CN106622343A - Catalyst for preparing propylene through fluidized bed methanol conversion - Google Patents

Catalyst for preparing propylene through fluidized bed methanol conversion Download PDF

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Publication number
CN106622343A
CN106622343A CN201510731274.2A CN201510731274A CN106622343A CN 106622343 A CN106622343 A CN 106622343A CN 201510731274 A CN201510731274 A CN 201510731274A CN 106622343 A CN106622343 A CN 106622343A
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catalyst
propylene
preparing propylene
zsm
fluid bed
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金文清
滕加伟
赵国良
李斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a fluidized bed catalyst for preparing propylene from methanol or methyl ether, and a preparation method thereof, wherein the catalyst basally comprises 20-80% of an active component phosphorus rare earth modified high-silicon ZSM-5 molecular sieve, 5-60% of a binder, and 0-60% of a filler, and the preparation process comprises material preparing, beating, spray molding, and calcining. According to the present invention, the catalyst has a methanol close to 100% and high propylene selectivity, further has characteristics of good thermal stability, good hydrothermal stability and good wear resistance, and can be used for continuous reaction-regeneration in industrial production.

Description

For the catalyst of fluid bed preparing propylene by methanol transformation
Technical field
The invention belongs to catalyst technical field, is related to one kind by methyl alcohol or dimethyl ether propylene fluid catalyst and its makes each Method.
Technical background
Propylene is the important organic chemical industry's basic material for being only second to ethene, mainly for the production of polypropylene, acrylonitrile, acrylic acid, The resins such as expoxy propane, isopropanol and Organic Chemicals.Recent two decades come, because the application of acryloyl derivative constantly expands, Demand is continuously increased, and the growth rate for making World Propylene demand is faster than ethene, and domestic production of propylene ability is constantly lifted, new production Method constantly forms scale.
At present propylene is mainly obtained by petroleum Jing steam crackings or catalytic cracking, and such as from about 60% propylene is filled by steam cracking Put production, the catalytic cracking unit accessory substance of 1/3rd propylene from oil plant.With the continuous decrease of petroleum resources, Oil price constantly rises so that the cost of material of production of propylene persistently rises, therefore, original oil is all being improved in countries in the world Route technology, makes full use of petroleum resources, such as butylene disproportionation technology, olefins by catalytic cracking technology and dehydrogenating propane technology, The scale of large-scale industrial application or exemplary production has all been reached, good result has been achieved, production of propylene cost has been reduced. Simultaneously various countries also actively research and develop Non oil-based route production propylene technology, and the propylene technology mainly utilizes coal, natural gas or life Material ECDC produces methyl alcohol or dimethyl ether, is combined by preparing propylene by methanol transformation substep realize coal propylene again into gas, coal in the technology Gasification and synthesizing methanol technology are highly developed, therefore the key of the technology is the catalysis by developing preparing propylene by methanol transformation Agent and its technology.
The existing substantial amounts of research report of existing methyl alcohol ethene, propylene technology, such as methyl alcohol ethene, propylene (MTO), first Alcohol propylene (MTP).
Such as United States Patent (USP) US6534692B1 and US2002/0147376A1, US 6,995,111, US 6,844,291 etc., using little The aluminium silicophosphate molecular sieve SAPO-34 or its modifier in hole is catalyst main active, greatly limit macromolecular product Produce, thus with the selectivity of the low-carbon alkenes such as very high propylene, ethene, one way overall selectivity reach 80% or more than, But generally its ethene is more than propylene, commonly referred to MTO.
Early stage, the Mobil companies of the U.S. at the eighties in 20th century found when preparing gasoline by methanol Catalytic processes are studied, using its invention ZSM-5 molecular sieve, as catalyst after certain modification, by adopting different technology conditions, discovery can turn methyl alcohol Turn to ethene, propylene and butylene petrochemicals.
