CN103962169B - It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed - Google Patents

It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed Download PDF

Info

Publication number
CN103962169B
CN103962169B CN201310040880.0A CN201310040880A CN103962169B CN 103962169 B CN103962169 B CN 103962169B CN 201310040880 A CN201310040880 A CN 201310040880A CN 103962169 B CN103962169 B CN 103962169B
Authority
CN
China
Prior art keywords
catalyst
serosity
weight
methanol
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310040880.0A
Other languages
Chinese (zh)
Other versions
CN103962169A (en
Inventor
王义君
张帆
芮果
甘永胜
张小莽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Bi Ke Clean Energy Technology Co Ltd
Original Assignee
Shanghai Bi Ke Clean Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Bi Ke Clean Energy Technology Co Ltd filed Critical Shanghai Bi Ke Clean Energy Technology Co Ltd
Priority to CN201310040880.0A priority Critical patent/CN103962169B/en
Priority to PCT/CN2014/071737 priority patent/WO2014117735A1/en
Publication of CN103962169A publication Critical patent/CN103962169A/en
Application granted granted Critical
Publication of CN103962169B publication Critical patent/CN103962169B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/16—Clays or other mineral silicates
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a kind of method for preparing catalyst, the method comprising the steps of：(1) 5 molecular sieves of ZSM, host material, binding agent and water are mixed, is configured to aqueous slurry, is counted on the basis of the gross weight of the aqueous slurry, wherein the total content of component in addition to water is 20 50 weight %；(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained；(3) roasting is carried out to graininess intermediate product obtained in step (2), the catalyst for alkene is prepared by methanol in fluid bed is obtained.Present invention also offers by obtained in methods described catalyst and the method that alkene is prepared by methanol in fluid bed using the catalyst.

Description

It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed
Technical field
The present invention relates generally to catalytic field, more particularly, the present invention relates to it is a kind of for fluidized-bed reactor by Methanol prepares catalyst of alkene and preparation method thereof.
Background technology
Ethylene, propylene, butadiene are important industrial chemicals, are usually obtained from naphtha pyrolysis and steam cracking, Another main source of propylene is ethylene propylene simultaneously and refinery's by-product propylene, but these modes of production are difficult to meet China's day The demand to propylene that benefit increases, China from resource distribution for many coals and few oil, methanol device production capacity surplus, Devoting Major Efforts To Developing The technology of methanol-to-olefins has very important economy and social meaning.It has been reported that various methanol-to-olefins technique In, with ZSM-5 molecular sieve as catalyst, people have been now subjected to using the MTP technologies that methanol is Material synthesis alkene great Pay attention to.
German LURGI develops methanol-to-olefins bed technology（WO2004/018089）, it is public using southern chemistry The ZSM-5 molecular sieve catalyst of department and fixed bed reactors carry out methanol to olefins reaction, and Propylene Selectivity is 35～40%, CN102531823A, CN101172918B, CN101279280B, CN101402049A, CN102211971A are also disclosed respectively The technique and method for preparing catalyst of preparing propylene from methanol are carried out using fixed bed reactors, mainly with ZSM-5 molecular sieve as work Property component, which is carried out it is various modified, so as to improve the one way selectivity of propylene.But the reaction of methanol-to-olefins is strongly exothermic Reaction, in the case of using fixed bed reactors, in laboratory stage, due to loaded catalyst it is fewer, and water/alcohol Than high, unnecessary heat can be removed by the water in reaction system.And after industrial amplification is carried out, fixed bed reactors are passed The feature of hot property difference is just highlighted at once, bad due to radiating, and can there are many overheated areas in fixed bed reactors Domain, catalyst are easy to as bed temperature is too high and coking and deactivation.In order to solve this problem, people take some and trade off Additional step.For example, at present, in the strange MTP technologies in industrialized Shandong, methanol feedstock first passes through dimethyl ether reactor, Methanol/dimethyl ether gaseous mixture is wherein converted into, MTP fixed beds is then entered back into and is reacted.In addition, in order to promote heat transfer, Reaction gas is uniformly divided into six sections in fixed bed reactors to enter in multi-layer fixed-bed reactor.Above measure is substantially increased Process complexity and operation cost.Even if in addition, in the case where these measures are taken, the heat transfer property of fixed bed reactors is still Desirable level is not fully reached so, the yield of propylene is extremely difficult to preferable level.
