % or less, more
It is preferred that 15 mass % or more and 90 mass % or less.
In addition, also can be by not recycling aromatic hydrocarbon for the residual component of recycling.In turn, reaction is supplied raw material into
It, can be with mixed diluting gas when device.As the diluent gas, can enumerate non-live such as hydrogen, methane, vapor, nitrogen
Property gas, it is preferred that for the diluent gas other than hydrogen.Although this is because there is the coking deterioration for inhibiting catalyst in hydrogen
Tendency, but cause the hydrogenation for generating propylene etc., cause purified propylene (density of propylene [mole %] in C3 fraction:
Propylene/(propylene+propane) × 100) reduction.In the manufacture for industrially implementing light alkene, purified propylene height is important.
In present embodiment, even if not using hydrogen, the coking deterioration of catalyst is also small, can steadily operate.
<shaped body catalyst containing zeolite>
(intermediate pore size zeolite)
The shaped body catalyst for containing zeolite of present embodiment contains zeolite as primary catalyst component.The zeolite is
Intermediate pore size zeolite.Intermediate pore size zeolite refers to havingAbove andThe zeolite of fine pore below.In addition, claiming
Refer to that " range of fine pore is in using type A zeolite as the thin of the small-bore zeolite of representative for the term of " intermediate pore size zeolite "
Aperture and using modenite, X-type, y-type zeolite as the zeolite of the centre of the fine pore of the large aperture zeolite of representative ", be its crystal
With the zeolite of so-called 10 member ring of oxygen in structure.
As intermediate pore size zeolite, be not limited to hereinafter, can enumerate such as ZSM-5, ZSM-8, ZSM-11, ZSM-12,
The zeolite of ZSM-21, ZSM-23, ZSM-35, ZSM-38 type.Among them, preferably ZSM-5 type zeolite.The structure type of zeolite
It can confirm by using X-ray powder resolver and compared with well known Zeolite Diffraction pattern.
(proton amount)
Zeolite in the shaped body catalyst containing zeolite of present embodiment contains substantially no proton.It is substantially free of
There is proton to refer to the proton in the zeolite found out by the ion exchange in solution/filtrate titration recorded in aftermentioned embodiment
Amount (acid amount) every 1 gram of zeolite is 0.02 mM or less.The proton amount of preferably above-mentioned every 1 gram of zeolite be 0.01 mM with
Under zeolite.
Ion exchange in solution/filtrate titration refers to Intrazeolite Chemistry, " ACS Symp.Ser. ",
218, P369-382 (1983, the U.S.), Japanization association will, [3], the method P.521-527 recorded in (1989) etc..It uses
The measurement of proton amount in the present embodiment of this method carries out as described below.For containing zeolite by roasting in air
Shaped body catalyst, using NaCl aqueous solution carry out ion-exchange treatment after, by filtering catalyst is recycled while, obtain
To filtrate.Obtained washing lotion total amount is recycled, is mixed with above-mentioned filtrate by the catalyst pure water recycled.It is acquired
Mixed solution in proton amount found out by acid-base titration, be scaled the value conduct of the zeolite unit mass contained in catalyst
The proton amount of zeolite.Proton amount is measured by the method recorded in aftermentioned embodiment.
The zeolite of ammonium ion type and multivalent metal cation type generates proton by heat treatment.Therefore, upper in utilization
Before stating the measurement that method carries out proton amount, calcination process is carried out for the shaped body catalyst containing zeolite.
(containing silver)
Zeolite in the shaped body catalyst containing zeolite of present embodiment contains silver.Refer to zeolite with silver containing silver
The state of corresponding cation (silver ion) contains silver.As the method for making zeolite contain silver, it can enumerate and for example pass through benefit
With the method that well known ion-exchange handles the zeolite without containing silver or shaped body catalyst containing zeolite come
The method contained., it is preferable to use the salt of silver can as the salt of silver in the case where making zeolite contain silver by ion-exchange
Enumerate such as silver nitrate, silver acetate and silver sulfate.
The amount for containing the silver in zeolite with cationic form is not particularly limited.But as described later, this reality
Apply the zeolite of mode silica alumina molar ratio be 800 or more and 2000 hereinafter, therefore by its ion exchange capacity and
Zeolite content in shaped body catalyst containing zeolite provides the preferred content.Therefore, silver-colored amount can pass through the phase of zeolite
The occupation rate of the silver cation in cationic site is indicated.That is, the silver cation relative to cationic site of zeolite accounts for
Have rate be preferably 10% or more and 70% or less, more preferable 10% or more and 50% or less, further preferred 10% or more and
30% or less.It is 10% or more by occupation rate, existing can be such that the activity of reaction is adequately inclined to, and be 70% by occupation rate
Hereinafter, in the presence of that can inhibit due to ion exchange ratio is excessively high and the tendency of hyperactivity.
The content of silver in zeolite or shaped body catalyst containing zeolite can pass through known method such as x-ray fluorescence
Analyze standard measure.On the other hand, the occupation rate relative to the silver cation in cationic site can be by for containing zeolite
Shaped body catalyst carries out ion exchange with sodium nitrate solution and measures the silver ion amount in filtrate to quantify, by this method,
The silver and silver in addition to this in the cationic site in zeolite can be distinguished.It should be noted that being not present in cation-bit
The silver of point will not be dissolved out by the ion exchange.In addition, the so-called silver sun relative to cationic site of present embodiment
The occupation rate of ion passes through the silica alumina of the zeolite found out using the analysis method recorded in aftermentioned embodiment
Than, the thus ratio table of the silver content (mM/g) for being present in cationic site relative to aluminium content (mM/g) that calculates
Show.It should be noted that the content of the silver in catalyst does not change before and after the processing in the steaming of aftermentioned present embodiment.
The zeolite of present embodiment utilizes the residual of silver cation exchange due to containing substantially no proton as described above
The cationic site stayed carries out ion exchange using the cation selected from least one of alkali and alkaline earth metal ions metal.
