CN104056653B - A kind of catalyst for producing propylene with methanol - Google Patents
A kind of catalyst for producing propylene with methanol Download PDFInfo
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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
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- 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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- 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
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
A kind of catalyst for producing propylene with methanol, it is characterised in that containing 30 95 weight % ZSM 5 combination of molecular sieve, 5 70 weight % inorganic oxides and and the clay of 0 50 weight %, in described combination of molecular sieve, on the basis of combination of molecular sieve, containing with P2O5The phosphorus of 0.1 10 weight % of meter and the rare earth of 0 10 weight % in terms of oxide, in described ZSM 5 molecular sieve, alkali metal content in terms of oxide is less than 0.2 weight %, SiO2With A12O3Molar ratio be 100 1000, nitrogen adsorption methods measure under BET method specific surface area be 300 600m2/ g, total pore volume is 0.2 0.6mL/g, bore dia > the mesoporous pore volume of 2nm accounts for the 30 70% of total pore volume.
Description
Technical field
The present invention relates to the catalyst containing ZSM-5 molecular sieve, further the present invention relates to a kind of phosphorous and dilute
The catalyst for producing propylene with methanol of the ZSM-5 molecular sieve of soil.
Background technology
Propylene is important Organic Chemicals, along with increasing rapidly of the derivative demands such as polypropylene, to propylene
Demand rise the most year by year.In the traditional source of production of propylene, about 70% from cracking petroleum hydrocarbon vapor technique,
Separately have 28% from heavy oil catalytic cracking process, be dependent on petroleum resources.The decline of oil production capacity and whole world oil
Significantly raising of valency forces researcher to develop new alternative energy source and new process to produce largeization
Product.By coal, natural gas, living beings etc. through synthesis gas to methanol conversion technology is ripe and realization is advised greatly
Mould industrialized production, is catalytic material dehydration preparing low-carbon olefins (MTO) and preparing propylene from methanol (MTP) by methyl alcohol
Technology is the new olefin production technology being hopeful most to replace petroleum path.The research of methanol-to-olefins technology,
Exploitation, industrialization become the focus of international each major oil companies technological development in recent years.
The low carbene of methyl alcohol system will be used for after preparing gasoline by methanol process modification from Mobil company of U.S. report in 1984
After hydrocarbon (MTO) (Chang, C D etc., J.Catal., SB, 289 (1984)), many zeolites or point
Son sieve is used as the catalyst of MTO reaction, through screening study for many years, currently mainly concentrates on two classes and divides
Sub-sieve catalyst.One type concentrates on the mesopore zeolite such as ZSM-5 zeolite etc..USP3911041 discloses
Use the ZSM-5 zeolite of at least about 0.78 weight % P Modification, make methyl alcohol convert at a temperature of 300-700 DEG C
For alkene.USP4049573 and 4088706 discloses the oxide by boron or magnesium, or adds further
Phosphorous oxides modified ZSM-5 zeolite, makes methyl alcohol be converted into alkene under 250-700 DEG C and 0.2-30 atmospheric pressure.
USP4480145 discloses the expansion of the silica filling reduction zeolite of use large crystal ZSM-5-5 zeolite and zeolite pores
Dissipate property, the ethylene yield that methyl alcohol converts can be improved.This patent also discloses by hydro-thermal at 180-820 DEG C
Process reduction zeolite alpha active, to 6-10, can improve cycle life and the methanol conversion activity of zeolite.
USP4549573 discloses when converting methanol into hydro carbons under 350-700 DEG C and 1-100 atmospheric pressure, uses
Constraint factor is 1-12 and silica/alumina mole ratio is the zeolite of 298-2000, can improve lightweight alkene
The productivity of hydrocarbon.
The another kind of important catalyst being converted into alkene for methyl alcohol is SAPO (SAPO) family molecular sieves.
This family molecular sieves is invented in the early 1980s by American Association carbon compound company (UCC)
(USP4440871), wherein SAPO-34 molecular sieve presents methanol-to-olefins preferably catalytic performance, but
Rich product ethene in this product, yield of ethene reaches 53.8%, and propylene is 29.1%, and P/E is than the lowest (USP
5817906).Recently have been reported that Propylene Selectivity reaches 45.4% in methanol to olefins reaction, ethylene contents
The highest, P/E (propylene/ethylene) weight ratio is less than 1.45 (USP6710218).SAPO Series Molecules sieves
Catalyst aperture is little, easy coking, and in product component, P/E ratio is low, is not suitable for MTP technique.
Last century the nineties, Lurgi company of Germany develops a set of complete based on modified ZSM-5 molecular sieve
Whole MTP technique, uses portion of product olefin recycle reactive mode, and Propylene Selectivity reaches 71.2% (PEP
Review98-13) so that cause again the pass of researcher about preparing propylene from methanol technology on ZSM-5 molecular sieve
Note.
CN1431982A discloses the method preparing propylene with methyl alcohol, enters series connection fixing after methanol fractions dehydration
Bed reactor, the mode utilizing portion of product to circulate make methyl alcohol be converted into light olefin, and used catalyst is
ZSM-5 zeolite catalyst, its alkali metal content is less than 380ppm.The ZnO content of described catalyst is less than 0.1
Weight %, CdO content is less than 0.1 weight %, and BET surface area is 300 to 600m2/ g, pore volume is 0.3
Measure to 0.5mL/g(mercury injection method).The more detailed preparation method of this catalyst see US05063187 and
US07229941, by the primary grains of Hydrothermal Synthesis a size of 0.1-0.9 μm (US05063187) or
The ZSM-5 zeolite of 0.01-0.1 μm (US07229941) be dispersed in account for catalyst 10-40% aluminum oxide glue
Prepared by knot agent.
CN1084431A disclose a kind of for methyl alcohol or dimethyl ether produce light olefin process phosphorous, rare earth is first
Element and pore structure conditioning agent ZSM-5 type zeolite catalyst and use dehydration reactor and 2～n react again and again
The course of reaction of the multistage insulation fixed bed cracking reactor of raw handover operation, at high temperature (> 400 DEG C) non-
Circulation operation, is to process day on the device of methyl alcohol 0.7-1 ton in scale, methanol conversion 100%, C2～C4
Olefine selective can be more than 85%, and the online duration of runs can be more than 600 hours, and the one-pass operation cycle can be big
In 24 hours.Wherein ZSM-5 zeolite silica alumina ratio is 40-80, and catalyst phosphorus content is 0.7-5%, lanthanum or richness
La mixed rare earth content is 0.9-6.5%.
CN1352627A discloses the catalyst that methyl alcohol or dimethyl ether selectivity are converted into light olefin, uses tool
There are zeolite such as ZSM-5 zeolite and the ZSM-11 zeolite of 10 ring cross aisles, by adding phosphorus-containing compound
And hydro-thermal processes and makes and the zeolite diffusion ginseng to 2,2-dimethylbutane when measuring under 120 DEG C and 8kPa
Number is less than 100s-1, use catalyst prepared by this zeolite for the reaction of methanol conversion, 370-480 DEG C, first
When alcohol dividing potential drop is 30-150PSia, the conversion per pass of methyl alcohol is less than 95%, owing to diffusion limits ethene
Selectively improve.
