CN104226363B - The preparation method of oxygenatedchemicals olefin hydrocarbon molecules sieve fluid catalyst - Google Patents

The preparation method of oxygenatedchemicals olefin hydrocarbon molecules sieve fluid catalyst Download PDF

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CN104226363B
CN104226363B CN201310237149.7A CN201310237149A CN104226363B CN 104226363 B CN104226363 B CN 104226363B CN 201310237149 A CN201310237149 A CN 201310237149A CN 104226363 B CN104226363 B CN 104226363B
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microsphere
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sapo
sieve
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CN104226363A (en
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王伟
刘红星
管洪波
张玉贤
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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

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Abstract

A kind of method that the present invention relates to preparing low-carbon olefin from oxygen-containing compounds molecular sieve fluid bed catalyst, is mainly used in solving catalyst Middle molecule sieve degree of crystallinity in prior art relatively low, for the poor problem of preparing low-carbon olefin from oxygen-containing compounds catalytic reaction activity.The present invention is comprised the following steps by employing: (a) will mix with water containing silicon source, aluminum source, the raw material of phosphorus source；B () adds binding agent and forms high speed shear suspension after suspension, obtain silicon phosphorus aluminum oxide microsphere by spray drying method；C () high-temperature roasting microsphere is designated as microsphere a, low-temperature bake microsphere is designated as microsphere b；D () uses hydrothermal synthesis method to produce molecular sieve mutually at microsphere surface and body after being mixed in proportion with microsphere b by microsphere a；E () roasting microsphere obtains the technical scheme of finished catalyst and preferably resolves this problem, can be applicable in the course of reaction of preparing low-carbon olefin from oxygen-containing compounds.

Description

The preparation method of oxygenatedchemicals olefin hydrocarbon molecules sieve fluid catalyst
Technical field
The present invention relates to a kind of method preparing molecular sieve fluid bed catalyst, fall especially with regard to a kind of preparation method for the molecular sieve fluid bed catalyst of preparing low-carbon olefin from oxygen-containing compounds.
Background technology
Low-carbon alkene, as the important basic organic chemical industry raw material of chemical industry, plays very important effect in modern petroleum and chemical industry.Ethylene is used for manufacturing various vinyon, and is used for manufacturing other chemicals such as vinyl chloride, oxirane, ethylo benzene and alcohol.Propylene is used for manufacturing various polypropylene plastics, and is used for manufacturing other chemicals such as acrylonitrile and expoxy propane.Along with the development of Chinese national economy, the demand of light olefin is day by day risen by especially modern chemical industry, the development of chemical industry, and imbalance between supply and demand also will become increasingly conspicuous.Up to now, the ethylene yield of more than 98% is still from steam cracking technology in the world, and the 67% of propylene yield produces the side-product of ethylene from steam cracking, and 30% produces vapour, the side-product of diesel oil from oil plant catalytic cracking (FCC).Yet with petroleum resources ongoing shortage in recent years, production capacity increases the non-renewable of limited and petroleum resources, crude oil price one tunnel is high, and this makes ethylene, the production cost of propylene rises therewith, and verified oil resource only can be exploited nearly 50 years by the existing level of production again.For the contradiction in terms of solution alkene supply and demand, exploitation non-petroleum feedstocks producing light olefins utilizes technology extremely the most urgent.