Poor in order to solve the problems, such as fixed bed reactors conductivity of heat, fluid bed is a kind of highly desirable selection, and fluid bed is anti- The heat transfer property of system is answered to be significantly better than fixed bed.But, fluidized-bed reactor is to the shape of catalyst, granule strength and wear-resisting Property require it is higher, the intensity and wearability of the fixed bde catalyst above with reference to described in document is poor, and its shape stream It is difficult to be fluidized in changing bed, therefore develops a kind of cheap, high catalytic activity and the catalysis with high intensity and high-wearing feature Agent, is the bottleneck of current methanol-to-olefins fluidized-bed process exploitation.
Studies have reported that it is a kind of in fluid bed by methanol-to-olefin catalyst technology of preparing, the technology uses ZSM-5 molecular sieve is active component, and the component such as addition rare-earth modifier, basic modifier is applied with improving the activity of molecular sieve The methanol-to-olefins fluidized-bed reaction that the catalyst is carried out reaches the Propylene Selectivity of highest 55%, but this kind of catalyst preparation work Skill is complicated, relatively costly, and strength ratio is relatively low, still unsatisfactory.Therefore, those skilled in the art are in the urgent need to opening Send out a kind of with high catalytic activity, high intensity, high-wearing feature cheap catalyst, for carrying out in fluidized-bed reaction system The reaction of alkene is prepared by methanol.
The content of the invention
In order to solve the above problems, the present invention using ZSM-5 molecular sieve be active component, wherein add host material, Binding agent, pore creating material and dispersant, are prepared by the forming method being spray-dried anti-for the fluid bed of methanol-to-olefins Catalyst is answered, this kind of catalyst preparation process is simple, low cost, compares with fixed bed MTP technology, it is not necessary to pre- using dimethyl ether Reactor, it is possible to use the methanol aqueous solution or methanol of low water alcohol ratio is directly entered fluidized-bed reactor as raw material to be carried out instead Should.The catalyst of the present invention has splendid intensity and wearability, and after reacting 200h in fluid bed, propylene still has very high Yield.
In the first aspect of the invention, there is provided a kind of method for preparing catalyst, the catalyst is to use In the catalyst for being prepared alkene in fluid bed by methanol, the method comprising the steps of：
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, is configured to aqueous slurry, it is aqueous with this Count on the basis of the gross weight of serosity, wherein the total content of component in addition to water is 20-50 weight %；
(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained；
(3) roasting is carried out to graininess intermediate product obtained in step (2), is obtained for being prepared by methanol in fluid bed The catalyst of alkene.
In an embodiment of the invention, on the basis of the gross weight of the component in the serosity in addition to water Meter, in the serosity, the content of ZSM-5 molecular sieve is 20-55 weight %, and the silica alumina ratio of the ZSM-5 molecular sieve is Si/Al= 20-400, preferred 200-400.
In yet another embodiment of the present invention, on the basis of the gross weight of the component in the serosity in addition to water Meter, the content of host material described in the serosity is 20-59 weight %, and the particle diameter of the host material is less than 2 microns, is selected from One or more in following material：Kaolin, calcined kaolin, kieselguhr, boehmite, montmorillonite.
In yet another embodiment of the present invention, on the basis of the gross weight of the component in the serosity in addition to water Meter, the content of binding agent described in the serosity is 20-50 weight %, the one kind or many of the binding agent in the following material Kind：Alkaline silica sol, acidic silicasol, Alumina gel, aluminum phosphate.
In yet another embodiment of the present invention, the serosity also includes pore creating material.Preferably, the pore creating material is selected from One or more in following material：Sesbania powder, polyvinyl alcohol, methylcellulose, with the group in the serosity in addition to water Count on the basis of the gross weight divided, the content of pore creating material described in the serosity is 0.01-1 weight %.In another preferred reality Apply in mode, the serosity also includes dispersant, one or more in following material of the dispersant：N-octyl alcohol, carbon Sour hydrogen ammonium, bicarbonate diammonium, are counted on the basis of the gross weight of the component in the serosity in addition to water, are disperseed in the serosity The content of agent is 0.01-1 weight %.