CN1803738A is disclosed uses moving bed technique and independent heavier olefins shift step by oxygen-containing organic
Compound is converted into the method for propylene, and ZSM-5 molecular sieve catalyst is preferably used, and converts at oxygenatedchemicals
Reactions steps uses moving-burden bed reactor technology, replaces the bed technology of prior art；Use independent
Heavier olefins shift step, makes the reaction temperature in oxygenate conversion reaction step reduce by 15 DEG C；Restriction is urged
< 700 hours circulation timei of agent；Product ethene returns oxygenate conversion reactor, decreases catalyst
On green coke so that the activity of catalyst, the conversion ratio of oxygenatedchemicals and Propylene Selectivity are essentially close to
Or be maintained at catalyst initial circulating levels, thus significantly improve oxygenatedchemicals and be converted into the average of propylene
Propylene circulation productivity.
CN101172246A discloses the preparation method of propylene catalyst from methanol conversion.By by sial mole
Than be 20-1000 ZSM-5 molecular sieve and adhesive mixed-forming after roasting, with selected from hydrochloric acid, nitric acid,
In sulfuric acid, phosphoric acid or tartaric acid, at least one acid solution or ammonium salt solution swap rear roasting, then experience temperature
The steam treatment that degree is 400-700 DEG C, the most again with in oxalic acid, citric acid, phosphoric acid or tartaric acid
After at least one acid solution dipping, roasting prepares modified molecular sieve catalyst.This catalyst converts system for methyl alcohol
When propylene is evaluated, methanol conversion is up to 100%, and propene yield reaches 47.1%, and P/E ratio is higher than 6.
CN101172918A discloses after methyl alcohol first contacts with aluminium oxide catalyst and contacts with above-mentioned catalyst
Realize two sections of method for transformation of preparing propylene from methanol.
CN101429085A discloses the method preparing propylene, ethylene light olefin hydrocarbon from methanol/dimethyl ether, used
Catalyst is silica alumina ratio > 50, the modified binderless ZSM-5 of 0.01-10% rare earth and 0.01-10% phosphorous oxides
Molecular sieve, including ZSM-5, ZSM-11, ZSM-23, ZSM-48 or its mixture.
CN101239326A discloses the preparation method of propylene catalyst from methanol conversion.By silica alumina ratio it is
ZSM-5 molecular sieve former powder roasting in air atmosphere of 20～1000, the ZSM-5 of removing segment template agent divides
Son sieves roasting after former powder exchanges with at least one acid solution in hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, then
Roasting after contacting with at least one aqueous slkali in alkali metal hydroxide or alkali carbonate, then
Required catalyst is prepared with roasting after at least one exchange in nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid.
Gained catalyst is at 470 DEG C, and methanol weight air speed is 1h-1, the methanol partial pressure methyl alcohol more than 70 kPas converts
Under the conditions of, Propylene Selectivity is more than 40%, and ethylene selectivity is less than 5%, and P/E (propylene/ethylene weight) ratio is big
In 9.
CN101279282A discloses the ZSM-5 molecular sieve catalyst for preparing propylene from methanol and preparation side thereof
Method.The ZSM-5 mesopore molecular sieve of silica alumina ratio 20-1000 is aoxidized with being selected from based on mass fraction 20-100%
After the binding agent mixing of silicon, clay or aluminum oxide, extrusion, compressing tablet or spray ball forming；Then through selected from hydrochloric acid,
The ammonium salt solution contact of at least one acid solution regulation pH value in nitric acid, sulfuric acid or acetic acid, product is in temperature
Soak with at least one solution in oxalic acid, citric acid or maleic acid after steam treatment under the conditions of 400-700 DEG C
Stain.Gained modified molecular sieve catalyst is in reaction temperature 500 DEG C, methyl alcohol air speed 4h-1Under the conditions of, methyl alcohol turns
Rate 100%, propene yield is up to 47%, and P/E ratio is more than 6.Catalyst disclosed in CN101279280A with
This is similar to.
The high stability molecular sieve catalyst of preparing propylene by methanol transformation disclosed in CN101279281A and preparation thereof
Silica alumina ratio is 20-1000 by method, and percentage by weight is calculated as the former powder of ZSM-5 molecular sieve of 25-99.9%
With selected from SiO2, clay, A12O3In at least one binding agent through extrusion, compressing tablet or spray ball forming；Pass through again
In ammonium nitrate, ammonium chloride, ammonium sulfate at least one ammonium salt solution or selected from hydrochloric acid, nitric acid, sulfuric acid,
In phosphoric acid, acetic acid, the acid solution of at least one processes at temperature 20-90 DEG C；Then percentage by weight meter is used
Being selected from least one solution in lanthanum, cerium nitrate or chloride for 0.1-5% is 20-90 DEG C of condition in temperature
Lower process；Steam treatment 2-15 hour under the conditions of temperature 400-700 DEG C；Again with selected from oxalic acid, lemon
In acid, phosphoric acid, maleic acid, at least one impregnates to obtain required modified molecular sieve catalyst.This catalyst is used for first
The preparing propylene transformed reaction of alcohol, in reaction temperature 470 DEG C, methyl alcohol air speed 1 hour-1Under the conditions of, methanol conversion
Up to 100%, propene yield is more than 45%, and the life-span reaches as high as 850 hours.
CN101306381A discloses ZSM-5 molecular sieve catalyst and the preparation thereof of a kind of preparing propylene by methanol transformation
Method.The ZSM-5 molecular sieve of silica alumina ratio 20-1000 is counted according to the mass fraction 20-99.8% accounting for catalyst
With at least one after the binding agent of silica, clay or aluminum oxide mixes, extrusion, compressing tablet or spray ball become
Type；Then the ammonium through at least one acid solution regulation pH value in hydrochloric acid, nitric acid, sulfuric acid or acetic acid is molten
Liquid contacts, then with at least one nitrate in barium, magnesium or calcium of percentage by weight meter 0.01-5% or
Chloride solution contacts, then with percentage by weight meter 0.01-5% press selected from phosphoric acid, metavanadic acid, ammonium molybdate
Or at least one salting liquid contact in ammonium tungstate；Product is under the conditions of temperature 400-700 DEG C after steam treatment
By at least one solution impregnation in oxalic acid, citric acid or maleic acid.Gained modified molecular sieve catalyst exists
Reaction temperature 470 DEG C, methyl alcohol air speed 1h-1Under the conditions of, methanol conversion 100%, propene yield up to 45%,
Life-span reaches 800 hours, improves that Propylene Selectivity is low, molecular sieve heat endurance and hydrothermal stability, no
Easily coking and deactivation.Disclosed in CN101279283A, preparing propylene from methanol ZSM-5 catalyst divides ZSM-5 further
The crystallite dimension of son sieve is limited in 0.2-1 micrometer range.
CN101347743A discloses the high propylene/ethylene preparation method than propylene catalyst from methanol conversion.