Oxygenatedchemicals especially alcohol, it is possible to change into low-carbon alkene.Preferably conversion process refers to oxygenatedchemicals-to-alkene (OTO) course of reaction, a kind of particularly preferred OTO technique is methanol-to-alkene (MTO) course of reaction, and wherein methanol is primarily converted into ethylene and/or propylene in the presence of molecular sieve catalyst.Methanol is a kind of common big industrial chemicals, can be produced as raw material by coal, natural gas, biomass, solid waste etc., and raw material sources are quite varied.The raw materials such as natural gas obtain synthesis gas (CO+H by partial oxidation process or steam reforming2), then under the effect of catalst for synthesis of methanol (such as cu zn oxide catalyst), convert in synthesis reactor and obtain methanol.Natural gas or coal produce methanol through synthesis gas and have realized industrialization, and scale constantly expands, technology becomes better and approaching perfection day by day.Non-oil resource such as natural gas resource relative abundance, although increasing with the highest consumption rate, but worldwide natural gas supply still can ensure more than 100 year.Therefore, methanol-to-olefins (Methanol to Olefin, it is called for short MTO) technology, as the new technology route being produced basic organic chemical industry raw material by coal or natural gas, it is to be hopeful most to replace or part substitutes the Petroleum route as waste alkene, is also the effective way realizing Coal Chemical Industry or gas chemical industry to petrochemical industry infiltration and development.This method can regulate product proportion in a big way, to meet the demand in market.Exploitation methanol-to-olefins technology, to guaranteeing national energy security, economy is quick, sustainable development has far reaching significance.
Methanol-to-olefins process, needs to carry out under the effect of molecular sieve shape selective catalysis.A lot of molecular sieves are used equally to the catalyst activity component of methanol-to-olefins, the ZSM-5 molecular sieve being such as widely known by the people, SAPO molecular sieve etc..Other molecular sieves that can be used for methanol to olefins reaction have T zeolite, ZK-5, erionite and chabasie etc..Up to the present, the molecular sieve being applied to methanol-to-olefins reaction process is optimal with SAPO-34 molecular sieve performance, SAPO-34 molecular sieve is a kind of SAPO microporous crystal, it is similar to that chabasie, belongs to trigonal system, there is three-dimensional open-framework, its orifice diameter is 0.43nm, there is strong shape selectivity, thus when methanol to olefins reaction performance functional, the selectivity of low-carbon alkene is higher.
When molecular sieve is applied to Industrial Catalysis, the molecular sieve of 100% typically can not be used to be prepared as catalyst and to be applied to industrial process.The bonds itself of molecular sieve is poor, and self granularity is the most tiny, it is difficult to be shaped to directly apply to the catalyst of industrial process.The manufacturing cost of molecular sieve is the highest, if the molecular sieve of employing 100% is as industrial catalyst, the operating cost making industrial process is increased.Industrial process typically requires that catalyst possesses certain shape and intensity to be adapted to industrial reactor.For fixed bed reactors, catalyst is after mounting without movement, but catalyst need to possess certain crush strength, to prevent catalyst during dress agent to be hit and damaged, and prevents the catalyst being arranged on lower floor owing to bearing pressure and damaged.For fluidized-bed reactor, owing to catalyst itself the most constantly circulates or turbulence, so catalyst is in addition to needing good activity and selectivity, also there are the various physical propertys such as certain sphericity, good particle size distribution, heap ratio.Therefore, either molecular sieve is applied to fixed bed reactors, is still applied to fluidized-bed reactor, be both needed to by the effect of binding agent, molecular sieve and carrier material are formed molecular sieve catalyst composition；This combination of molecular sieve can have catalysis activity, selectivity, stability, shape and intensity concurrently simultaneously, thus meets the industrial process requirement to catalyst.
At present, be applied to the main preparation methods of fluid catalyst of preparing low-carbon olefin from oxygen-containing compounds reaction be molecular sieve, substrate, binding agent and structural promoter are sufficiently mixed after make uniform sizing material, then be shaped by the dry means such as press atomization, centrifugal spray.CN200810043249.5 reports a kind of method that molecular sieve, binding agent, carrier material mixed atomizing are prepared as fluid catalyst；CN1132533A reports the preparation of the wear-resistant catalyst converting low-carbon alkene for methanol, improves the abrasion resistant effect of catalyst by reducing the content of catalyst Middle molecule sieve.CN200810043248.0 reports a kind of by controlling the method that proportioning process strengthens molecular sieve fluid bed catalyst abrasion.USP5248647 reports and SAPO-34 molecular sieve, Kaolin, Ludox is made slurry, and spray shaping prepares the way of fluid catalyst.USP6153552 reports a kind of microspherical catalyst preparation method containing SAPO molecular sieve, by spray shaping after SAPO molecular sieve, inorganic oxide sol, phosphorus-containing compound mixing making beating.