That is, zeolite contains the cation selected from least one of alkali and alkaline earth metal ions metal.The cation of the metal is preferably
Cation selected from least one of alkali metal metal is more preferably selected from least one of the group being made of sodium and potassium metal
Cation.That is, the zeolite in the shaped body catalyst containing zeolite of present embodiment is containing selected from alkali metal and alkaline earth
The zeolite of at least one of metal metal and silver the two.It should be noted that in the same manner as silver, " also containing alkali metal "
It refers to containing with the state of corresponding cation, such as carries out ion exchange with the nitric acid of 0.1N, for the alkali in filtrate
Metal ion is measured by inductively coupled plasma emission spectrographic analysis (ICP-AES), it is possible thereby to will be present in sun
The alkali metal of ionic sites is quantitative.It should be noted that the alkali metal for being not present in cationic site will not be by above-mentioned ion
It exchanges and dissolves out.The occupation rate of the alkali metal cation relative to cationic site of zeolite be take into account above-mentioned record silver sun from
Sub- occupation rate, Bronsted acid amount provide, are preferably in 30% or more and 90% or less range, are more preferably in 50% or more
And in 90% or less range, further preferably in 70% or more and 90% or less range.
Such as the zeolite as present embodiment, in the case where being fabricated to silver/sodium cation crossover, if in zeolite
There are alkali composition, then a part of silver cannot be loaded with silver-colored cationic form for the part in not cationic site, thus by catalyst at
When shape, zeolite is preferably converted into proton type.Therefore the forming containing zeolite that will preferably be shaped with proton type forms of zeolite
Zeolite in body catalyst is exchanged for sodium form (it is preferable to use sodium nitrate aqueous solutions) first, after forming sodium form (aprotic), is handed over
Change the method for importing silver cationic (it is preferable to use silver nitrate aqueous solutions).In addition, by for constituting the formed body containing zeolite
The content of the alkali metal component in ingredient other than the zeolite of catalyst is controlled, and carries out ion exchange for zeolite in advance
Afterwards, it can also fabricate as shaped body catalyst.
(silica alumina molar ratio)
Silica alumina molar ratio (the SiO of the zeolite of present embodiment2/Al2O3Molar ratio) be 800 or more and
2000 or less.The selection rate of the light alkene containing propylene reduces if silica alumina molar ratio is less than 800, in addition turns
Change the deterioration acceleration for reacting the adjoint shaped body catalyst caused by coking containing zeolite.Such as present embodiment
In the case that manufacturing method is implemented in such a way that 2 tower of fixed bed is swung, conversion frequency accelerates, therefore regeneration frequency increases.Therefore,
Regeneration deterioration accelerate.On the other hand, it is generated if silica alumina molar ratio is more than 2000 in catalyst manufacture
The problem of.In order to maintain high silicon dioxide alumina molar ratio the shaped body catalyst containing zeolite catalyst activity, system
When making the silver content for isodose, need to improve the cationic occupation rate of silver of zeolite.But the zeolite of present embodiment is passed through
Ion exchange and when being fabricated to non-proton, silver-colored crossover, if it is desired to improving the cationic occupation rate of silver, then exchange efficiency gradually becomes
Difference.In order to avoid this problem, need to increase the metal concentration in exchange liquid, if but the silica alumina molar ratio of zeolite
It is all difficult to carry out using the ion exchange of alkali metal progress, using the ion exchange that silver carries out more than 2000, therefore in industry
In the case where the upper manufacturing method for implementing present embodiment, catalyst manufacture needs for a long time, to additionally need increase ion exchange
Number.In addition, generate need overdose of medicine liquid measure, the problems such as waste liquid amount that generates therewith is also excessive.
The silica alumina molar ratio of zeolite in the shaped body catalyst containing zeolite of present embodiment is preferred
It is 800 or more and 1500 or less, more preferable 900 or more and 1200 or less.The silica alumina molar ratio of zeolite can lead to
Cross well known method, be for example dissolved completely in aqueous alkali or hydrofluoric acid aqueous solution, for obtained solution using plasma
Body emission spectrometry method is analyzed to find out.Specifically, being measured by the method recorded in aftermentioned embodiment.
As the zeolite of present embodiment, for example, also can be used constitute zeolite skeleton aluminium atom a part by Ga,
Metal aluminosilicates made of the element substitutions such as Fe, B, Cr, constitute zeolite skeleton aluminium atom all by above-mentioned element substitution and
At metal silicate.At this point, the content of the above-mentioned element in metal aluminosilicates or metal silicate is scaled aluminium oxide
Molal quantity after, calculate silica alumina molar ratio.
<binder>
For the shaped body catalyst containing zeolite of present embodiment, by aluminium oxide, silica, titanium dioxide
The porosity fire resistance inorganic oxide such as silicon/aluminium oxide, zirconium oxide, titanium dioxide, diatomite, clay is as binder or forming
With diluent (matrix) (also the two is merged be known as " binder etc. " below), is mixed in above-mentioned zeolite and obtain mixture, it will
Mixture forming, uses obtained formed body as catalyst.From the viewpoint of the intensity of catalyst and catalyst performance,
Preferably aluminium oxide, silica, from the viewpoint of not will form unwanted acid point from catalyst, more preferably titanium dioxide
Silicon.
As the raw material of silica, it is not limited to hereinafter, such as colloidal silicon dioxide, waterglass (silicic acid can be enumerated
Sodium), fumed silica, among them, the preferably colloidal state of the poor NH4 stable type of colloidal silicon dioxide, more preferable Na
Silica.
In the case that the Contact operation of present embodiment is carried out with fixed bed, preferably by well known method, for example squeeze out
Forming, tabletting forming shape zeolite and binder.