Use first with selected from NaOH, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate
In at least one former powder of alkaline solution treatment ZSM-5 molecular sieve, then selected from hydrochloric acid, nitric acid, sulfuric acid or second
At least one acid solution in acid processes, then mixes with binding agent after temperature is 400-700 DEG C of steam treatment
After synthesis type, roasting, then by least one solution impregnation in oxalic acid, citric acid, phosphoric acid or tartaric acid,
ZSM-5 Type Zeolites agent is obtained after fired.This catalyst make material benzenemethanol conversion ratio up to 100%,
Propene yield is up to 48.2%, and P/E weight ratio is up to 10.
CN101234353A discloses a kind of preparing propylene from methanol catalyst, accounting for molecular sieve mass ratio is
The cerium modified H-ZSM-5 molecular sieve of 0.005-0.15, reacts for preparing propylene from methanol, and reaction condition is temperature
300-500 DEG C, pressure is 0-1Mpa, and liquid hourly space velocity (LHSV) is 0.1-10h-1。
CN101176849A disclose a kind of by methyl alcohol or dimethyl ether in high selectivity prepare propylene catalyst and
Preparation method.Rare earth element stable molecule sieve structure, alkaline matter is used to change surface acidity and online silicon
Alkanisation carries out the modes such as modification and is modified active constituent ZSM-5 molecular sieve catalyst processing duct, warp
It is spray-dried and prepares the high catalyst for fluidized-bed reaction selectively producing propylene；The group of this catalyst
Become by following percentage by weight: rare earth 0.1-8%, basic modifier 0.5-30%, binding agent 20-80%, silicon
Alkanisation silicone content 0.05-10%, remaining is ZSM-5 molecular sieve.
CN101433858A discloses the HZSM-5 molecular sieve catalyst of a kind of producing propylene from methanol/dimethyl ether, adopts
HZSM-5 molecular sieve catalyst is modified, for first with accounting for the wolfram element that molecular sieve mass fraction is 0.005-10%
Alcohol propylene reacts, and reaction condition is temperature 300-500 DEG C, and pressure is 0-1Mpa, and liquid hourly space velocity (LHSV) is
0.1-10h-1。
CN101624192A discloses the HZSM-5 molecular sieve catalytic for a kind of producing propylene from methanol/dimethyl ether
Agent, the silica alumina ratio of this ZSM-5 molecular sieve is 250-1150, and particle diameter is 65-250nm.The preparation of this molecular sieve
Method includes mixing aluminium source with organic directing agent, adds silicon source and becomes gel with organic additive, then exists
Hydrothermal crystallizing 24-240h at 60-200 DEG C.Wherein organic additive and SiO2Mol ratio be 0.5-8, plant
Class is one or more in methyl alcohol, ethanol, acetone and polyvinylpyrrolidone.
CN102050691A discloses the method preparing low-carbon alkene with coupling between methanol carbon 4 hydrocarbon, uses silica alumina ratio
Phosphorous modified ZSM-5 molecular sieve for 15-80 is catalyst.
CN101780417A discloses a kind of methyl alcohol and converts paraxylene processed and the catalyst of low-carbon alkene, by mistake
Cross metal and rare-earth metal modified after ZSM-5 molecular sieve acid through silicone-based compound modification of surfaces again and
Prepared by pore structure, wherein levels of transition metals is the 0.1-10% weight of catalyst, and rare earth metal content is catalysis
The 0.1-5% weight of agent, silicone-based compound accounts for the 0.1-8% weight of catalyst in terms of Si.
CN102125866A discloses a kind of H-ZSM-5 molecular sieve catalyst preparing propylene for methyl alcohol, for
Evaporate during by Hydrothermal Synthesis molecular sieve initiation material after portion of water forms gel and carry out crystallization beam system
The standby crystallite dimension obtained is less than 300nm, specific surface area 380-420m2/ g, the H-ZSM-5 of silica alumina ratio 80-100
Molecular sieve.
Summary of the invention
The most extremely complex preparation technology route, such as in the initial reactant of synthesis of molecular sieve
Adding organically or inorganic assistant, method synthesizes and changes to use the silicone-based compound of high price modified etc.
Property ZSM-5 molecular sieve, but it still has much room for improvement for process for preparing propylene from methanol gained olefine selective.Send out
A person of good sense a large amount of ZSM-5 molecular sieves develop on the basis of it was unexpectedly observed that when use fluosilicic acid hydro-thermal method process
After the ZSM-5 molecular sieve of low sodium content, then with phosphorous and carry out the molecular sieve after activation process containing earth solution
Composition, has special pore size distribution$, more it was unexpected that work as the activity using it as MTP catalyst
During component, while keeping methyl alcohol high conversion, propylene/ethylene mass ratio is significantly improved, based on this,
Form the present invention.
It is an object of the invention to provide one to have acid especially and pore property on the basis of existing technology
Be applicable to catalyst for producing propylene with methanol.
It is a further object of the present invention to provide the preparation method of this catalyst.
The catalyst for producing propylene with methanol that the present invention provides, it is characterised in that containing 30-95 weight % molecular sieve
Composition, 5-70 weight % inorganic oxide and and the clay of 0-50 weight %, described combination of molecular sieve
In, on the basis of combination of molecular sieve, containing with P2O5Meter 0.1-10 weight % phosphorus and in terms of oxide
The rare earth of 0-10 weight %, in described ZSM-5 molecular sieve, alkali metal content in terms of oxide is less than
0.2 weight %, SiO2With A12O3Molar ratio be 100-1000, nitrogen adsorption methods measure under BET
Method specific surface area is 300-600m2/ g, total pore volume is 0.2-0.6mL/g, bore dia > the mesoporous pore volume of 2nm accounts for
The 30-70% of total pore volume.
Present invention also offers the preparation method of above-mentioned described catalyst, it is characterised in that the method includes
The former powder of the ZSM-5 molecular sieve fired removing organic formwork agent of alkali metal-free or low alkali is obtained roasting
Powder；Roasting powder carries out liquid phase acid treatment and obtains pickling filter cake；And, described pickling filter cake is carried out containing phosphatization
Reclaim after the activation process of compound and compounds containing rare earth and obtain the step of ZSM-5 molecular sieve composition, wherein,
Described roasting powder carries out liquid phase acid treatment and obtains the step of pickling filter cake by roasting powder and containing fluosilicic acid
Acidic aqueous solution making beating non-uniform components screening the pulp liquid, and temperature 100-200 DEG C, pressure in airtight still
Under 0.1-2Mpa, hydro-thermal processes, and described fluosilicic acid with the mass ratio of the butt of described roasting powder is
0.0001-0.1:1, in described molecular sieve pulp, water is 3-20:1 with the mass ratio of the butt of roasting powder.
The present invention is by using the ZSM-5 molecular sieve of the alkali metal-free of removed template method or low alkali through fluorine silicon
Dealuminzation introduce the activation process of the hetero atoms etc. such as phosphorus under sour water heat condition, makes ZSM-5 molecular sieve have Gao Jie
Hole pore volume and suitable acidity.In methyl alcohol prepares the reaction of light olefin, high mesoporous pore volume and appropriate acid
ZSM-5 molecular sieve composition is conducive to improving reactant methanol and the diffusion rate of product light olefin, is conducive to
Methanol dewatered propylene react in suppress the intermediate product light olefin such as propylene, butylene occur further hydrogen migration,
The side reactions such as overlapping, condensation green coke, improve the selectivity of purpose product propylene；And catalyst can be improved
Appearance charcoal amount, improve catalyst anti-coking deactivation ability, extend catalyst single pass life.