German LURGI takes the lead in fixed bed preparing propylene by methanol transformation (MTP) technology developed, and has carried out industrial metaplasia Produce, it is relatively simple with respect to MTO because the technique only has the products such as propylene and gasoline, ethene and four～C 6 olefin of carbon not as Product and be recycled back into reactor, re-start reaction, to improve propylene product yield, therefore the handicraft product separate need not The Technology for Ethylene Plant of high energy consumption and favored by related application enterprise.The catalyst that the technology is adopted is German southization Learn, disclose according to its patent US7,015,369 and CN1431982, the catalyst is ZSM-5 molecular sieve, and specific surface area reaches 460M2, and through the modified of 0.05%ZnO+CdO, react under the conditions of methyl alcohol air speed 1.The technique is adopted more than three strings The reactor of connection, and in order to make full use of reaction heat, sectional feeding is carried out between the reactor of series connection, and react the second for generating Alkene, butylene return charging Jing after initial gross separation, and as a result the content of propylene is in last reactor outlet, the product of generation 20～50%.Because catalyst through certain hour after reacting, reactivity is lost because of coking, in order to continue reaction, urged Agent must stop carries out coke burning regeneration.For the continuity for ensureing to produce, LURGI employs reactor assembly two, and to open one standby The equipment mode of regeneration, therefore reaction system is complicated, and there is potential safety hazard in high temperature switching.And preparing propylene from methanol reaction is Strong exothermal reaction, often generates 1 mole of ethene heat release about 23KJ/mol, generates 1 mol propylene heat release 93KJ/mol, generates 1 and rubs The heat release of your butylene reaches 150KJ/mol, such strong exothermal reaction in fixed bed reactors when obtaining effectively dispersed, Easily cause inside reactor hot-spot, and cause side reaction to increase, therefore temperature control is crucial for its operation and difficulty is big. To guarantee product propene yield, the design such as the charging distribution of reactor and interlayer cooling becomes increasingly complex, and is likely to occur short slab.
In order to realize catalyst continuous reaction-regenerative operation technique, by China National Chemical Engineering Group Corporation, Tsing-Hua University, peace Three unit consolidations of Hui Zhunhua groups develop fluid bed preparing propylene from methanol (FMTP) technique, and its patent CN103263944A is disclosed Its key core catalyst is that the SAPO-18/34 with multi-level nano-structure hands over phase co-crystalline zeolite catalyst.The technique is adopted The first step is methanol-to-olefins MTO reactions, and product Jing gas separation system isolates C2 and C2 following components, C4 And the component of more than C4 returns second fluidized bed reaction unit, the EBTP that olefin cracking is carried out in high reaction temperatures is anti- Should, reaction product gas are combined into piece-rate system and are separated (CN100551883)；Its MTO reactions propene yield is about 38.2%, P/E ratio about 1.18, and after EBTP reactions, propene yield brings up to 67%.(Henan is reported according to it Work, 2011 (28), 34), due to carrying out MTO and EBTP reactions using same catalyst, SAPO-18/34 molecular sieves are urged The activity and propene yield that agent is reacted EBTP is relatively low, causes the circulation ratio of freshening higher, and catalyst abrasion consumes height etc. It is unfavorable.
A kind of aperture phosphorus aluminium SAPO-34 molecular sieve catalysts disclosed in US6049017, its fixed bed evaluation carries out C4 alkene Freshening test reaction, as a result Propylene Selectivity is relatively low, and only 25～30%, and produce substantial amounts of methane.
USP5171921, by P Modification, improves catalysis using a kind of Hydrogen ZSM-5 molecular sieve of silica alumina ratio 20～60 The hydrothermal stability of agent, at 600 DEG C, WHSV366h-1Condition fluidized bed at elevated is checked and rated, and the use of pure butene-2 is cracking stock, Conversion ratio is 59.5%, Propylene Selectivity 49.7%.
US 4025576, US3979472 patent is divided with methyl alcohol or dimethyl ether as raw material using ZSM-5 or Jing Zn are modified Son sieve is catalyst, produces ethene, propylene and gasoline.Molecular sieve catalyst adopts aluminum oxide for binding agent, binder content 35%.
Patent US2006229482, JP2006008655, WO2005056504 (A1) provide a kind of technique for producing propylene, The ethene that reaction is generated is returned in the mixture of methanol/dimethyl ether, is reacted under catalyst action, by the amount for controlling ethene, The yield for making propylene is more than 40mol%.Used catalyst is solid acid catalyst, the such as modified crystallizable silicate of porous Zeolite or thin layer zeolite.Invention JP2005281254 provides a kind of method for producing propylene, with very high yield and selectivity, Meanwhile, by the way that the ethene in product is further reacted with methyl alcohol and dimethyl ether under catalyst, to improve the ratio of propylene/ethylene.