In the case that the Contact operation of present embodiment is carried out with fluidized bed, it is configured to be suitable for preferably by spray drying process
The particulate shot of fluidized bed.As described above, from the viewpoint of catalyst performance, the preferably binder etc. of silica.Make
For binder etc., in the case where using colloidal silicon dioxide, the partial size of silica preferably small, more preferable 4.0nm or more and
20nm or less, further preferred 4.0nm or more and 15nm or less.By using the small colloidal silicon dioxide of partial size, there is fluidisation
The tendency that the abrasion performance of the shaped body catalyst containing zeolite containing silica of bed improves.Here, silica
Partial size can be measured by dynamic light scattering formula particle size distribution analyzer.In the case where using binder etc., they contain
The total amount (100 mass %) relative to zeolite and binder etc. is measured, 10 mass % or more is preferably in and 90 mass % is below
Range is more preferably in 20 mass % or more and 70 mass % ranges below.
In addition, the raw material as silica, preferably mixed in spray-drying feedstock in the case where selecting colloidal silicon dioxide
It is water-soluble to close at least one of group for existing in liquid and being selected from and being made of nitrate, acetate, carbonate, sulfate and chloride
Compound.So-called herein " water soluble compound " refers to the solubility at 25 DEG C for the water of 100g with 1g or more
Compound.As water soluble compound, preferably respective ammonium salt, more preferable ammonium nitrate.
These water soluble compounds can also be simultaneously using a variety of.By the way that there are these in spray-drying feedstock mixed liquor
Water soluble compound, there are available excellent wear resistance, the internal tight structure for having gap few containing zeolite at
The tendency of shaped body catalyst is consequently adapted to the catalyst applications of fluidized-bed reaction.
The shaped body catalyst containing zeolite of present embodiment is in order to improve propene yield, further increase for coking
The patience of deterioration, as the pre-treatment before Contact operation, preferably for catalyst in the presence of steam, with 500
DEG C or more heated (hereinafter also referred to " steaming processing "), more preferably 500 DEG C or more and 900 DEG C temperature below,
More than 0.01 atmospheric pressure of steam partial pressure to carry out steaming processing.Steaming in this is handled, in order to be controlled in above-mentioned water
Partial vapour pressure, the progress under the coexisting as the nitrogen of removing gas, air and its mixed gas.Steaming processing is preferably total in oxygen
Progress is left, lower progress more preferably coexists in the oxygen of at least 0.1 mole % or more.The case where lower progress steaming processing coexists in oxygen
Under, desired active catalyst can be obtained well with reproducibility, thus it is speculated that this is because lower progress steaming processing coexists in oxygen
In the case where, the silver in the cationic site in zeolite can steadily exist.
The method of the activity control of shaped body catalyst usually as zeolite and containing zeolite, can be used above-mentioned steaming
Heat treatment.But in the case where using previous H-type zeolite catalyst, the processing method, the suitable performance range of manufacture are used
The catalyst of the narrow reaction for being most suitable for present embodiment is difficult.On the other hand, present embodiment contains zeolite
Shaped body catalyst handled by silver load capacity and steaming, can be easy and reproducibility manufacture well suitable for present embodiment
Light alkene manufacturing method desired performance catalyst.
The shaped body catalyst containing zeolite of present embodiment is possible to generate coking if being used for conversion reaction for a long time
Deterioration, in this case, usually in air or in the mixed gas comprising oxygen and non-active gas, with 400 DEG C or more and 700
DEG C temperature below burns the coke on catalyst removal, it is possible thereby to by produce coking deterioration catalyst regeneration (with
Under also by the processing be known as " regeneration treatment ").As described above, the shaped body catalyst containing zeolite of present embodiment is above-mentioned
The dealuminzation adjoint as the regeneration treatment of problem when be not easy to produce when regeneration treatment using common H-type zeolite catalyst.
Regeneration treatment can be implemented by well known method.In fixed bed, such as 2 towers swing mode, it can also hand over
For being reacted and regenerated.In addition, in fluid bed process, it can be using the catalyst regeneration and return for extracting autoreactor out
Method regenerator is arranged simultaneously makes a part of catalyst regeneration method while reactor and regenerator recycle.In addition,
The amount of coke for being piled up in catalyst can be found out by the mass change before and after thermogravimetric amount measurement etc., the regeneration of extraction catalyst.
In the Contact operation of present embodiment, the shaped body catalyst containing zeolite is filled into reactor, carries out original
The contact conversion reaction of material.Reaction temperature be preferably 400 DEG C or more and 600 DEG C or less, more preferable 450 DEG C or more and 580 DEG C with
Under.Operation pressure be preferably 0.01MPaG or more and 1.0MPaG or less, more preferable 0.05MPaG or more and 0.5MPaG with
Under.The weight time and space speed (WHSV) of raw material relative to catalyst quality is preferably 0.1hr-1Above and 100hr-1With
Under, more preferable 1hr-1Above and 10hr-1Below.
<reactor>
The reactor of present embodiment can use in fixed-bed type, moving-bed type, fluidized bed type and air-flow conveying type
Any one reactor controls easy viewpoint from reactivity and temperature and examines it is preferred that being fluidized bed type or fixed-bed type
Consider, more preferably fluidized bed type.Here, the generation reaction of the dimethyl ether carried out by methanol using dehydration is rubbed for 23kJ/
Your exothermic reaction.Therefore in the case where being implemented with fixed bed, it is desirable in the case where being reacted by material benzenemethanol with a stage,
Relatively difficult tendency is controlled there are the temperature of catalyst layer.
2CH3OH→CH3OCH3+H2O (23kJ/ moles)
Accordingly it is also possible to be set as 2 containers using reactor, dimethyl ether is synthesized, in the second reaction in first reactor
The method of device manufacture light alkene；In advance to the catalyst filling up and down of reactor, dimethyl is synthesized using the catalyst of upper section
Ether utilizes the method for the catalyst manufacture light alkene of lower section.At this point, this reality also can be used in dimethyl ether synthetic reaction
Known alumina catalyzation in known method also can be used in the shaped body catalyst containing zeolite for applying mode
Agent etc. is used as dimethyl ether catalyst for synthesizing.