Accompanying drawing explanation
Accompanying drawing 1 is the XRD diffraction pattern of the ZSM-5 molecular sieve composition of synthesis in embodiment 1-4.
Accompanying drawing 2 is that the MTP of embodiment 8 and comparative example 2 catalyst reacts life assessment result.
Detailed description of the invention
The catalyst for producing propylene with methanol that the present invention provides, it is characterised in that containing 30-95 weight % molecular sieve
Composition, 5-70 weight % inorganic oxide and and the clay of 0-50 weight %, described combination of molecular sieve
In, on the basis of combination of molecular sieve, containing with P2O5Meter 0.1-10 weight % phosphorus and in terms of oxide
The rare earth of 0-10 weight %, in described ZSM-5 molecular sieve, alkali metal content in terms of oxide is less than
0.2 weight %, SiO2With A12O3Molar ratio be 100-1000, nitrogen adsorption methods measure under BET
Method specific surface area is 300-600m2/ g, total pore volume is 0.2-0.6mL/g, bore dia > the mesoporous pore volume of 2nm accounts for
The 30-70% of total pore volume
In described combination of molecular sieve, described phosphorus is with P2O5The content of meter is 0.2-5 weight %, described
The content counted with oxide of rare earth for 0-5 weight %, described alkali metal content in terms of oxide is less than
0.1 weight %.SiO2With A12O3Molar ratio be preferably 150-500, nitrogen adsorption methods measure under BET
Method specific surface area is preferably 350-500m2/ g, total pore volume is preferably 0.3-0.5mL/g, its median pore diameter > 2nm
Mesoporous pore volume preferably comprise the 40-60% of total pore volume.
In described composition, described rare earth preferably is selected from one or more in yttrium, lanthanum, cerium, praseodymium, more
Preferably lanthanum and/or cerium.
Catalyst described in the present invention is strip catalyst or the bead catalysis for a diameter of 0.5-5.0mm
Agent, or use the microspherical catalyst of a diameter of 15-150 μm that spray drying process obtains.
The present invention also provides for the preparation method of catalyst, it is characterised in that the method includes preparing a kind of molecule
Screen composition, then by combination of molecular sieve and inorganic oxide binder and be with or without clay and urge at interior
The step that agent precursor mixture is shaped, the wherein described process preparing a kind of combination of molecular sieve
Roasted including by the former powder of the ZSM-5 molecular sieve fired removing organic formwork agent of alkali metal-free or low alkali
Burn powder；Roasting powder carries out liquid phase acid treatment and obtains pickling filter cake；And, described pickling filter cake carries out phosphorous
The step obtaining ZSM-5 molecular sieve composition is reclaimed after the activation process of compound and compounds containing rare earth, its
In, described roasting powder carry out liquid phase acid treatment obtain the step of pickling filter cake be by roasting powder with containing fluorine silicon
The acidic aqueous solution making beating non-uniform components screening the pulp liquid of acid, and temperature 100-200 DEG C, pressure in airtight still
Under 0.1-2Mpa, hydro-thermal processes, and described fluosilicic acid with the mass ratio of the butt of described roasting powder is
0.0001-0.1:1, in described molecular sieve pulp, water is 3-20:1 with the mass ratio of the butt of roasting powder
In described method, described alkali metal-free or low alkali metal content (alkali metal refers mainly to sodium or potassium,
Less than 0.2 weight % in terms of oxide) the former powder of ZSM-5 molecular sieve can derive from multiple channel, such as business
Buying, such as alkali metal obtains, preferably at the sial body of alkali metal-free or low alkali through ammonium exchange
The lower Hydrothermal Synthesis of system obtains.Under described alkali metal-free or the sial system of low alkali, Hydrothermal Synthesis obtains
The process of the former powder of ZSM-5 molecular sieve is that aluminium source, silicon source, water and organic formwork agent are thoroughly mixed to form reaction
Mixture, by reactant mixture under agitation, under the temperature of 70～200 DEG C, self-generated pressure hydrothermal crystallizing
20～200 hours, crystallization product, through filtering, washing, was dried, mole composition of described reactant mixture
Scope is organic formwork agent/SiO2=0.03-0.3, SiO2/Al2O3=100-1000, H2O/SiO2=5-30, wherein,
Described aluminium source is selected from hydrated alumina, aluminum sulfate, aluminum nitrate, aluminium hydroxide, aluminium isopropoxide；Described
Silicon source is selected from the solid silicon source such as solid silicone, white carbon；Described organic formwork agent is tetraethyl ammonium hydroxide
Or TPAOH.
The described organic formwork agent in the roasting removing former powder of ZSM-5 molecular sieve, obtains ZSM-5 molecular sieve roasting
Burning the step of powder, roasting condition is preferably ingress of air roasting 0.5-50h at 300-800 DEG C.
Described roasting powder carries out liquid phase acid treatment and obtains pickling filter cake, be in particular by roasting powder with contain
Have fluosilicic acid acidic aqueous solution making beating non-uniform components screening the pulp liquid, and in airtight still temperature 100-200 DEG C,
Process under pressure 0.1-2Mpa, generally process 0.5-30h；In a preferred embodiment, described general's roasting
Burn powder and the acidic aqueous solution making beating non-uniform components screening the pulp liquid containing fluosilicic acid, and process in airtight still
Temperature is 105-180 DEG C, pressure is 0.11-1Mpa, more preferably temperature 105-150 DEG C, pressure
0.12-0.7Mpa.The mass ratio of described fluosilicic acid and the butt of described roasting powder be 0.0001-0.1,
Preferably 0.001-0.05, more preferably 0.002-0.01, water and the butt of roasting powder in described molecular sieve pulp
Mass ratio be 3-20, preferred 4-15, more preferably 5-10.After described process, through being cooled to less than 80 DEG C,
Pressure release, to normal pressure, by products therefrom through filtering, obtains alkali metal content in terms of oxide, such as Na2O content < 0.2
The pickling filter cake of weight %.The described acidic aqueous solution containing fluosilicic acid also can contain further selected from hydrochloric acid,
One or more in sulfuric acid, nitric acid, phosphoric acid and oxalic acid etc..
Described is carried out ZSM-5 molecular sieve pickling filter cake at the activation of phosphorus-containing compound and compounds containing rare earth
Reason, is that the solvable inorganic phosphor-contained compound of required amount of calculation is dissolved in water, is selected from containing of required amount of calculation
The aqueous solution of the soluble salt of one or more rare earth elements in yttrium, lanthanum, cerium and praseodymium is mixed into activator, will
Activator mixes with the making beating of ZSM-5 molecular sieve pickling filter cake, be then dried at a temperature of 80-800 DEG C,
Roasting.Described solvable inorganic phosphor-contained compound is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, di(2-ethylhexyl)phosphate
One or more mixtures in hydrogen ammonium；The aqueous solution of the soluble salt of described rare earth element selected from yttrium, lanthanum,
Cerium or the soluble salt of praseodymium element, such as, include chloride, nitrate etc..