Patent US 4,499,314 is reacted under Si-Al zeolite catalyst action there is provided a kind of methyl alcohol and is produced based on ethene and propylene Want the hydrocarbon products of product.Catalyst can be faujasite, mordenite, ZSM-5 etc., and steady at 250 DEG C～500 DEG C Surely hydrothermally stableization process has been carried out, course of reaction adds aromatic compound as the accelerator for preparing alkene.
Patent US4767886 discloses a kind of method that methyl alcohol or dimethyl ether produce low charcoal alkene, in 0.1～20h-1Air speed, 300～ Under 650 DEG C of temperature, 0.1～100 atmospheric pressure, using a kind of Jing alkali-earth metal modified boracic al silicate molecular sieve as it Catalyst, but the concrete classification of undeclared molecular sieve.
Patent of invention WO0032543 provides one kind under porous particle catalyst action, and methyl alcohol conversion prepares ethylene/propene Method.The technique can improve or reduce the ratio of the ethylene/propene of product by change condition.
EP0105591, JP59082319 (A) provide one kind under the zeolite catalysises of ZSM-12 containing magnesium, methanol feedstock conversion production The technique of light olefin, the technique rich can produce C2-C4Alkene, particularly propylene.
Patent US 4,062,905 discloses one kind with methyl alcohol as raw material, and with eight Yuans ring small pore molecular sieves as catalyst, preparation is rich in The method of ethene, the hydrocarbon mixture of propylene, its methane, propane yield are more, reduce the selectivity of alkene.
Patent US 4,079,095, US 4,079,096, US 4,449,961, US 4, the method for 471,150 inventions is with methyl alcohol as original Material, adopts erionite, ZSM-34 or modified ZSM-34 molecular sieves for catalyst, prepares the hydro carbons rich in ethene, propylene and mixes Compound.
Invention US 4,359,595, adopt with methyl alcohol as raw material, ZSM Series Molecules sieve is catalyst, and adds 10 in raw material The nitrogen-containing organic compound of -5000ppm to suppress product in aromatic hydrocarbons generate method, prepare rich in ethene, propylene hydro carbons mix Compound, molecular sieve is not through any modified.
The patents of US 5,157,193 adopt A types, X-type or Y type molecular sieve for catalyst with methyl alcohol as raw material, prepare and are rich in second The hydrocarbon mixture of alkene, propylene.
Methanol/dimethyl ether is converted into alkene by Japan Patent JP62070324 inventions, can improve the yield of purpose product, and is extended The life-span of catalyst.Used catalyst is (i) alkali-earth metal modified zeolite catalyst；(ii) modified point of boiling of alkali and alkaline earth metal ions Stone catalyst, (iii) alkali-earth metal modified ZSM catalyst.
The JP56135424 present invention produces alkene by methanol/dimethyl ether, ethene and propylene is particularly produced, with very high reaction Activity and selectivity.Used catalyst includes special silicon-aluminum structure, different from traditional ZSM-5 catalyst, with special Version.
CN1489563 is disclosed and is related to one kind by the way that molecular sieve catalyst is carried out with oxygenatedchemicals in oxygenatedchemicals zone of transformation Contact, makes a part of oxygenatedchemicals be converted into olefin product；Catalyst is separated with olefin product, and a part is separated Catalyst sends into regenerator；By regenerated catalyst and selected from methyl alcohol, ethanol, 1- propyl alcohol, n-butyl alcohol or their mixture Alcohol is contacted in alcohol contact zone；Come from the process that alcohol contact zone is sent to oxygenatedchemicals zone of transformation with the catalyst after alcohol is contacted The technique for preparing ethene, propylene and butylene.
It is containing C by methyl alcohol or dimethyl ether conversion that CN1352627 provides one kind2～C4The method of olefin product, the method includes making The step of material containing methyl alcohol or dimethyl ether contacts with the catalyst containing zeolite, wherein zeolite have 10 ring intersecting channels, such as ZSM-5, and when measure under being 8KPA in the pressure of 120 DEG C and 2,2- dimethylbutane zeolite to 2,2- dimethyl butyrates The diffusion parameter of alkane is less than 100 seconds- 1.It in 370～480 DEG C, methanol partial pressure is 30～150PSIA and the list of methyl alcohol that contact procedure is Journey conversion ratio is less than what is carried out under 95%.
CN1084431 discloses a kind of method that methanol/dimethyl ether is produced into alkene, using a kind of absolute thermosetting fixed bed reactor work Skill, catalyst is the embodiment with lanthanum, phosphorous modified ZSM-5 molecular sieve active component and～35% silica as binding agent Disclose only reaction gas phase C2～C4Olefin yields are more than 85%, and the only 24 hours regeneration period of catalyst is strong.