Above as disclosing in this specification, the shaped body catalyst containing zeolite of present embodiment realizes high third
While alkene (alkene) yield, it is not likely to produce the deterioration when deterioration caused by coking, the regeneration treatment of combustion of coke, because
This reactor even if using fixed-bed type, can manufacture propylene steadily in the long term.In addition, even if using the anti-of fluidized bed type
In the case where answering device, the frequency of the circular regeneration processing of catalyst can also be low, is not likely to produce and deteriorates year in year out, therefore catalyst is mended
Charge can lack.It, can easily and reproducibility manufactures well has the property in addition, method according to the disclosure in this specification
The catalyst that the most suitable activity of energy is controlled.These features are industrially implemented extremely beneficial in present embodiment.
Embodiment
It is exemplified below out specific embodiment and present embodiment is described in more detail in comparative example, as long as but originally
Embodiment is no more than its purport then not by embodiment below and any restriction of comparative example.For find out aftermentioned embodiment and
The analysis method of the various physical property and evaluation that carry out in comparative example is as described below.
The proton amount that (physical property 1) is obtained using ion exchange in solution/filtrate titration
The formed body containing zeolite for being crushed with mortar, in air at a temperature of 400~600 DEG C by roasting is urged
Agent 2.5g in the NaCl aqueous solution 25mL of 3.4 mol/Ls, carries out 10 minutes ion exchanges under ice cooling.It will be obtained
After mixture filtering, with the pure water zeolite of 50mL, the filtrate total amount containing water used in washing is recycled.For the filter
Liquid (containing water used in washing) carries out acid-base titration by the NaOH aqueous solution of 0.1N, finds out proton amount by the point of neutralization, by
Zeolite content in shaped body catalyst containing zeolite is scaled zeolite quality criteria, as proton amount.
(physical property 2) silica alumina ratio
Zeolite 0.2g is added to the NaOH aqueous solution 50g of 5N.It is transferred into band teflon (registered trademark) inner tube processed
Stainless steel miniature gas storage bottle, miniature gas storage bottle is closed.It is kept for 15~70 hours in oil bath, thus makes zeolite completely molten
Solution.The solution of obtained zeolite is diluted with ion exchange water, and the silicon, aluminum concentration in dilution utilize plasma emission spectroscopy
Analysis meter (ICP device) measurement, the silica alumina molar ratio of zeolite is calculated by the result.ICP device described below and
Its determination condition.
Device: JOBIN YVON (JY138ULTRACE) Neo-Confucianism electric corporation system
Silicon substrate IC's wavelength: 251.60nm
Aluminium measures wavelength: 396.152nm
Plasma power: 1.0kw
Atomizer gas: 0.28L/ minutes
Sheath gas: 0.3~0.8L/ minutes
Cooling gas: 13L/ minutes
The yield of (evaluation 1) methanol and/or dimethyl ether conversion ratio and each ingredient
Conversion ratio (conversion ratio of methanol and/or dimethyl ether benchmark) is calculated by following formula.
Conversion ratio=(methanol+dimethyl ether in raw material)-(methanol+dimethyl ether in exported product gas) ×
100 }/(methanol+dimethyl ether in raw material) (quality %)
In addition, the yield of each ingredient is set as the concentration (quality %) of the standard of the alkyl other than the amount of moisture in product.
(evaluation 2) PY purity
Purified propylene (" PY purity " is expressed as in table) is dense as the propylene in the C3 fraction (propylene and propane) of product
It spends [mole %], is calculated and found out by following formula.
Purified propylene [mole %]=propylene [mole]/(propylene [mole]+propane [mole]) × 100
[embodiment 1] fluidized-bed reaction
(process 1: the manufacture of catalyst raw mixture)
While by colloidal silicon dioxide (34 mass % of dioxide-containing silica) 882g stirring, 61 mass % nitric acid aqueous solutions are added
Solution (and the pure medicine system of light, special grade chemical) 18g after forming pH=1, further adds the ammonium nitrate as water soluble compound
(and the pure medicine system of light, special grade chemical) 100g.While by silicon dioxde solution stirring, the NH4 type of Zeolyst corporation is added
(trade name " ZD05020 " is completely dissolved, is measured using ICP MFI-1000 zeolite, as a result the silica alumina of the zeolite
Molar ratio is 980) 300g, is eventually adding water 1034g, is adjusted so that the solid component content of catalyst raw material is 30 matter
% is measured, is futher stirred at 25 DEG C 1 hour, obtains catalyst raw mixture.
(process 2: spray drying process)
Obtained catalyst raw material is mixed using spray dryer (the model OC-16 of great river original chemical industry machine corporation)
Object spray drying, thus obtains hirudo leech.Collar plate shape sprayer is used by spraying, in 230 DEG C of hot-wind inlet temperature, outlet temperature
It is carried out at 130 DEG C.
(process 3: calcining process)
Using Muffle furnace by obtained hirudo leech in air atmosphere, 700 DEG C roast 1 hour, obtain containing zeolite
Shaped body catalyst (contains 50 mass % of silica binder, 55 μm of average grain diameter).
(process 4: acid exchange process)
(10cc/g- molded zeolite is dispersed in 1N- aqueous solution of nitric acid by the obtained shaped body catalyst containing zeolite
Body), 1 hour ion-exchange treatment is carried out at room temperature.Then it is filtered, washes, dries, manufacture H crossover ZSM-5/
SiO2Shaped body catalyst (shaped body catalyst A).