By first preparing phosphorus silicon aluminium microsphere, then changing sintering temperature and can control the state of activation of the phosphorus on microsphere, silicon, aluminum oxide, the molecular sieve fluid bed catalyst that after proportionally adding the microsphere of different sintering temperature, fabricated in situ obtains has its unique advantage.Owing to when can more preferably control synthesis, active phosphorus, silicon, aluminum oxide ratio make synthetic reaction more complete, in catalyst spheres body, duct is enriched and is also beneficial to diffusion thus improves the selectivity of preparing low-carbon olefin from oxygen-containing compounds；On the other hand, also will be enhanced by chemical bonds, the wear-resisting intensity of its spheroid due to molecular sieve and matrix.
Relevant in-situ synthesis prepare fluid catalyst be applied to preparing low-carbon olefin from oxygen-containing compounds reaction report less, patent CN101157057B also relates to this type of preparation method, but its molecular sieve fluid bed catalyst degree of crystallinity prepared is relatively low, poor for preparing low-carbon olefin from oxygen-containing compounds catalytic reaction activity.
Summary of the invention
The technical problem to be solved be overcome in existing document report to utilize in-situ synthesis to prepare molecular sieve fluid bed catalyst Middle molecule sieve degree of crystallinity relatively low, the problem that activity is relatively low when converting oxygen-containing compound to low-carbon olefins, it is provided that a kind of new molecular sieve fluid bed catalyst preparation method.The molecular sieve crystallinity that the method has prepared fluid catalyst is high, the advantage that activity is high when converting oxygen-containing compound to low-carbon olefins.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of a kind of molecular sieve fluid bed catalyst, in turn includes the following steps:
A silicon source, aluminum source, phosphorus source are mixed to form mixed liquor with water by ()；In mixed liquor, the mol ratio of each oxide consists of: Al2O3∶aSiO2∶bP2O5, wherein the span of a is 0.05～5, and the span of b is 0.05～5；
B () adds binding agent and forms the suspension of slurry, wherein binding agent accounts for the ratio of suspension gross mass and is: binding agent/suspension=0.001～0.4；
C () high speed shear suspension is until the particle scale of 90% is less than 8 microns in suspension；
D () is spray-dried suspension, obtain silicon phosphorus aluminum oxide microsphere；
E silicon phosphorus aluminum oxide microsphere is divided into two parts, part roasting at temperature T1 by (), be designated as microsphere a, and temperature T1 scope is 400～1000 DEG C；Another part roasting at temperature T2, is designated as microsphere b, and temperature T2 scope is 200～800 DEG C;Burnt the most every time and kept T1 > T2；
F microsphere a, microsphere b are mixed by () with water, template, put into crystallizing kettle and carry out hydrothermal crystallizing, and crystallization temperature is 120～220 DEG C, crystallization time 6～72 hours；Template, water, the mass ratio of microsphere is wherein used to be followed successively by: template/water=0.1～10；Template/microsphere=0.1～10；Microsphere A/ microsphere B=0.01～100；
G the microsphere after () roasting hydrothermal crystallizing obtains finished catalyst.
In technique scheme, preferred technical scheme be the molecular sieve of fluid catalyst be at least one in SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-44, SAPO-47, SAPO-56；Phosphorus source is at least one in orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphorus compound, phosphorous oxides；Aluminum source is at least one in activated alumina, boehmite, aluminum isopropylate., Kaolin, aluminium salt；Silicon source is at least one in Ludox, active silica, tetraethyl orthosilicate, Kaolin；At least one in Ludox, Silica hydrogel, Alumina gel, silicon-aluminum sol of binding agent；Template is a kind of organic amine, selected from diethylamine, triethylamine, n-propylamine, 2-aminopropane., Tri-n-Propylamine, Tris(isopropylamine)., di-n-propylamine, diisopropylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, 1, at least one in 6-hexamethylene diamine, cyclohexylamine, morpholine, ethanolamine, diethanolamine, triethanolamine；Microsphere A/ microsphere B=0.1～10；Crystallization temperature is 150～200 DEG C, and crystallization time is 12～48 hours.Preferably technical scheme is that the span of a is 0.1～3, and the span of b is 0.1～3.