It is catalyst such as using SAPO-34 molecular sieves in these technologies, presence when its methyl alcohol is converted produces a large amount of ethene and needs Circulation freshening, and because the catalyst reaction activity is relatively low, the temperature requirement of alkene freshening reaction reaches nearly 600 DEG C, etc. Shortcoming, and when carrying out fluidized-bed reaction using ZSM-5 molecular sieve, the selectivity of propylene is mostly relatively low or only fixed bed examination Performance.
There is the shortcomings of reacting low propene yield or wear-resistant bad mechanical strength in these catalyst and technique, still difficulty meets fluid bed Technological requirement.
The content of the invention
It is an object of the invention to overcome the shortcoming of above-mentioned prior art, there is provided a kind of preparing propylene from methanol fluid catalyst and its system Each method, i.e. fluid bed fine grained microspherical catalyst, the catalyst has very high methyl alcohol reactivity and Propylene Selectivity, together When there is at reaction conditions higher alkene activity of conversion and Propylene Selectivity similar；Catalyst can be used for successive reaction-regeneration Technique, with fluidization characteristics such as the high heap density of good mechanical strength, comparison.
Another object of the present invention is the return freshening catalytic material cracking that the catalyst of invention can be used in alkene or mixed olefins Obtain higher propene yield.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：
A kind of catalyst for fluid bed preparing propylene by methanol transformation, catalyst by weight percentage, including following components：
A) 20～80% ZSM type molecular sieves；
B) 0.01～10% rare-earth oxide；
C) 0.01～10% phosphorous oxides；
D) 5～60% binding agent.
According to the present invention, in above-mentioned technical proposal, preferred ZSM types molecular sieve is ZSM-5, ZSM-11 or ZSM-35 In at least one；Preferred scheme is ZSM-5 and/or ZSM-11；Most preferably ZSM-5；The sial mole of molecular sieve Compare SiO2/Al2O3Preferably 100～2000, more preferably scope is 200～1500；Most preferably scope is 1000～1500.
In above-mentioned technical proposal, preferred zeolite crystal size be less than 10～2000 nanometers, preferred scope be 10～ 1000 nanometers.
The preferred scope of phosphorous oxides weight content (in terms of oxide) in the catalyst is 0.1～6%；Rare earth oxide The preferred scope of weight content (in terms of oxide) in the catalyst is 0.1～6%；
According to catalyst of the present invention, the preferred scope of molecular sieve consumption is 30～60% weight, compared with low silica-alumina ratio molecular sieve due to Its sour density is high, and reactivity is strong, and ethylene selectivity is high and propylene is relatively low, and has the alkane such as substantial amounts of hydrogen migration product such as propane Hydrocarbon, coking etc. are produced, and the Propylene Selectivity of high silica alumina ratio molecular sieve is higher, and the side reaction such as alkane is relatively fewer.
The present invention uses high performance binding agent, improves the content of the sieve of molecules of active components in catalyst, by optimization of C/C composites and Using rational pulping process, spray art and roasting condition so that the catalyst of preparation has higher reactivity and propylene It is selective, while the good resistance to mechanical tear strength of catalyst.And increased its water because rare earth and P elements introduce molecular sieve Heat endurance and anticaking carbon ability, improve the reactivity worth of catalyst, achieve unexpected effect.
Preparing the raw material that catalyst of the present invention uses is：
Filler is selected from such as montmorillonite, tired de- soil, galapectite, sepiolite natural clay or kaolinic at least one, preferably Kaolin.
Binding agent selected from one or more of Alumina gel, peptization boehmite, Ludox and silicon-aluminum sol or gel etc., preferably For Alumina gel.
Modified rare earth is at least one water soluble salt of mischmetal or lanthanum and cerium, such as nitrate, chloride etc.；It is modified It is phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and various water soluble phosphorous compounds with phosphorus compound.
Method for preparing catalyst used in the present invention is：
The preparation of catalyst of the present invention with well known FCC catalyst preparation technology, i.e. slurrying, spraying shaping, be roasted to it is main Three steps.Generally first clay is added into appropriate deionized water, is then stirred with high shear beater, then add the binding agent of required amount, If it is desired, the pH value of slurry is adjusted with acid or ammoniacal liquor, and to protect molecular sieve not destroyed by too strong acid or alkali, usual point Son sieve is being eventually adding.For the intensity and performance of catalyst, the charging order change of various raw materials has no difference too greatly, Thus charging order can be arbitrarily adjusted as needed.So prepared slurry is uniform suspension, typically can be placed 24 hours And be not substantially layered.