In the method for the methyl alcohol light olefin of present invention offer, particularly propylene.Described ZSM-5 molecular sieve
Composition and inorganic oxide binder are mixed with as preformed catalyst, such as, roll the bead catalysis of shaping
Agent, the bar shaped catalyst of extruded moulding or the microspherical catalyst of spray shaping.Described preformed catalyst is also
Including inorganic oxide binder, clay etc., wherein, the ZSM-5 molecular sieve composition of the present invention accounts for 30-95
Weight %, preferred 50-90%, binding agent accounts for 5-70 weight %, preferred 10-50 weight % in terms of inorganic oxide,
Clay accounts for 0-50 weight %, preferred 0-30 weight %.The example of described inorganic oxide binder include but
It is not limited to following kind: in aluminum oxide, silica, aluminum phosphate, amorphous silica-alumina, zirconium oxide and titanium oxide
The mixture of one or more.Described its precursor of aluminum oxide includes Alumina gel, polymeric aluminum chloride, thin
Diaspore and boehmite etc.；Described its precursor of silica includes silester, Ludox etc..Institute
The clay said comprises Prof. Du Yucang or naturally-produced material, such as kaolin, kaolinite, montmorillonite, talcum
Mixture with one or more in bentonite, it is also possible to be through peracid or alkali-treated journey by above-mentioned clay
Product after processing, preferred clay is kaolin and the product processed through acid or alkali thereof.
In the method for described methanol dewatered light olefin, material benzenemethanol can be refined and aqueous not essence
Methyl alcohol processed, can add steam or inert gas to regulate methyl alcohol charging dividing potential drop, reaction used in course of reaction
Temperature is 250 DEG C-600 DEG C, is preferably 350 DEG C-500 DEG C；Reaction pressure used be 0.1-50 atmospheric pressure,
Preferably 0.5-5 atmospheric pressure, weight space velocity used (WHSV) is 0.01-50h-1, be preferably 0.1-10h-1。
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
It is Germany that the X-ray powder diffraction of each embodiment and comparative example Middle molecule sieve measures instrument
Bruker D5005 diffractometer, uses CuK alpha ray；Molecular sieve composition x ray fluorescence spectrometry
Measure.N2Adsorption analysis uses U.S.'s Micromeritics ASAP2400 adsorption instrument to be measured, wherein > 2nm
Mesoporous pore volume=total pore volume-Micropore volume.
In embodiment raw materials used except as expressly described, be chemically pure reagent.
Example 1-4 illustrates the catalyst with the present invention and preparation process thereof.
Embodiment 1
By 7.8 kilograms of dry glue powders (containing 74% weight Al2O3, Sinopec catalyst Chang Ling branch company produces, under
Join together) 1694 kilograms of TPAOH aqueous solution (containing the TPAOH of 20% weight) molten
Solving, add 577 kilograms of solid silicones (Qingdao Marine Chemical Co., Ltd. produces, lower same), stirring is mixed
Close 2 hours.Mole consisting of of gained reactant mixture: TPAOH/SiO2=0.2, SiO2/Al2O3=140,
H2O/SiO2=9.5.Reactant mixture is loaded stainless steel crystallizing kettle, 130 DEG C, continuously stir and spontaneous pressure
Crystallization 90 hours under power.Then crystallization product is filtered, wash and dry 16h, i.e. score at 120 DEG C
Son sieves former powder product A 1.
By above-mentioned dry former powder A1 as in Muffle furnace, in 550 DEG C of roasting 6h, obtain roasting molecular sieve powder A2.
Take 400 kilograms of butt above-mentioned roasting molecular sieve powder A2 to join 2800 kilograms of deionized waters stir and beat
Slurry, is subsequently adding 8.84 kilograms of fluorine silicic acid aqueous solutions (containing 30% fluosilicic acid, lower same), is placed in exchange still
Seal, be warming up to 130 DEG C under continuous stirring, under still pressure is for 0.28Mpa, keeps 1h, is then cooled to
70 DEG C of filtrations, washings, obtain filter cake product A 3.
14.17 kilograms of ammonium dihydrogen phosphates are dissolved in 300 kilograms of deionized waters, add 350 kilograms of butts
Above-mentioned molecular sieve filter cake A3 stirring to pulp is uniform, then at 140 DEG C, slurries is dried 16h, obtains the present invention
Combination of molecular sieve product A 4.
Take the zeolite product A4 that part is above-mentioned, measure through X-ray powder diffraction, its result such as Fig. 1
Shown in middle diffraction pattern, illustrate that it is ZSM-5.Na in XRF analysis, A4 molecular sieve2O content is 0.04%,
P2O5Content is 2.69%, and silica alumina ratio is 158.Through low temperature N2-adsorption analysis, the BET method of A4 molecular sieve
Specific surface area is 469m2/ g, total pore volume is 0.393mL/g, and its mesoporous is > the mesoporous pore volume of 2nm is
0.203mL/g, accounting for total pore volume ratio is 51.4%.
By 300 grams of butt molecular sieve-4 As 4 and 349 grams of Alumina gel (Sinopec catalyst asphalt in Shenli Refinery product,
Al containing 21.5% weight2O3) be sufficiently mixed uniformly, in bowling machine, then rotate into pellet catalyst, screening
Obtain the bead of diameter 1.4-2.0mm, the little ball warp of gained 120 DEG C dry 16h, then 550 DEG C of temperature,
Roasting obtains pellet catalyst CA4 in 4 hours.
CA4 catalyst consists of 80% weight molecule sieve A4 and 20% weight Al2O3。
Embodiment 2
By 4.5 kilograms of dry glue powders and the 1271 kilograms of TPAOH aqueous solution (tetrapropyls containing 20% weight
Ammonium hydroxide, Sinopec catalyst Jian Chang branch company produces) load stainless steel crystallizing kettle and dissolve, add
260 kilograms of deionized waters and 577 kilograms of solid silicones, stirring mixing 2 hours.Gained reactant mixture
Mole consist of: TPAOH/SiO2=0.15, SiO2/Al2O3=180, H2O/SiO2=9.Reactant mixture is existed
140 DEG C, continuously stir and crystallization under self-generated pressure 75 hours.Then by crystallization product filter, washing and
Dry 16h at 120 DEG C, obtain molecular screen primary powder product B 1.
By above-mentioned dry former powder B1 as in Muffle furnace, in 550 DEG C of roasting 4h, obtain roasting molecular sieve powder B2.
Take 200 kilograms of butt above-mentioned roasting molecular sieve powder B2 to join 1800 kilograms of deionized waters stir and beat
Slurry, is subsequently adding 2.97 kilograms of fluorine silicic acid aqueous solutions, is placed in exchange still and seals, heats up under continuous stirring
To 105 DEG C, under still pressure is for 0.13Mpa, keep 1h, be then cooled to 60 DEG C of filtrations, washing, obtain filter cake
Product B 3.
4.37 kilograms of ammonium dihydrogen phosphates are dissolved in double centner deionized water, then by 6.1 kilogram of six hydration
Yttrium nitrate salt is dissolved in 80 kilograms of deionized waters, and joins formation colloid in ammonium dihydrogen phosphate, to
This colloid adds 180 kilograms of butt above-mentioned molecular sieve filter cake B3 stirring to pulps uniform, then slurries are existed
Dry 24h, obtain combination of molecular sieve product B 4 of the present invention for 120 DEG C.