(process 5: ion-exchange process)
It disperses obtained shaped body catalyst A in 1N sodium nitrate aqueous solution (10cc/g- Zeolite formed product), room temperature
The ion-exchange treatment of lower repetition 1 hour 3 times.Then it is filtered, washes, dries, manufacture Na crossover ZSM-5/SiO2At
Shaped body catalyst.It is scattered in 0.00054N silver nitrate aqueous solution (10cc/g- Zeolite formed product), it is small to carry out 2 at room temperature
When ion-exchange treatment.Then it is filtered, washes, dries and manufacture shaped body catalyst B.It is surveyed using x-ray fluorescence analysis
Surely the silver content of the shaped body catalyst B obtained is 0.0465 mass %.It should be noted that being asked furthermore with ion-exchange
Silver content out is 0.047 mass %, roughly the same.In addition, by the silica alumina of raw material zeolite than the 980, zeolite
The cationic occupation rate of silver relative to cationic site is 25.7%.
(process 6: steaming treatment process)
Obtained shaped body catalyst B 40g is filled into internal diameter 23.9mm φ, be provided with as catalyst supports and
The stainless steel fluid bed-type of reactor of the SUS wire mesh (10 μm of aperture) of gas supplier, in 650 DEG C of temperature, pressure
0.2MPaG, steam flow 9.6g/hr, air 530NCCM condition (27.3 moles of % of vapour concentration, oxygen concentration 15.3 rub
Your %) under carries out steaming in 24 hours and handles.The proton amount of steaming treated shaped body catalyst B by ion exchange in solution/
Filtrate titration is found out, and result is 0.0012 mM/g- zeolite.
(process 7: Contact operation)
By steaming, treated that shaped body catalyst B 25.5g is filled into internal diameter 23.9mm φ, is provided with as catalyst
The stainless steel fluid bed-type of reactor of the SUS wire mesh (10 μm of aperture) of bearing and gas supplier, in temperature 550
DEG C, carry out methanol under the condition (LV2.2cm/sec, time of contact 2.95sec) of pressure 0.14MPaG, methanol flow 25.0g/hr
Conversion reaction.Reaction product is importing directly into gas-chromatography (TCD, FID by reactor outlet immediately after by raw material supply
Detector) analysis composition.It should be noted that being carried out under the following conditions using the analysis that gas-chromatography carries out.
(analytical conditions for gas chromatography)
Device: the trade name " GC-17A " of Shimadzu Scisakusho Ltd
Chromatographic column: customized capillary column, trade name " SPB-1 " (internal diameter 0.25mm, length of U.S.'s SUPELCO corporation
It is 3.0 μm thick to spend 60m, film)
The sample gas scale of construction: 1mL (sampling line is held in 200~300 DEG C)
Temperature program: it is kept for 12 minutes at 40 DEG C, after being then warming up to 200 DEG C with 5 DEG C/min, is kept at 200 DEG C
22 minutes.
Split ratio: 200:1
Carrier gas (nitrogen) flow: 120mL/ minutes
Fid detector: (about 50mL/ points of air supply pressure 50kPa (about 500mL/ minutes), hydrogen supply pressure 60kPa
Clock)
Measuring method: TCD detector and fid detector are connected in series, the hydrocarbon TCD detector of hydrogen and carbon number 1 and 2
Detection, the hydrocarbon of 3 or more carbon number are detected with fid detector.Analysis starts after ten minutes, and the output of detection is converted to FID by TCD.
While being appropriately carried out the analysis of reaction product, it is carried out continuously reaction 100 hours.Each time (in embodiment 1,4 hours, 25 small
When, 50 hours, 100 hours) when analysis the results are shown in Table 1.
[comparative example 1]
In process 5, without the manufacture of shaped body catalyst B, in process 6, shaped body catalyst B is replaced by formed body
Catalyst A carries out steaming processing, in process 7, by steaming treated shaped body catalyst B the is replaced by steaming treated at
Shaped body catalyst A carries out the reaction of methanol conversion, in addition to this implements similarly to Example 1.The results are shown in Table 1.
[comparative example 2]
In process 6, the processing of steaming in 48 hours is changed into the processing of steaming in 24 hours, in addition to this real in the same manner as comparative example 1
It applies.The 3rd hour since the reaction of methanol conversion, the gas of assay reactor outlet.As a result, detection dimethyl ether,
Know that Dehydration of methanol is not over, therefore reaction evaluating stops.The results are shown in Table 1.
[comparative example 3]
In process 1, NH4 type MFI-1000 zeolite is replaced with to the trade name of Clariant Catalysts K.K.
" MFI-240 " (ZSM-5 type zeolite of the nominal silica alumina than 240) manufactures catalyst raw mixture, except this it
Implement in the same manner as comparative example 1 outside.That is, carry out process 2~4 as a result, obtain shaped body catalyst C, urged using the formed body
Agent C carries out process 6,7.The results are shown in Table 1.
[table 1]
By embodiment 1 and comparative example 1~3 it is found that having used the shaped body catalyst containing zeolite of present embodiment
Manufacturing method is compared with the manufacturing method for having used H-ZSM-5 type catalyst, the lower olefin yields such as low, propylene of aromatic series yield
In addition height shows high resistance to coking deterioration performance.In addition at least it is found that using the feelings of H-ZSM-5 zeolite as catalyst
Under condition, its silica alumina molar ratio is selected to be important for improving propene yield.But even if using dioxy
The H-ZSM5 of SiClx alumina molar ratio 980, implement steaming processing to it, containing by using present embodiment is also not achieved
Olefin yields, the resistance to deterioration energy for thering is the manufacturing method of the shaped body catalyst of zeolite to obtain.If wanting to handle item by steaming
Part makes up this achievement difference and then knows that activity is greatly reduced, it is known that when utilizing H-ZSM-5 type catalyst, it is difficult at steaming
Manage bar part control activity.
[embodiment 2] fixed bed reaction
Then by being urged for related with the function and effect of present embodiment using methanol as the fixed bed reaction of raw material
The active control method of agent is studied.