Generally the solid content of slurry is 25～50wt%, is to reduce evaporation of water amount, reduces energy consumption, and solid content should try one's best height.
Under the conditions of 500 DEG C of inlet temperature, 200 DEG C of outlet, spray drying granulation shaping obtains the microsphere particle containing a small amount of water to slurry, 600 DEG C of roastings 2 hours in Muffle furnace again.
Obtained microsphere particle catalyst, if it is necessary, further can exchange or wash for several times in water or ammonium salt solution intermediate ion, So that the sodium ions content of catalyst is less than 0.1%, dry catalyst sample.By sample by standard method determine abrasion index, Bulk density and granularity, test its physical and chemical indexes.
Prepared catalyst is 20～150 microns of spheric granules, and average grain is 60～70 microns, heap density 0.7～0.9 Grams per milliliter.
According to elements such as the present invention, the phosphorus and rare earth of catalyst modification, can prepare the slurry stage add can also be in catalyst Dipping method is introduced after roasting, but its modified effect is poor, preferred method be it is modified with molecular sieve powder dipping, its effect compared with Substantially.
In the present invention catalyst is by introducing rare earth and P elements, the highly acid position that " neutralization " moieties are sieved, modulation molecule The acid strength of sieve, by adjust modifying element number, do not only reach almost 100% methanol conversion, and improve reaction Propylene Selectivity.And because rare earth and phosphorus have the stabilization to framework of molecular sieve aluminium, delayed aluminium atom in high-temperature water The speed come off from framework of molecular sieve structure under steam effect, maintains for a long time the acidity of molecular sieve, namely improves catalysis The hydrothermal stability of agent, can more be applied to the environment that the continuous high temperature regeneration of catalyst burns..
The presence of catalyst filling and binding agent in the present invention substantially improves the mechanical strength and pore passage structure of catalyst, forms big The macropore and mesopore of amount, be conducive to raw material olefin be diffused into up to molecular sieve reacted and product propylene quick desorption, it is slight Coking is unlikely to completely plugged catalyst duct.And the toxic poisoning of catalyst can be delayed, disperseed when air burn regenerates Heat, prevents molecular sieve structure avalanche.
Preparing propylene from methanol, ethylene reaction test are carried out using catalyst of the present invention, inventors have surprisingly found that, in methyl alcohol one way When conversion ratio reaches～99%, Propylene Selectivity achieves preferable technique effect up to more than 41%.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Step one, by the HZSM-5 molecular sieves (Nankai University) of 500 grams of moles of silica alumina ratios 200, and containing Ce2O35.0 grams 500 milliliters of cerous nitrate solution is well mixed, and impregnates 5 hours, and under agitation heating evaporation is to dry, then 120 DEG C of drying 10 are little When, 550 DEG C of roastings 2 hours.
Step 2, above-mentioned sample is then added in the solution that 8.1 gram of 85% phosphoric acid and 500 grams of water are made into, is soaked after being well mixed Stain 5 hours, is evaporated under then stirring, then 120 DEG C dry 10 hours, 550 DEG C of roastings 2 hours, finally crush.
Step 3, by 177 grams of kaolin (igloss 15%), add water 350 grams and soak 10 minutes, be then beaten 10 minutes, The Alumina gel for adding 480 grams (alumina content 21%) is stirred 5 minutes, and it is 3.5 or so to add 20% nitric acid to adjust pH value, The molecular sieve for being eventually adding 250 grams of step 2 methods preparations is beaten 15 minutes, obtains the slurry of 40% solid content.This slurry is existed 500 DEG C of import air temperature, goes out 200 DEG C of conditions of one's intention as revealed in what one says and is spray-dried shaping, the sample of spray shaping through 650 DEG C of roastings 3 hours, Catalyst sample is obtained, test catalyst heap is than ρ and abrasion index DI.The results list 1.