In yet another embodiment of the present invention, in the step (2), using atomizer exsiccator or pressure type Spray dryer is spray-dried, and the inlet temperature of spray dryer is 250-300 DEG C, and outlet temperature is 150-200 DEG C, slurry It is 100-500ml/min that liquid is input into the feed rate of the spray dryer；In the step (3), 400-600 DEG C, it is excellent Select.
Another aspect of the present invention provides a kind of catalyst prepared by method of the present invention, is urged with described On the basis of the gross weight of agent count, the catalyst comprising 25-60 weight %, the ZSM-5 molecular sieve of preferred 25-40 weight %, 20-50 weight %, the component and 10-45 weight % from the host material of preferred 30-45 weight %, preferred 25-40 The component from the binding agent of weight %, the particle diameter of the catalyst is 50-110 microns.
The third aspect of the invention provides a kind of method for preparing alkene by methanol, and the method includes, be enough to make Methanol be converted under the reaction condition of alkene, in a fluidized bed reactor so that the aqueous solution of methanol or methanol with by this Catalyst prepared by the method for invention is contacted, and the reaction condition is：Methanol quality air speed 0.5-5h-1, reaction temperature 430- 550 DEG C, reaction pressure 0-1MPa.
Specific embodiment
" scope " disclosed herein is in the form of lower limit and the upper limit.One or more lower limits, and one can be respectively Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower limit and upper limit limit The border of special scope is determined.The all scopes that can be defined by this way be comprising and can be combined, i.e., any lower limit Can combine to form a scope with any upper limit.For example, the scope of 60-120 and 80-110 is listed for special parameter, is managed The scope solved as 60-110 and 80-120 is also what is expected.If additionally, the minimum zone value 1 and 2 listed, and if listed Maximum magnitude value 3,4 and 5, then following scope can all expect：1-3,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, numerical range " a-b " represents the contracting of any real combinings between a to b Sketch form shows that wherein a and b is real number.Such as numerical range " 0-5 " is represented Whole real numbers, " 0-5 " are that the breviary of these combinations of values is represented.
If be not specifically stated, the term " two kinds " used by this specification refers to " at least two ".
In the present invention, if special explanation, all embodiments mentioned in this article and the side of being preferable to carry out Formula can be mutually combined to form new technical scheme.
In the present invention, if not special illustrate, all technical characteristics mentioned in this article and preferred feature can New technical scheme to be formed to be mutually combined.
In the present invention, if not special illustrate, all steps mentioned in this article sequentially can be carried out, it is also possible to Carry out at random, it is preferred that order is carried out.For example, methods described includes step (a) and (b), represents that methods described can be wrapped Include (a) and (b) the step of order is carried out, it is also possible to the step of carrying out including order (b) and (a).For example, it is described to mention the side Method may also include step (c), represent that step (c) can be added to methods described with random order, and for example, methods described can include Step (a), (b) and (c), may also comprise step (a), (c) and (b), it is also possible to including step (c), (a) and (b) etc..
In the present invention, if not special illustrate, " including " mentioned in this article represents open, or envelope Enclosed.For example, described " including " can represent and can also include the other elements do not listed, it is also possible to only including the unit for listing Part.
The catalyst of the present invention has excellent catalysis activity and splendid mechanical strength, is highly suitable for fluidized-bed reaction Alkene is prepared by methanol in system.In one embodiment, when using the present invention catalyst enter in a fluidized bed reactor When the reaction of row methanol-to-olefins, in product, the selectivity of propylene is higher than 40%, more preferably higher than 45%.
Active component in the catalyst of the present invention is ZSM-5 molecular sieve, and this is that a kind of molecular sieve well known in the art is urged Agent material, directly commercially can buy, it is also possible to synthesize according to literature method.Used in following examples of the present invention The silica alumina ratio of ZSM-5 molecular sieve is 20-400, preferably 250-400.