(process 1: ion-exchange process)
It (will be completely dissolved the shaped body catalyst for containing zeolite to be used in combination containing silica alumina molar ratio 1040
ICP method measure to find out) ZSM5 type zeolite shaped body catalyst (containing SiO230 mass %, 1.6mm φ * 5 of binder~
10mmL Nikki-Universal Co., Ltd. system) the H-type shaped body catalyst that contains zeolite be scattered in 1N sodium nitrate water
In solution (10cc/g- Zeolite formed product), repeatedly 1 hour ion-exchange treatment 3 times at room temperature.Then be filtered, wash,
It is dry, manufacture Na type molded zeolite body catalyst.It is scattered in 0.0020N silver nitrate aqueous solution (10cc/g- molded zeolite
Body) in, 2 hours ion-exchange treatments are carried out at room temperature.Then it is filtered, washes, dries and manufacture shaped body catalyst D.
The silver content of the shaped body catalyst D measured using x-ray fluorescence analysis is 0.084 mass %.In addition, the zeolite of silver
The cationic occupation rate of silver relative to cationic site is 34.8%.
(process 2: steaming treatment process)
Obtained shaped body catalyst D 10g is filled into the quartz glass reactor of internal diameter 27.2mm φ, normal
Pressure, 650 DEG C of temperature, steam flow 31.8g/hr, nitrogen flow 73NCCM, air 103NCCM condition (vapour concentration 80 is rubbed
Your 2.5 moles of %, oxygen concentration %) under carries out steaming in 36 hours and handles.The proton amount of steaming treated shaped body catalyst D is
0.0014 mM/g- zeolite.
(process 3: Contact operation)
The 8.6g of steaming treated shaped body catalyst D is filled into and is attached to the internal diameter 15mm φ of thermometer sheath not
Become rusty steel fixed bed reaction pipe (sectional area 1.6cm2), in 550 DEG C of temperature, pressure 0.14MPaG, methanol flow 12.3g/hr, nitrogen
Condition (time of contact 1.76sec, WHSV1.44hr of gas 36NCCM-1) under carry out the reaction of methanol conversion.It should be noted that anti-
Temperature curve ongoing change is answered, therefore so that catalyst layer maximum temperature is 550 DEG C to be suitably adjusted using external electric furnace.
Reaction product gas-chromatography (TCD, fid detector) is importing directly by reactor outlet by raw material supply to analyze in due course
Composition.It should be noted that the reaction was continued until confirming dimethyl ether in reactor outlet product gas.It detects within 35th hour
Dimethyl ether.The results are shown in Table 2.
[embodiment 3] fixed bed reaction (compliance test result of silver load capacity)
In process 1,0.0020N silver nitrate aqueous solution (10cc/g- Zeolite formed product) replaces with 0.0015N silver nitrate water
Solution (10cc/g- Zeolite formed product) in addition to this manufactures shaped body catalyst E by method same as Example 2.In work
In sequence 2, shaped body catalyst E replace with shaped body catalyst D carry out steaming processing, in process 3, steaming treated forming
Body catalyst D replaces with the steaming treated that shaped body catalyst E carries out the reaction of methanol conversion.The results are shown in Table 2.It utilizes
The silver content of shaped body catalyst E before the steaming processing that x-ray fluorescence analysis measures is 0.057 mass %, the zeolite
The cationic occupation rate of silver relative to cationic site is 23.6%.In addition, the steaming of process 2 treated shaped body catalyst
The proton amount of E is 0.0015 mM/g- zeolite.In turn, in process 3, in the 52nd hour detection dimethyl ether.As a result such as table
Shown in 2.
[comparative example 4]
Then, as compared with embodiment 2,3, in the shaped body catalyst that previous H-type contains zeolite, pass through by
Fixed bed reaction of the methanol as raw material, for carrying out the catalyst activity of the project as present embodiment using steaming processing
Studied using the method that pre-treatment is controlled.
In process 2, shaped body catalyst D is replaced with is containing the silica alumina molar ratio before sodium and silver exchange
The shaped body catalyst of 1040 ZSM-5 type zeolite (contains SiO230 5~10mmL of mass %, 1.6mm φ * of binder
Nikki-Universal Co., Ltd. system) H-type contain the shaped body catalyst (shaped body catalyst F) of zeolite, except this it
The reaction of methanol conversion is carried out by method same as Example 2 outside.In turn, for the steaming treatment conditions in process 2 by 36
Shaped body catalyst F obtained from hour is changed into 12 hours, 72 hours respectively similarly carries out the reaction of methanol conversion.As a result
As shown in table 3.It should be noted that starting 4 by reaction for steaming 72 hours shaped body catalysts of heat treatment time
Sampling after hour and detect dimethyl ether, therefore stopped reaction.
[comparative example 5]
In process 2, shaped body catalyst D replace with containing silica alumina molar ratio be 42 ZSM-5 type zeolite
H-type contain the shaped body catalyst of zeolite (containing SiO250 mass % of binder, compression molding, the broken classification of 6~20 mesh
Product) (shaped body catalyst G), the reaction of methanol conversion is in addition to this carried out by method same as Example 2.As a result such as table 3
It is shown.
By embodiment 2, embodiment 3, comparative example 4 and comparative example 5 at least it is found that in present embodiment containing zeolite at
Shaped body catalyst can control silver load capacity by changing ion-exchange treatment liquid to be treated concentration, by the silver load capacity,
It can carry out as required by the catalyst as used in the present embodiment of methanol and/or dimethyl ether manufacture light alkene
Extremely delicate activity control.On the other hand at least it is found that the formed body for using H-ZSM-5 type to contain zeolite as catalyst is urged
In the case of agent, its silica alumina molar ratio is selected to be important.But even if using silica alumina mole
H-ZSM-5 type zeolite and then progress steaming processing, the formed body containing zeolite that present embodiment is also not achieved than 1000 are urged
The resistance to deterioration energy of agent, if it is desired to this species diversity, which is made up, by steaming treatment conditions then at least knows that activity is greatly reduced, until
It will be manufactured used in the present embodiment of light alkene as methanol and/or dimethyl ether known to few by Pretreatment
Extremely delicate activity control most appropriate required by catalyst is difficult.