Taking the zeolite product B4 that part is above-mentioned, measure through X-ray powder diffraction, its diffraction pattern is with figure
1 feature, illustrates that it is ZSM-5.Na in XRF analysis, B4 molecular sieve2O content is 0.02%, P2O5
Content is 1.49%, Y2O3Content is 1.16%, and silica alumina ratio is 188.Through low temperature N2-adsorption analysis, B4
The BET method specific surface area of molecular sieve is 418m2/ g, total pore volume is 0.31mL/g, and its mesoporous is > 2nm
Mesoporous pore volume is 0.14mL/g, and accounting for total pore volume ratio is 45.2%.
22.34 grams of kaolin (China Kaolin Co., Ltd's product, igloss 16%) are added 150 grams of deionizations
Water and 261 grams of Alumina gel making beating, add 300 grams of butt molecular sieve B4 and be sufficiently mixed uniformly, then existing
Spray shaping microspherical catalyst on small spraying drying shaping apparatus, screening obtains diameter 38-150 μ m
Microballoon, thus obtained microsphere is dried 16h through 120 DEG C, then within 4 hours, is obtained microballoon catalysis in 550 DEG C of temperature, roasting
Agent CB4.
CB4 catalyst consists of 80% weight molecule sieve B4,15% weight Al2O3With 5% weight kaolin.
Embodiment 3
0.8 kg of hydrogen aluminum oxide is joined 330 kilograms of TPAOH aqueous dissolution, adds
150 grams of deionized waters and 150 kilograms of white carbons (production of Guangdong Hai Hua Chemical Co., Ltd.), stir mixing 2
Hour.Mole consisting of of gained reactant mixture: TPAOH/SiO2=0.17, SiO2/Al2O3=300,
H2O/SiO2=12.Reactant mixture is loaded stainless steel crystallizing kettle, 120 DEG C, continuously stir and spontaneous pressure
Crystallization 100 hours under power.Then crystallization product is filtered, wash and dry 16h, i.e. score at 120 DEG C
Son sieves former powder products C 1.
By above-mentioned dry former powder C1 as in Muffle furnace, in 600 DEG C of roasting 2h, obtain roasting molecular sieve powder C2.
Take double centner butt above-mentioned roasting molecular sieve powder C2 to join 1000 kilograms of deionized waters stir and beat
Slurry, is subsequently adding 1.11 kilograms of fluorine silicic acid aqueous solutions, is placed in exchange still and seals, heats up under continuous stirring
To 150 DEG C, under still pressure is for 0.48Mpa, keep 4h, be then cooled to 40 DEG C of filtrations, washing, obtain filter cake
Products C 3.
0.68 kilogram of ammonium dihydrogen phosphate is dissolved in 40 kilograms of deionized waters, adds with RE2O3Meter
(Sinopec catalyst asphalt in Shenli Refinery product, rare earth partition is for containing for the mixed chlorinated rare earth solution of 100g/L
60%La2O3, 40%CeO2) 4.4L, add 70 kilograms of butt above-mentioned molecular sieve filter cake C3 stirring to pulps uniformly,
Then slurries are dried 16h at 120 DEG C, obtain combination of molecular sieve products C 4 of the present invention.
Taking the zeolite product C4 that part is above-mentioned, measure through X-ray powder diffraction, its diffraction pattern is with figure
1 feature, illustrates that it is ZSM-5.Na in XRF analysis, C4 molecular sieve2O content is 0.04%, P2O5
Content is 0.69%, La2O3Content is 0.42%, CeO2Content is 0.26%, and silica alumina ratio is 374.Through too low
Temperature N2-adsorption analysis, the BET method specific surface area of C4 molecular sieve is 440m2/ g, total pore volume is 0.323mL/g,
Its mesoporous is > the mesoporous pore volume of 2nm is 0.171mL/g, accounting for total pore volume ratio is 52.9%.
By 85 grams of butt molecular sieve C4 and 15 grams of dry glue powders (production of Sinopec catalyst Chang Ling branch company)
Being sufficiently mixed, the aqueous acetic acid adding 1.5% weight is mediated, and then extrudes diameter 1.5mm with banded extruder
Bar shaped catalyst, dry 16h through 120 DEG C, then 550 DEG C of temperature, roasting 2 hours bar shaped catalysis
Agent CC4.
CC4 catalyst consists of 90% weight molecule sieve C4 and 10% weight Al2O3。
Embodiment 4
Take the roasting molecular sieve powder B2 of preparation in double centner butt embodiment 2 and join 800 grams of deionized waters
Middle stirring to pulp, is subsequently adding 7.48 kilograms of fluorine silicic acid aqueous solutions and 1 kilogram of aqueous hydrochloric acid solution (containing 10% weight
Hydrochloric acid), it is placed in exchange still and seals, be warming up to 120 DEG C under continuous stirring, in still pressure under 0.21Mpa
Keep 2h, be then cooled to 50 DEG C of filtrations, washing, obtain filter cake product D3.
1.46 kilograms of ammonium dihydrogen phosphates are dissolved in 50 kilograms of deionized waters, then by 2.39 kilogram of six hydration
Lanthanum nitrate salt is dissolved in 40 kilograms of deionized waters, and joins formation colloid in ammonium dihydrogen phosphate, to
This colloid adds 90 kilograms of butt above-mentioned molecular sieve filter cake D3 stirring to pulps uniform, then by slurries 120
DEG C dry 24h, obtain combination of molecular sieve product D4 of the present invention.
Taking the zeolite product D4 that part is above-mentioned, measure through X-ray powder diffraction, its diffraction pattern is with figure
1 feature, illustrates that it is ZSM-5.Na in XRF analysis, D4 molecular sieve2O content is 0.02%, P2O5
Content is 0.99%, La2O3Content is 1.17%, and silica alumina ratio is 274.Through low temperature N2-adsorption analysis, D4
The BET method specific surface area of molecular sieve is 432m2/ g, total pore volume is 0.32mL/g, and its mesoporous is > 2nm
Mesoporous pore volume is 0.15mL/g, and accounting for total pore volume ratio is 46.9%.
300 grams of butt molecular sieve D4 (are weighed SiO containing 25% with 211.6 grams of Ludox2) be sufficiently mixed,
Then rotating into pellet catalyst in bowling machine, screening obtains the bead of diameter 1.4-2.0mm, and gained is little
Ball warp 120 DEG C dries 16h, after in Muffle furnace through 600 DEG C of temperature, roasting 8 hours pellet catalyst CD4.
CD4 catalyst consists of 85% weight molecule sieve D4 and 15% weight SiO2。
Comparative example 1
The preparation process of the ZSM-5 molecular sieve catalyst that the explanation of this comparative example is conventional.
(Sinopec catalyst Jian Chang branch company produces, the trade mark to take 500 grams of butt ZSM-5 molecular sieves
ZRP-5B, silica alumina ratio 120～150) after 550 DEG C of roasting 4h take off amine process, add 3000mL deionization
Water is pulled an oar, and adds 100 grams of ammonium chlorides and 10 grams of aqueous hydrochloric acid solutions (containing 10% geavy salt acid), and in stirring
Under be warming up to 70 DEG C exchange 1h, filter, wash, filter cake again add 3000mL deionized water making beating, then
Add after 100 grams of ammonium chlorides and 10 grams of aqueous hydrochloric acid solutions (containing 10% geavy salt acid), be under agitation warming up to 70 DEG C
Exchange 1h, filter, wash after through 120 DEG C dry 16h, sieve sample DBA must be contrasted.