【Embodiment 2】
Will【Embodiment 1】60 grams of catalyst is arranged in the fixed fluidized-bed reactor of Φ 30, and reactor is first urged with nitrogen fluidisation Agent, and temperature reaction device, in the close phase section temperature of reactor 500 DEG C are reached, and after stablizing 1 hour, close nitrogen, are opened Dynamic measuring pump, conveys 50% methanol aqueous solution catalyst test raw material, in air speed WHSV3 hour-1, carry out methyl alcohol fluidisation The preparing propylene transformed test of bed, reaction end gas outflow reactor after separating catalyst is directly entered chromatographic after insulation Six-way valve, regularly carries out on-line period analysis, and calculates reaction result.List 2.
【Embodiment 3～7】
With the identical preparation process of embodiment 1, change the feed components ratio of slurry either modifying element ratio or different molecular Sieve silica alumina ratio, obtains different microspherical catalysts.Physical property measurement and appraisal result list 1,2.
【Embodiment 8～12】
Step one, by the HZSM-5 molecular sieves of 500 grams of difference mole silica alumina ratios, and containing Ce2O35.0 grams of cerous nitrate solution 500 milliliters are well mixed, and impregnate 5 hours, and under agitation heating evaporation is to dry, then 120 DEG C dry 10 hours, 550 DEG C of roastings Burn 2 hours.
Step 2, above-mentioned sample is then added in the solution that 8.1 gram of 85% phosphoric acid and 500 grams of water are made into, is soaked after being well mixed Stain 5 hours, is evaporated under then stirring, then 120 DEG C dry 10 hours, 550 DEG C of roastings 2 hours, finally crush.
Step 3, by 177 grams of kaolin (igloss 15%), add water 350 grams and soak 10 minutes, be then beaten 10 minutes, The Alumina gel for adding 480 grams (alumina content 21%) is stirred 5 minutes, and it is 3.5 or so to add 20% nitric acid to adjust pH value, The molecular sieve for being eventually adding 250 grams of step 2 methods preparations is beaten 15 minutes, obtains the slurry of 40% solid content.This slurry is existed 500 DEG C of import air temperature, goes out 200 DEG C of conditions of one's intention as revealed in what one says and is spray-dried shaping, the sample of spray shaping through 650 DEG C of roastings 3 hours, Catalyst sample is obtained, test catalyst heap is than ρ and abrasion index DI.The results list 1.
With embodiment 2, evaluation result is shown in Table 2 to appreciation condition.
Table 1.
Table 2.
【Embodiment 13】
Step one, by the HZSM-5 molecular sieves (Nankai University) of 500 grams of moles of silica alumina ratios 300, and containing Ce2O35.0 grams 500 milliliters of cerous nitrate solution is well mixed, and impregnates 5 hours, and under agitation heating evaporation is to dry, then 120 DEG C of drying 10 are little When, 550 DEG C of roastings 2 hours.
Step 2, above-mentioned sample is then added in the solution that 16.3 gram of 85% phosphoric acid and 500 grams of water are made into, is soaked after being well mixed Stain 5 hours, is evaporated under then stirring, then 120 DEG C dry 10 hours, 550 DEG C of roastings 2 hours, finally crush.
Step 3, by 147 grams of kaolin (igloss 15%), add water 350 grams and soak 10 minutes, be then beaten 10 minutes, The Alumina gel for adding 238 grams (alumina content 21%) is stirred 5 minutes, and it is 3.5 or so to add 20% nitric acid to adjust pH value, 188 grams of stirrings of 40% Ludox are added, the molecular sieve for being eventually adding 250 grams of step 2 methods preparations is beaten 30 minutes, obtains The slurry of 40% solid content.By this slurry in 500 DEG C of import air temperature, go out 200 DEG C of conditions of one's intention as revealed in what one says and be spray-dried shaping, spray into The sample of type obtained catalyst sample through 650 DEG C of roastings 3 hours, and test catalyst heap is than ρ 0.78g/ml, and abrasion index DI 3.1, using easy to operate after compound binding agent, tear strength keeps substantially.
Catalyst test the results list 3.
【Embodiment 14～16】
By the HZSM-5 molecular sieves that 500 grams of moles of grain sizes of silica alumina ratio 300 are 2000,1000,300 nanometers, press respectively According to【Embodiment 13】It is prepared into catalyst.Test catalyst heap is than ρ 0.8g/ml or so, abrasion index DI 3.0 or so.Catalysis Agent appraisal result list 3.