[table 2]
[table 3]
[embodiment 4] fixed bed reaction/regeneration cycle test (catalyst permanently deteriorates evaluation)
It will be used for the catalyst E recycling of fixed bed reaction evaluation in embodiment 3, is roasted 5 hours with Muffle furnace at 580 DEG C,
The coke removal regeneration of catalyst will be attached to.Using the catalyst after roasting regeneration, using with the process 3 of embodiment 3: contacting
The identical method of process carries out the reaction of methanol conversion.While repeating the reaction and regeneration treatment, evaluation response achievement, thus really
Recognize the presence or absence of catalyst activity deterioration.In 4th, 5 circulation until confirm dimethyl ether in reactor outlet product gas
Time (methanol converts hold time completely) be respectively 54,53 hours, catalyst activity, coking deterioration behavior do not change.
It follows that catalyst as used herein will not generate the deterioration of the activity caused by regeneration treatment (caused by dealuminzation
Deterioration).The results are shown in Table 4.
[table 4]
The influence of [embodiment 5] catalyst pre-treatment method
In order to confirm present embodiment catalyst reproducibility, and then carry out and same verifying 2 times of embodiment 3.It is first
Catalyst E is first manufactured similarly to Example 3.The work with embodiment 2 is utilized sequentially for a part of obtained catalyst E
The identical method of sequence 2 implements steaming processing, obtains catalyst E-2S.In addition, for a part utilization of catalyst E and embodiment
The 2 identical method of process 2 implements steaming processing, obtains catalyst E-3S.The proton amount of catalyst E-2S and the proton of E-3S
Amount is respectively 0.0013,0.0015 mM/g- zeolite.Using catalyst E-2S, E-3S, 3 phase of process with embodiment 2 is utilized
Same method carries out Contact operation.As a result table 5 is shown in together with the result of embodiment 3.
The influence of [embodiment 6] catalyst pre-treatment method
In order to confirm influence that the oxygen in steaming treatment process coexists, for catalyst E obtained in embodiment 3 following
Steaming treatment conditions under handled.
(process 2: steaming treatment process)
Shaped body catalyst E 10g is filled into the quartz glass reactor of internal diameter 27.2mm φ, under normal pressure, temperature
650 DEG C, steam flow 31.8g/hr, nitrogen flow 176NCCM condition (80 moles of % of vapour concentration, nitrogen gas concn 20 rub
Your %) under carries out steaming in 36 hours and handles, obtain catalyst E-4S.In addition, under conditions of identical with catalyst E-4S,
Steaming processing is implemented for other shaped body catalyst E, obtains catalyst E-5S.The proton amount of catalyst E-4S and E-5S's
Proton amount is 0.0014,0.0012 mM/g- zeolite.Using catalyst E-4S, E-5S, 3 phase of process with embodiment 2 is utilized
Same method carries out Contact operation.The results are shown in Table 5.
[table 5]
By embodiment 3,5 and embodiment 6 at least it is found that the catalyst for passing through the progress present embodiment under oxygen concurrent conditions
Steaming processing, preferred catalyst performance can be manufactured into better with reproducibility.
[comparative example 7]
Prepare catalyst H made of the SAPO-34 compression molding that Si/Al/P molar ratio is 2/12.6/9.9.By catalyst H
It is broken, 8~20 mesh catalyst are classified as, catalyst 8.56g is filled into and is attached to the internal diameter 15mm φ of thermometer sheath not
Become rusty steel fixed bed reaction pipe (sectional area 1.6cm2), it is reacted under the following conditions.
Raw material feed speed: methanol 6.2g/hr, nitrogen 18NCCM
Reaction pressure: 0.14MPa/G
Reaction temperature: 420 DEG C of WHSV:0.72hr-1
The results are shown in Table 6.
For SAPO-34 antigravity system, although showing high selectivity for light alkene, activity is low,
Need a large amount of catalyst.In addition, activity deterioration is significant, in sampling in only 5.83 hours, dimethyl ether, methanol are detected.Therefore
It is extremely disadvantageous for industrially implementing above-mentioned catalyst.
[table 6]
[embodiment 7] utilizes the fixed bed reaction of dimethyl ether raw material
Using methanol as in the fixed bed evaluation experimental of raw material, heat release when to the dehydration of dimethyl ether is big, it is difficult to
Uniformly maintain catalyst layer temperature, it is believed that it is possible that impacting to catalyst performance evaluation, therefore, carry out supply dimethyl ether
With the evaluation response of water.
By steaming used in embodiment 3, treated that shaped body catalyst E 4.56g is filled into is attached to thermometer sheath
Stainless steel fixed bed reaction pipe (the sectional area 1.6cm of the internal diameter 15mm φ of pipe2), in 550 DEG C of temperature, pressure 0.10MPaG, two
Methyl ether flow 8.2g/hr, steam 3.2g/hr condition (LV3.16cm/sec, time of contact 1.3sec) under carry out dimethyl
Ether conversion reaction.It should be noted that the variation of reaction temperature curve is inhibited, so that catalyst layer mean temperature is 550
It DEG C is suitably adjusted using external electric furnace.Reaction product is importing directly into gas by reactor outlet by raw material supply
Phase chromatography (TCD, fid detector) analysis composition.The reaction was continued 24 hours, but without detecting unreacted dimethyl ether.Knot
Fruit is as shown in table 7.
By the result of the present embodiment it is found that the catalyst of present embodiment can be real for dimethyl ether raw material system
Now compare the reaction of isothermal, the olefin yields such as propylene further increase.