In technique scheme, finished catalyst Middle molecule sieve is present in surface and the body phase of catalyst microspheres, and preferred technical scheme is the 70-90% that body phase molecule sieve accounts for finished catalyst gross weight.Preferably technical scheme is that temperature T1 scope is 400～600 DEG C；Temperature T2 scope is 500～700 DEG C.Preferably technical scheme is, high speed shear suspension is until the particle scale of 90% is less than 5 microns in suspension.Preferably technical scheme is, high speed shear suspension is until the particle scale of 95% is less than 3 microns in suspension.
Obtained catalyst can be applicable to the course of reaction of preparing low-carbon olefin from oxygen-containing compounds.
Obtained catalyst is placed in the evaluation carrying out methanol to olefins reaction on the fixed bed reactors that the stainless steel tube of Φ 10mm × 1mm is made, apparatus with catalyst inside 2.0 grams, charging is pure methanol, and reaction temperature is 400～500 DEG C, and reaction velocity is 2～10 grams of methanol/gram catalyst hour.
The present invention is by being introduced into a certain proportion of high temperature and the method for ratio that low-temperature bake microsphere improves active phosphorus in liquid phase synthesis, silicon, aluminum oxide is incorporated into in-situ synthesis and prepares in molecular sieve fluid bed catalyst technique, improve the degree of crystallinity of molecular sieve fluid bed catalyst Middle molecule sieve, when being used for converting oxygen-containing compound to low-carbon olefins as catalyst, activity is improved, methanol conversion is close to 100%, ethylene can reach 84.4% with the yield of propylene, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[comparative example 1]
Joining according to oxide dry basis content 30wt% and take slurry, the orthophosphoric acid (content 85wt%) of metering, boehmite (content 70wt%), tetraethyl orthosilicate (content 30wt%) are added sequentially in deionized water, the mol ratio now adding each component is Al2O3∶P2O5∶SiO2=1:1:1.25, adds Ludox (content 30wt%) after stirring 10min, and Ludox accounts for the 5% of slurry gross mass.Continuing colloid mill 30min after stirring 10min, measure the granularity of this suspension with laser particle analyzer, its mean diameter is less than 3 microns.
Being spray-dried by slurry centrifugal spray dryer, spray condition is inlet temperature 260 DEG C, leaving air temp 140 DEG C, and obtained phosphorus sieve and silica-sesquioxide bead laser particle analyzer measures its granularity, and mean diameter is 78 microns.
Put into teflon-lined crystallizing kettle after obtained phosphorus sieve and silica-sesquioxide bead is put into 700 DEG C of high-temperature roastings of Muffle furnace 5 hours, being added sequentially water and morpholine again, the mass ratio of the most each component is: phosphorus sieve and silica-sesquioxide bead: water: morpholine=1:10:3.Baking oven is put into, in 180 DEG C of crystallization 18 hours after being sealed by crystallizing kettle.Crystallization carries out after completing washing, is dried, roasting.Using X-ray diffraction spectrogrph to be analyzed sample, recording crystal on synthesized catalyst is SAPO-34 molecular sieve, it is stipulated that its relative crystallinity is 100%.
[comparative example 2]
According to each Step By Condition of comparative example 1, but the template morpholine in reactor being changed to triethylamine, the degree of crystallinity finally obtaining SAPO-34 is 90.2%.