For prepare catalyst of the present invention host material be Kaolin, calcined kaolin, kieselguhr, boehmite, One or more in montmorillonite, with the particle diameter less than 2 microns.By using the host material, raising can be played and urged The effect of agent intensity, wearability.The host material in roasting process it may happen that a certain degree of dehydration and/or point Solution, such as boehmite in roasting process are understood dehydration and ultimately form aluminium oxide, it is also possible to which some host material is not Generation dehydration and/or decomposition.In the present invention, all these components included in product catalyst are referred to as " being derived from described The component of host material ".
Component from the binding agent of the catalyst of the present invention comprising 10-45 weight %, the component is by binding agent The remaining component after spray drying and roasting is carried out.The binding agent can improve whole slurry system in slurry stage Uniformity and fluid property, while being also beneficial to improve the overall mechanical strength of final obtained catalyst, significantly improve which resistance to Mill property.According to specific needs, the composition of binding agent can be controlled by the species and content of regulation binding agent.For this One or more in following material of bright precursor：Alkaline silica sol, acidic silicasol, Alumina gel, aluminum phosphate etc..Alkali Property Ludox represent colloid that silica dioxide granule is formed in water, the mean diameter of the silica dioxide granule is that 8-20 is micro- Rice, its pH scope are 9-10, and the molecular formula of silicon dioxide contained therein can be denoted as SiO2·nH2O, with the gross weight of the Ludox Count on the basis of amount, calculate in the form of an oxide, wherein the silicon dioxide comprising 15-40 weight %, 0.2-0.4 weight % Na2O, and the water of surplus.The viscosity of the alkaline silica sol（25℃）For 2-2.5MPaS, density（25℃）For 1.1-1.3 Gram per centimeter3.Acidic silicasol is also called hydrosol of silicic acid, is that polymeric silica microgranule is dispersed in water the acidity to be formed Colloid, its pH value are 2-4, are counted, are calculated in the form of an oxide, wherein including on the basis of the gross weight of the acidic silicasol The silicon dioxide of 30-31 weight %, less than the Na of 0.006 weight %2O, and the water of surplus.The viscosity of the acidic silicasol （25℃）Less than 6MPaS, density（25℃）For 1.19-1.21 gram per centimeters3, the mean diameter of silica dioxide granule receives for 5-20 Rice, under normal temperature condition can stably keep three months and not form any precipitation.Alumina gel is alumina particle shape in water Into colloid, wherein solid concentration is 10-40 weight %, and pH value is 1-3, and the mean diameter of alumina particle is 10-50 nanometers, Wherein the chemical formula of alumina particle can write Al2O3·nH2O。
Method for preparing catalyst of the present invention includes mixing ZSM-5 molecular sieve, host material, binding agent and water Get up, make aqueous slurry, then the serosity is spray-dried and roasting.On the basis of the gross weight of the aqueous slurry Meter, wherein the total content of component in addition to water is 20-50 weight %.
In a preferred embodiment of the present invention, it is also contemplated that pore creating material, institute are added in the aqueous slurry It is can be burned out during roasting to state pore creating material, so as to leave the material in the hole of required size in the catalyst.Pore-creating Agent is mainly used in giving catalyst pore-creating, increases the contact area of catalyst and material, it is possible to use pore creating material well known in the art Material, such as starch, graphite etc., but more preferably use sesbania powder, polyvinyl alcohol, methylcellulose.In order to avoid affecting to urge The catalytic performance of agent, and in order to prevent pore creating material be burned out in roasting process, the consumption of the pore creating material is less.With Count on the basis of the gross weight of the component in the serosity in addition to water, the content of the pore creating material is about 0.01-1 weight %.
In addition, in order to promote full and uniform dispersion of the various raw materials in aqueous slurry, can also add wherein few Perhaps dispersant.Can use any dispersant material well known in the art, preferred n-octyl alcohol, ammonium hydrogen carbonate, carbonic acid diammonium hydrogen, These dispersants also can decompose in roasting process completely and be removed.With the gross weight of the component in the serosity in addition to water Count on the basis of amount, the content of the dispersant is about 0.01-1 weight %.