[comparative example 8,9]
In comparative example 8,9, treated that shaped body catalyst E is replaced with used in comparative example 4 36 hours respectively for steaming
Treated the shaped body catalyst G of steaming in 36 hours used in steaming treated shaped body catalyst F, comparative example 5, removes this
Except carry out dimethyl ether conversion reaction similarly to Example 7.The reaction was continued 24 hours, but does not all detect unreacted diformazan
Base ether.The results are shown in Table 7.
[table 7]
By embodiment 7 and comparative example 8,9 at least it is found that if for methanol feedstock fixed bed reaction, 1 molecular dehydration will be used as
The dimethyl ether of reactor product for raw material, then stablize by catalyst layer temperature, can be realized the reaction for comparing isothermal.Even if above-mentioned
Under the conditions of, the olefin yields such as propylene of the shaped body catalyst containing zeolite of present embodiment are also high, dominant.
[embodiment 8] utilizes dimethyl ether/olefin feedstock fixed bed reaction
As the substitution of methanol feedstock, dimethyl ether and water are supplied, the hybrid system with olefin feedstock is formed, is passed through
The fixed bed evaluation response that the supply of 1- butene gas carries out.
By steaming used in embodiment 3, treated that shaped body catalyst E 7.7g is filled into is attached to thermometer sheath
Stainless steel fixed bed reaction pipe (the sectional area 1.6cm of internal diameter 15mm φ2), in 550 DEG C of temperature, pressure 0.10MPaG, diformazan
Condition (LV5.29cm/sec, time of contact of base ether flow 8.2g/hr, 1- butylene flow 22.8g/hr, steam 3.2g/hr
Butylene/dimethyl ether conversion reaction is carried out under 1.3sec).It should be noted that so that catalyst layer mean temperature is 550 DEG C next
Suitably it is adjusted using external electric furnace.Reaction product is importing directly into gas phase color by reactor outlet by raw material supply
Compose (TCD, fid detector) analysis composition.The reaction was continued 24 hours, but without detecting unreacted dimethyl ether.As a result such as
Shown in table 8.
[comparative example 10]
Catalyst E 5.35g is filled into the stainless steel fixed bed reaction pipe of internal diameter 15mm φ for being attached to thermometer sheath
(sectional area 1.6cm2), the condition in above-mentioned fixed bed reaction is set as 550 DEG C of temperature, pressure 0.10MPaG, 1- butylene flow
22.8g/hr, nitrogen 92.6SCCM/ minutes (LV3.68cm/sec, time of contact 1.3sec), in addition to this similarly to Example 8
Ground carries out butenc reaction.It should be noted that embodiment 8, comparative example 10 are assumed to dimethyl ether dehydration and generate ethylene
In the case where, concentration of olefin in supply gas is equal, is 62.1 moles of %.The results are shown in Table 8.
[table 8]
By embodiment 8 and the result of comparative example 10 at least it is found that present embodiment is compared with the independent raw material system of butylene, lead to
It crosses while supplying dimethyl ether (i.e., methanol), among light alkene, the high income of ethylene, propylene can recycle C4, C5
Alkene.
Industrial availability
In the manufacturing method of light alkene of the invention, if the formed body containing zeolite using present embodiment is catalyzed
Agent while then realizing high propylene (light alkene) yield, is not likely to produce the deterioration caused by coking, coke burning again
Deterioration when raw, thus reactor even if using fixed-bed type, can manufacture propylene steadily in the long term.In addition, even if making
In the case where fluidized-bed reactor, the circular regeneration frequency of zeolite catalyst is also low, is not easy to produce and deteriorates year in year out, therefore urges
Agent magnitude of recruitment can lack.Meanwhile for the work that methanol and/or dimethyl ether is extremely delicate as the catalyst requirement of raw material
Property control, and the shaped body catalyst containing zeolite of present embodiment can also be manufactured with easy method with desired work
The catalyst of property.It is extremely beneficial when these true industrially implementation present embodiments.
Claims (7)
1. a kind of manufacturing method of light alkene, have make containing in the group being made of methanol and dimethyl ether at least
A kind of raw material, the Contact operation contacted in reactor with the shaped body catalyst containing zeolite,
Total amount of the raw material relative to the raw material contains at least one in the group being made of methanol and dimethyl ether
Kind 10 mass % or more,
Zeolite in the shaped body catalyst containing zeolite meets following (1)~(4):
(1) zeolite is intermediate pore size zeolite,
(2) zeolite contains substantially no proton,
(3) zeolite contains silver,
(4) silica alumina molar ratio, that is, SiO of the zeolite2/Al2O3Molar ratio is 800 or more and 2000 or less.
2. the manufacturing method of light alkene according to claim 1, wherein in the shaped body catalyst containing zeolite
Zeolite also contain alkali metal.
3. the manufacturing method of light alkene according to claim 1 or 2, wherein for the formed body containing zeolite
Catalyst is heated in the presence of vapor and oxygen, at 500 DEG C or more.
4. the manufacturing method of light alkene described in any one of claim 1 to 3, wherein it is described containing zeolite at
The cationic occupation rate of the silver relative to cationic site of zeolite in shaped body catalyst is 10% or more and 70% or less.
5. the manufacturing method of light alkene according to any one of claims 1 to 4, wherein it is described containing zeolite at
Shaped body catalyst also contains silica.
6. the manufacturing method of light alkene according to any one of claims 1 to 5, wherein the reactor is fluidisation
The reactor of bed or fixed-bed type.
7. the manufacturing method of light alkene described according to claim 1~any one of 6, wherein the raw material also contains alkene
Hydro carbons.
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| JPWO2017179108A1 (en) | 2018-11-08 |
| JP6600082B2 (en) | 2019-10-30 |
| CN109071378B (en) | 2022-08-05 |
| WO2017179108A1 (en) | 2017-10-19 |
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