[embodiment 1]
Joining according to oxide dry basis content 30wt% and take slurry, the orthophosphoric acid (content 85wt%) of metering, boehmite (content 70wt%), tetraethyl orthosilicate (content 30wt%) are added sequentially in deionized water, the mol ratio now adding each component is Al2O3∶P2O5∶SiO2=1:1:1.25, adds Ludox (content 30wt%) after stirring 10min, and Ludox accounts for the 5% of slurry gross mass.Continuing colloid mill 30min after stirring 10min, measure the granularity of this suspension with laser particle analyzer, its mean diameter is less than 3 microns.
Being spray-dried by slurry centrifugal spray dryer, spray condition is inlet temperature 260 DEG C, leaving air temp 140 DEG C, and obtained phosphorus sieve and silica-sesquioxide bead laser particle analyzer measures its granularity, and mean diameter is 78 microns.
Obtained a part of phosphorus sieve and silica-sesquioxide bead is put into 900 DEG C of high-temperature roasting 5 hour-symbols of Muffle furnace is microsphere a, is microsphere b by another part phosphorus sieve and silica-sesquioxide bead input 400 DEG C of roasting 5 hour-symbols of Muffle furnace.
Being put into teflon-lined crystallizing kettle according to mass ratio 1:1.5 by microsphere a and microsphere b, then be added sequentially water and morpholine, the mass ratio of the most each component is: phosphorus sieve and silica-sesquioxide bead: water: morpholine=1:10:3.Baking oven is put into, in 180 DEG C of crystallization 18 hours after being sealed by crystallizing kettle.Crystallization carries out after completing washing, is dried, roasting.Using X-ray diffraction spectrogrph to be analyzed sample, recording crystal on synthesized catalyst is SAPO-34 molecular sieve, and recording its relative crystallinity is 110%.
[embodiment 2]
According to each Step By Condition of embodiment 1, but the template morpholine in reactor being changed to triethylamine, the degree of crystallinity finally obtaining SAPO-34 is 98%.
[embodiment 3]
According to each Step By Condition of embodiment 1, but with microsphere b mass ratio, microsphere a in reactor being adjusted to 1:1, the degree of crystallinity finally obtaining SAPO-34 is 121%.
[embodiment 4]
According to each Step By Condition of embodiment 1, but with microsphere b mass ratio, microsphere a in reactor being adjusted to 1.5:1, the degree of crystallinity finally obtaining SAPO-34 is 102%.
[embodiment 5]
According to each Step By Condition of embodiment 1, but crystallization temperature being adjusted to 160 DEG C, the degree of crystallinity finally obtaining SAPO-34 is 115%.
[embodiment 6]
According to each Step By Condition of embodiment 1, but the sintering temperature of microsphere a being adjusted to 850 DEG C, the degree of crystallinity finally obtaining SAPO-34 is 111%.
[embodiment 7]
According to each Step By Condition of embodiment 1, but the sintering temperature of microsphere b being adjusted to 550 DEG C, the degree of crystallinity finally obtaining SAPO-34 is 114%.