Taking the molecular screen primary powder DBA that part is above-mentioned, measure through X-ray powder diffraction, its diffraction pattern is with figure
1 feature, illustrates that it is ZSM-5.Na in XRF analysis, DBA molecular sieve2O content is 0.01%, silicon
Aluminum ratio is 145.Through low temperature N2-adsorption analysis, the BET method specific surface area of DBA molecular sieve is 355m2/ g,
Total pore volume is 0.21mL/g, and its mesoporous is > the mesoporous pore volume of 2nm is 0.03mL/g, accounts for total pore volume ratio
It is 14.3%.
By above-mentioned 80 grams of butt molecular sieve DBA and 20 grams of butt boehmite mixing, continuously add 1.5%
The aqueous acetic acid of weight is fully mediated, then through the bar shaped catalyst of banded extruder extrusion diameter 1.5mm,
Dry 16h by 120 DEG C, then within 8 hours, obtain bar shaped catalyst CDBA in 600 DEG C of temperature, roasting.
CDBA catalyst consists of 80% weight molecule sieve DBA and 20% weight Al2O3。
Comparative example 2
The explanation of this comparative example uses fluosilicic acid, the ZSM-5 molecular sieve obtained under the conditions of non-aqueous heat treatment equally
Composition is the catalyst that active component obtains.
(Sinopec catalyst Jian Chang branch company produces, the trade mark to take 1000 grams of butt ZSM-5 molecular sieves
ZRP-5, silica alumina ratio 80～100) join stirring to pulp in 8000 grams of deionized waters, it is subsequently adding 460.8
Gram fluorine silicic acid aqueous solution, is placed in exchange still, is warming up to 70 DEG C under continuous stirring, keep 2h, then drop
Temperature, to 60 DEG C of filtrations, washings, obtains filter cake.15.0 grams of ammonium dihydrogen phosphates are dissolved into 500 grams of deionized waters
In, then 30.0 grams of lanthanum nitrate hexahydrate salt are dissolved in 400 grams of deionized waters, and join biphosphate
Ammonium salt solution is formed colloid, in this colloid, adds 900 grams of butt above-mentioned molecular sieve filter cake stirring to pulps uniformly,
Then slurries are dried 24h at 120 DEG C, sieve sample DBB must be contrasted.
Taking the zeolite product DBB that part is above-mentioned, measure through X-ray powder diffraction, its diffraction pattern is with figure
1 feature, illustrates that it is ZSM-5.Na in XRF analysis, DBB molecular sieve2O content is 0.01%, P2O5
Content is 1.02%, La2O3Content is 1.47%, and silica alumina ratio is 285.Through low temperature N2-adsorption analysis, DBB
The BET method specific surface area of molecular sieve is 384m2/ g, total pore volume is 0.20mL/g, and its mesoporous is > 2nm
Mesoporous pore volume is 0.03mL/g, and accounting for total pore volume ratio is 15.0%.
Above-mentioned 600 grams of butt molecular sieve DBB (are weighed SiO containing 25% with 423.2 grams of Ludox2) fully
Mixing, then rotates into pellet catalyst in bowling machine, and screening obtains the bead of diameter 1.4-2.0mm,
The little ball warp of gained 120 DEG C dries 16h, after in Muffle furnace through 600 DEG C of temperature, roasting 4 hours bead is urged
Agent CDBB.
CDBB catalyst consists of 85% weight molecule sieve DBB and 15% weight SiO2。
Embodiment 5-8
The MTP course of reaction of embodiment 5-8 explanation present invention offer and result.
MTP reaction evaluating is carried out on atmospheric fixed bed micro anti-evaluation device, and this device is by sampling system, anti-
Answer device, product collection system, regenerative system and temperature control system five part composition.The catalyst of filling is in reaction
Purging to reaction temperature with High Purity Nitrogen when evaluating pre-heating temperature elevation, methanol aqueous solution raw material micro-injection pump injects
In reactor, product cools down laggard promoting the circulation of qi liquid product and separates, and gaseous products is collected through draining water gathering of gas law and gone forward side by side
Row chromatography, liquid-phase product carries out chromatography after collecting；After having reacted, temperature of reactor is risen to
600 DEG C, being passed through oxygen simultaneously and regenerate, regeneration gas is fully oxidized by oxidation furnace, the CO of generation2Gas
Body is by the infrared CO of QGS-08D2Gas analyzer measures, and obtains the long-pending of post catalyst reaction after integrated computing
Carbon content.
The catalyst sample of embodiment 1-4 become 20-40 mesh particle standby after crushing and screening.MTP reaction is commented
During valency, catalyst in reactor loadings is 2 grams.Use 50% weight methanol aqueous solution charging, in reaction temperature
The MTP reaction mass that the lower charging of degree starts after stablize 1h to measure in 10min subsequently balances.Gained methyl alcohol converts
Rate and product are distributed as the mean value in 10min feed time section.The carbon back productivity (%) of propylene is product third
Carbon in alkene accounts for the mass percent of carbon in charging methyl alcohol.Evaluation response temperature is 470 DEG C, methyl alcohol charging WHSV
For 11h-1, reaction pressure is slightly above normal pressure.
Gained reaction evaluating result is listed in table 1.
Comparative example 3,4
This comparative example explanation catalyst containing conventional ZSM-5 molecular sieve is applied to commenting of MTP course of reaction
Valency result.
With embodiment 5, difference, process is that catalyst used is comparative example 1, the catalyst of comparative example 2.
Table 1
From the evaluation result of table 1 it can clearly be seen that compared with the catalyst of prior art, use the present invention
The catalyst of molecular sieve catalysis methanol conversion can obtain propylene effectively, through peracidity and the modulation of pore structure,
While keeping methyl alcohol high conversion, propylene/ethylene mass ratio is significantly improved, and this advantageously reduces instead
Answer the separating energy consumption of ethene in product subsequent separation system, improve the benefit of MTP reaction unit.
Embodiment 9
This example demonstrates that the catalyst of the present invention life assessment result when MTP process.
Become 20-40 mesh particle standby after crushing and screening the catalyst sample of embodiment 8.
MTP reaction life assessment still uses the MAT device in embodiment 9 description, and catalyst in reactor fills
The amount of filling out is 8 grams.Use the methanol aqueous solution charging of 50% weight, under 460 DEG C of reaction temperatures, methyl alcohol charging
WHSV is 1.5h-1, reaction pressure slightly above normal pressure carries out life assessment.With methanol conversion less than 96% work
Standard for catalysqt deactivation.
Gained methanol conversion is listed in Fig. 2 with the result of variations in reaction time.
Comparative example 5
The comparative catalyst of this comparative example explanation comparative example 2 is applied to the life assessment result of MTP course of reaction.
Process is, with embodiment 9, difference, the comparative catalyst that catalyst used is comparative example 2.