Above-mentioned aqueous slurry is spray-dried by spray dryer in the present invention.In spray-drying process, Interior is being dried by slurry spraying first, itself and hot air is then being made so that the moisture in serosity droplet gasifies rapidly, from And obtain the dry products with general uniform granularity and shape.Present invention preferably uses atomizer exsiccator or pressure type Spray dryer is spray-dried.The difference of both spray dryers is that the mode being atomized to serosity is different. In atomizer exsiccator, serosity is transported in the centrifugal turntable for being rotated in nebulizer at a high speed, serosity is quickly thrown away and It is atomized which.Serosity is spurted into using high-pressure pump and is dried interior by press spray exsiccator so as to form vaporific.
Embodiment
The present invention is conducted further description with reference to embodiment.In the examples below, the ZSM-5 catalysis for using The silica alumina ratio of agent is 20-400, preferred 250-400；Alkaline silica sol is the Ludox that solid concentration is 30 weight %, and pH value is 9, solid particle mean diameter is 14nm；Acidic silicasol is the Ludox that solid concentration is 30 weight %, and pH value is 2, solid Mean particle size is 14nm；Alumina gel is the Alumina gel that solid concentration is 30 weight %, and pH value is 2, the average grain of solid particle Footpath is 20nm；Polyvinyl alcohol is buied from the market, and its molecular weight is 16000-20000；Kaolin, boehmite, sesbania powder, N-octyl alcohol, calcined kaolin, kieselguhr, ammonium hydrogen carbonate, montmorillonite, bicarbonate diammonium and methanol are buied from commercial source, not Jing is further purified process and directly uses.
The catalyst of the present invention is prepared in below example 1-5.
Embodiment 1
Add 600g ZSM-5 catalyst fineses (silica alumina ratio is 250), 1200g alkalescence silicon in the stainless steel cauldron of 5L Colloidal sol, 600g Kaolin, 400g boehmites, 2g sesbania powders, 1g n-octyl alcohols, 4000g deionized waters, stir system Aqueous slurry is obtained, is spray-dried using atomizer exsiccator, the inlet temperature of the atomizer exsiccator is 300 DEG C, outlet temperature is 180 DEG C, and the charging rate of serosity is 100ml/min, is produced in the middle of the pellet type catalyst of gained of spraying Thing roasting 2h under conditions of 650 DEG C, air atmosphere in Muffle furnace, obtains catalyst 1#.
Embodiment 2
Add 800g ZSM-5 catalyst fineses (silica alumina ratio is 300), 750g acidity silicon in the stainless steel cauldron of 5L Colloidal sol, 1200g calcined kaolins, 900g boehmites, 4000g deionized waters, sesbania powder 10g, n-octyl alcohol 35g are fully stirred Uniformly prepared aqueous slurry is mixed, it is spray-dried using atomizer exsiccator, the atomizer exsiccator enters Mouthful temperature is 300 DEG C, and outlet temperature is 180 DEG C, and the charging rate of serosity is 250ml/min, the particulate catalytic of gained of spraying Agent intermediate product roasting 4h under conditions of 600 DEG C, air atmosphere in Muffle furnace, obtains catalyst 2#.
Embodiment 3
In the stainless steel cauldron of 5L add 700g ZSM-5 catalyst fineses (silica alumina ratio is 350), 900g Alumina gels, 100g acidic silicasols, 1400g kieselguhr, 30g sesbania powders, 10g n-octyl alcohols, 5000g deionized waters, stir prepared Aqueous slurry, is spray-dried using press spray exsiccator, and the inlet temperature of the press spray exsiccator is 250 DEG C, outlet temperature is 180 DEG C, and the charging rate of serosity is 275ml/min, and the pellet type catalyst intermediate product of gained of spraying exists In Muffle furnace under conditions of 500 DEG C, air atmosphere roasting 6h, obtain catalyst 3#.