[embodiment 8]
Obtained SAPO-34 molecular sieve catalyst is placed in the evaluation carrying out methanol to olefins reaction on the fixed bed reactors that the stainless steel tube of Φ 10mm × 1mm is made, built-in SAPO-34 molecular sieve catalyst 2.0 grams, charging is pure methanol, reaction temperature is 460 DEG C, 6 grams of methanol/gram catalyst hour of reaction velocity.Product carries out chromatography after gas-liquid separation.Analytical tool is HP7890 type gas chromatogram, Φ 0.53mm × 0.4 μ m 30m HP-Q capillary column, flame ionization ditector.Result is as shown in table 1:
Table 1

Claims (10)

1. a preparation method for oxygenatedchemicals olefin hydrocarbon molecules sieve fluid catalyst, comprises the following steps:
A silicon source, aluminum source, phosphorus source are mixed to form mixed liquor with water by ()；In mixed liquor, the mol ratio of each oxide consists of: Al2O3∶aSiO2∶bP2O5, wherein the span of a is 0.05～5, and the span of b is 0.05～5；
B () adds binding agent and forms the suspension of slurry, wherein binding agent accounts for the ratio of suspension gross mass and is: binding agent/outstanding Supernatant liquid=0.001～0.4；
C () high speed shear suspension is until the particle scale of 90% is less than 8 microns in suspension；
D () is spray-dried suspension, obtain silicon phosphorus aluminum oxide microsphere；
E silicon phosphorus aluminum oxide microsphere is divided into two parts, part roasting at temperature T1 by (), be designated as microsphere a, temperature T1 Scope is 400～1000 DEG C；Another part roasting at temperature T2, is designated as microsphere b, and temperature T2 scope is 200～800 ℃；Wherein roasting keeps T1 > T2 every time；
F microsphere a, microsphere b are mixed by () with water, template, put into crystallizing kettle and carry out hydrothermal crystallizing, crystallization temperature be 120～ 220 DEG C, crystallization time 6～72 hours；Wherein use template, water, the mass ratio of microsphere to be followed successively by: template/water=0.1～ 10；Template/microsphere=0.1～10；Microsphere a/ microsphere b=0.01～100；
G the microsphere after () roasting hydrothermal crystallizing obtains finished catalyst.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy the molecular sieve being in catalyst be SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-44, At least one in SAPO-47, SAPO-56.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be that phosphorus source is at least one in orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphorus compound, phosphorous oxides；Aluminum Source is at least one in activated alumina, boehmite, aluminum isopropylate., Kaolin, aluminium salt；Silicon source be Ludox, At least one in active silica, tetraethyl orthosilicate, Kaolin；Binding agent selected from Ludox, Silica hydrogel, Alumina gel, At least one in silicon-aluminum sol.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be that template is organic amine, selected from diethylamine, triethylamine, n-propylamine, 2-aminopropane., Tri-n-Propylamine, Tris(isopropylamine)., Di-n-propylamine, diisopropylamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, 1,6-hexamethylene diamine, At least one in cyclohexylamine, morpholine, ethanolamine, diethanolamine, triethanolamine.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be microsphere a/ microsphere b=0.1～10.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be that crystallization temperature is 150～200 DEG C；Crystallization time is 12～48 hours.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levying surface and the body phase being that finished catalyst Middle molecule sieve is present in catalyst microspheres, wherein body phase molecule sieve accounts for finished product catalysis The 70-90% of agent gross weight.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be that temperature T1 scope is 400～600 DEG C；Temperature T2 scope is 500～700 DEG C.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levy and be high speed shear suspension until the particle scale of 90% is less than 5 microns in suspension.
The preparation method of oxygenatedchemicals olefin hydrocarbon molecules the most according to claim 1 sieve fluid catalyst, it is special Levying and be that the span of a is 0.1～3, the span of b is 0.1～3.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248647A (en) * 1991-02-28 1993-09-28 Uop Sapo catalysts and use thereof in methanol conversion processes
CN1822902A (en) * 2003-06-13 2006-08-23 埃克森美孚化学专利公司 Method of protecting SAPO molecular sieve from loss of catalytic activity
CN101157057A (en) * 2006-08-08 2008-04-09 中国科学院大连化学物理研究所 A method for synthesizing oxygen-containing compound conversion olefinic hydrocarbon microspherical catalyst
CN102701232A (en) * 2012-06-08 2012-10-03 西北化工研究院 Preparation method of NaY molecular sieve

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248647A (en) * 1991-02-28 1993-09-28 Uop Sapo catalysts and use thereof in methanol conversion processes
CN1822902A (en) * 2003-06-13 2006-08-23 埃克森美孚化学专利公司 Method of protecting SAPO molecular sieve from loss of catalytic activity
CN101157057A (en) * 2006-08-08 2008-04-09 中国科学院大连化学物理研究所 A method for synthesizing oxygen-containing compound conversion olefinic hydrocarbon microspherical catalyst
CN102701232A (en) * 2012-06-08 2012-10-03 西北化工研究院 Preparation method of NaY molecular sieve

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