Gained methanol conversion is listed in Fig. 2 with the result of variations in reaction time.
Figure it is seen that compared with comparative catalyst, use ZSM-5 molecular sieve composition of the present invention
Process, the one way active lifetime of its catalyst is obviously prolonged, and advantageously reduces the regeneration times of catalyst, prolongs
The long use cycle.
Claims (22)
1. a catalyst for producing propylene with methanol, it is characterised in that containing 30-95 weight % combination of molecular sieve,
5-70 weight % inorganic oxide and the clay with 0-50 weight %, in described combination of molecular sieve, with
On the basis of combination of molecular sieve, containing with P2O5Meter 0.1-10 weight % phosphorus and in terms of oxide
The rare earth of 0-10 weight %, the described molecular sieve in combination of molecular sieve is ZSM-5 molecular sieve, described
ZSM-5 molecular sieve in, alkali metal content in terms of oxide be less than 0.2 weight %, SiO2With A12O3
Molar ratio be 100-1000, nitrogen adsorption methods measure under BET method specific surface area be
300-600m2/ g, total pore volume is 0.2-0.6mL/g, bore dia > the mesoporous pore volume of 2nm accounts for total pore volume
30-70%.
2. according to the catalyst of claim 1, wherein, in described combination of molecular sieve, described phosphorus be with
P2O5The content of meter is 0.2-5 weight %, the content that described rare earth is counted with oxide for 0-5 weight %,
Described alkali metal content in terms of oxide is less than 0.1 weight %.
3. according to the catalyst of claim 1, in wherein described combination of molecular sieve, SiO2With A12O3Rub
Your ratio is 150-500.
4., according to the catalyst of claim 1, in wherein described combination of molecular sieve, described BET method compares table
Area is 350-500m2/ g, total pore volume is 0.3-0.5mL/g, its median pore diameter > the mesoporous pore volume of 2nm
Account for the 40-60% of total pore volume.
5. according to the catalyst of claim 1, in wherein described combination of molecular sieve, described rare earth selected from yttrium,
One or more in lanthanum, cerium, praseodymium.
6. according to the catalyst of claim 1, wherein, containing 50-90 weight % combination of molecular sieve, 10-50
Weight % inorganic oxide and and the clay of 0-30 weight %.
7., according to the catalyst of claim 1, the bead for strip catalyst or for a diameter of 0.5-5.0mm is urged
Agent, or use the microspherical catalyst of a diameter of 15-150 μm that spray drying process obtains.
8. the preparation method of the catalyst of one of claim 1-7, it is characterised in that the method includes preparation one
Combination of molecular sieve, then by combination of molecular sieve and inorganic oxide binder and be with or without clay and exist
The step that interior catalyst precursor mixture is shaped, wherein described preparation one molecular sieve combination
The process of thing includes organic for the ZSM-5 molecular sieve fired removing of former powder of alkali metal-free or low alkali
Template obtains roasting powder；Roasting powder carries out liquid phase acid treatment and obtains pickling filter cake；And, described acid
Filter wash cake reclaims after carrying out the activation process of phosphorus-containing compound and compounds containing rare earth and obtains ZSM-5 molecule
The step of screen composition, wherein, described roasting powder carries out liquid phase acid treatment and obtains the step of pickling filter cake
It is by roasting powder and the acidic aqueous solution making beating non-uniform components screening the pulp liquid containing fluosilicic acid, and in airtight still
Under middle temperature 100-200 DEG C, pressure 0.1-2Mpa, hydro-thermal processes, described fluosilicic acid and described roasting
The mass ratio of butt burning powder is 0.0001-0.1:1, and in described molecular sieve pulp, water and roasting powder is dry
The mass ratio of base is 3-20:1.
9. the former powder of according to the method for claim 8, wherein, described ZSM-5 molecular sieve is to obtain through following process:
Aluminium source, silicon source, water and organic formwork agent are thoroughly mixed to form reactant mixture, and molar composition ranges is
Organic formwork agent/SiO2=0.03-0.3, SiO2/Al2O3=100-1000, H2O/SiO2=5-30, Qi Zhongyou
Machine template is tetraethyl ammonium hydroxide or TPAOH, by reactant mixture under agitation,
Hydrothermal crystallizing 20～200 hours under the temperature of 70～200 DEG C, self-generated pressure, crystallization product through filtering,
It is dried at a temperature of 80-200 DEG C after washing, obtains the former powder of ZSM-5 molecular sieve.
10. according to the method for claim 9, wherein, described aluminium source is selected from hydrated alumina, aluminum sulfate, nitric acid
Aluminium, aluminium hydroxide or aluminium isopropoxide；Described silicon source is selected from solid silicone or white carbon.
11. according to the method for claim 8, wherein, described roasting removing organic formwork agent, its condition be
Ingress of air roasting 0.5-50h at 300-800 DEG C.
12. according to the method for claim 8, and wherein, described hydro-thermal processes, and its condition be in airtight still, warm
Spend 105-180 DEG C, pressure 0.11-1Mpa.
13. according to the method for claim 8, and wherein, described hydro-thermal processes, and its condition be in airtight still, warm
Spend 105-150 DEG C, pressure 0.12-0.7Mpa.
14. according to the method for claim 8, wherein, and the quality of described fluosilicic acid and the butt of described roasting powder
Ratio is 0.001-0.05.
15. according to the method for claim 14, wherein, and the matter of described fluosilicic acid and the butt of described roasting powder
Amount ratio is 0.002-0.01.
16. according to the method for claim 8, wherein, and the matter of water and the butt of roasting powder in described molecular sieve pulp
Amount ratio is 4-15.
17. according to the method for claim 16, wherein, and the butt of water and roasting powder in described molecular sieve pulp
Mass ratio is 5-10.
18. according to the preparation method of claim 8, and wherein, described pickling filter cake carries out phosphorus-containing compound and containing dilute
The activation process of earth compounds is that the solvable inorganic phosphor-contained compound of required amount of calculation is dissolved in water, with institute
Need the soluble salt containing one or more rare earth elements in yttrium, lanthanum, cerium and praseodymium water-soluble of amount of calculation
Liquid is sufficiently mixed into activator, is mixed, so with the making beating of ZSM-5 molecular sieve pickling filter cake by activator
After at a temperature of 80-800 DEG C be dried, roasting.
The method of 19. 1 kinds of methyl alcohol light olefins, it is characterised in that the method is with the catalyst of one of claim 1-7
In the presence of carry out.
20. according to the method for claim 19, and wherein, described light olefin is propylene.
21. according to the method for claim 19, adds steam or inert gas regulates methyl alcohol charging dividing potential drop, institute
It it is 250 DEG C-600 DEG C by reaction temperature；Reaction pressure used is 0.1-50 atmospheric pressure, and weight used is empty
Speed is 0.01-50h-1。
22. according to the method for claim 21, and wherein, reaction temperature used is 350 DEG C-500 DEG C；Reaction used
Pressure is 0.5-5 atmospheric pressure, and weight space velocity used is 0.1-10h-1。
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| CN107970985B (en) * | 2016-10-21 | 2020-02-28 | 中国石油化工股份有限公司 | Aromatization auxiliary agent and preparation method thereof |
| CN107970984B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof |
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