Table 3
Embodiment Methanol conversion, % Propylene Selectivity, % Ethylene selectivity, % Four～carbon of carbon six is selective, %
13 98.32 37.12 10.91 41.52
14 98.11 33.52 11.52 45.65
15 99.04 38.57 10.51 41.23
16 99.13 41.09 9.32 39.55
【Comparative example 1】
By 177 grams of kaolin (igloss 15%), add water 350 grams and soak 10 minutes, be then beaten 10 minutes, add 480 The Alumina gel of gram (alumina content 21%) is stirred 5 minutes, and it is 3.5 or so to add 20% nitric acid to adjust pH value, finally plus The HZSM-5 molecular sieves (Nankai University) for entering 250 grams of moles of silica alumina ratios 300 are beaten 30 minutes, obtain the slurry of 40% solid content Material.By this slurry in 500 DEG C of import air temperature, go out 200 DEG C of conditions of one's intention as revealed in what one says and be spray-dried shaping, the sample of spray shaping is passed through 650 DEG C of roastings 3 hours, obtain catalyst sample.Appraisal result be methanol conversion 99.08%, Propylene Selectivity 34.21%, second Alkene selective 10.52%, four～carbon of carbon six selective 41.5%.

Claims (10)

1. a kind of catalyst for fluid bed preparing propylene by methanol transformation, catalyst by weight percentage, including following components：
A) 20～80% ZSM type molecular sieves；
B) 0.01～10% rare-earth oxide；
C) 0.01～10% phosphorous oxides；
D) 5～60% binding agent.
2. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that with percentage by weight Meter is 30～60% selected from the consumption of ZSM type molecular sieves, the silica alumina ratio SiO of molecular sieve2/Al2O3For 100～ 2000。
3. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 2, it is characterised in that ZSM type molecules At least one of the screening from ZSM-5, ZSM-11 or ZSM-35, the silica alumina ratio of molecular sieve is 200～1500.
4. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that the crystal grain of molecular sieve 10～2000 nanometers of size range.
5. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that the crystal grain of molecular sieve 10～1000 nanometers of size range.
6. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 2, it is characterised in that ZSM type molecules Screen from ZSM-5.
7. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that with percentage by weight The consumption of meter phosphorous oxides is 0.1～6%.
8. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that with percentage by weight The consumption of meter rare-earth oxide is 0.1～6%；Rare earth metal is selected from lanthanum, cerium or its mixture.
9. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that binding agent is selected from aluminium At least one in colloidal sol, gelling boehmite, Ludox or silicon-aluminum sol.
10. the catalyst of fluid bed preparing propylene by methanol transformation is used for according to claim 1, it is characterised in that molecular sieve elder generation Using the process of phosphorus rare-earth oxide modified.
CN201510731274.2A 2015-11-02 2015-11-02 Catalyst for preparing propylene through fluidized bed methanol conversion Pending CN106622343A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110882718A (en) * 2019-12-05 2020-03-17 大连海鑫化工有限公司 Metal modified MFI @ MFI core-shell type molecular sieve catalyst and preparation thereof
CN116422362A (en) * 2021-12-30 2023-07-14 卓悦环保新材料（上海）有限公司 Anti-crushing catalyst for preparing propylene from methanol, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704163A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Molecular screen microspherical catalyst
CN101429085A (en) * 2007-11-07 2009-05-13 中国石油化工股份有限公司 Method for producing propylene, ethylene light olefin hydrocarbon
CN101733143A (en) * 2008-11-21 2010-06-16 中国石油化工股份有限公司 ZSM-5 molecular sieve with small crystal grains and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1704163A (en) * 2004-05-28 2005-12-07 中国石油化工股份有限公司 Molecular screen microspherical catalyst
CN101429085A (en) * 2007-11-07 2009-05-13 中国石油化工股份有限公司 Method for producing propylene, ethylene light olefin hydrocarbon
CN101733143A (en) * 2008-11-21 2010-06-16 中国石油化工股份有限公司 ZSM-5 molecular sieve with small crystal grains and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110882718A (en) * 2019-12-05 2020-03-17 大连海鑫化工有限公司 Metal modified MFI @ MFI core-shell type molecular sieve catalyst and preparation thereof
CN110882718B (en) * 2019-12-05 2022-06-28 大连海鑫化工有限公司 Metal modified MFI @ MFI core-shell type molecular sieve catalyst and preparation thereof
CN116422362A (en) * 2021-12-30 2023-07-14 卓悦环保新材料（上海）有限公司 Anti-crushing catalyst for preparing propylene from methanol, and preparation method and application thereof

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Application publication date: 20170510