Embodiment 4
Add 3000g ZSM-5 catalyst fineses (silica alumina ratio is 400), 600g alkalescence silicon in the stainless steel cauldron of 5L Colloidal sol, 1400g Kaolin, 600g boehmites, 10g polyvinyl alcohol, 10g ammonium hydrogen carbonate, 5000g deionized waters are fully stirred Uniformly prepared aqueous slurry is mixed, it is spray-dried using atomizer exsiccator, the atomizer exsiccator enters Mouthful temperature is 300 DEG C, and outlet temperature is 150 DEG C, and the charging rate of the aqueous slurry is 500ml/min, spraying gained Granular catalyst intermediate product roasting 6h under conditions of 550 DEG C, air atmosphere in Muffle furnace, obtains catalyst 4#.
Embodiment 5
Add 900g ZSM-5 catalyst fineses (silica alumina ratio is 300), 1600g silicon in the stainless steel cauldron of 5L molten Glue, 800g montmorillonites, 5g sesbania powders, 5g bicarbonate diammonium, 12000g deionized waters, stir prepared aqueous slurry, It is spray-dried using atomizer exsiccator, the inlet temperature of the atomizer exsiccator is 300 DEG C, outlet temperature Spend for 200 DEG C, the charging rate of the aqueous slurry is 250ml/min, and the pellet type catalyst intermediate product of gained of spraying exists In Muffle furnace under conditions of 600 DEG C, air atmosphere roasting 4h, obtain catalyst 5#.
Technique using prior art in following comparative example prepares the catalyst for control experiment.
Comparative example
Take ZSM-5 molecular sieve original powder 1000g（SiO2/Al2O3=200）, in the lanthanum nitrate hexahydrate that La concentration is 3 weight % The dipping of La in 1500g, is carried out at room temperature, after room temperature immersion 24h, is warming up to boiling, while stirring, after into after thick, 120 DEG C of drying, then in 600 times roasting 3h, La/ZSM-5 is obtained, utilize and operate to La/ZSM-5 molecular sieves with dipping La identicals Carry out impregnating Mg process, Mg loadings are 3.2%, weigh Kaolin 3567g, deionized water 6000g that contents on dry basis is 84%, Mix with above-mentioned Mg-La/ZSM-5 molecular sieves, stir 30min, colloid mill grinding 30min, spray shaping control spray dryer Inlet temperature 400, outlet temperature 200, inject pressure 2.0MPa.The catalyst microspheres of molding are used after cooling in 600 roasting 3h 0.1mol/L hydrochloric acid is swapped, liquid volume（ml）Ratio with catalyst solid (g) is 10ml/g, and exchange temperature is 90, 1h, exchanges 2 times every time, is washed with deionized to picking without chloride ion, and 110 drying, 600 roastings more than 2 hours obtain PLa/ HZSM-5 microspherical catalysts, 10gPLa/HZSM-5 microspherical catalysts are loaded in fluidized-bed reactor, carry out silane in 500 Change, tetraethyl orthosilicate is dissolved in methanol, its weight content is 10%, reaction 1 in reactor is passed through with the speed of 30ml/h little When, after Silanization reaction terminates, air is passed through in 600 DEG C of roastings more than 2 hours, to remove the carbon deposit of catalyst surface, is obtained 0# catalyst.
Embodiment 6
The above-mentioned catalyst 1#-5# of 150g and 0# catalyst are weighed respectively, load diameter 50mm, high 110 centimetres of fluidisation In bed, fed using the methanol aqueous solution that volumetric concentration is 50%, 460-500 DEG C of temperature of reactor, the mass space velocity of methanol is 2h-1, reaction pressure 0.1MPa carries out reacting the composition of obtained product using these catalyst using gas chromatographic detection.Survey Methanol conversion 100% is obtained, concrete products distribution when 8 hours after starting to react is shown in Table 1.
Products distribution of 1 catalyst of table in methanol to olefins reaction（Mass percent）
As can be seen from Table 1, compared with existing catalyst, there is the catalyst of the present invention substantially suitable propylene to select Property, the synthesis step of catalyst of the present invention is more simply too much than existing process in addition, can significantly simplify production technology, reduces into This.
Embodiment 7
In order to test the life-span of catalyst of the present invention, weigh 150 grams of above-mentioned catalyst 1# and load diameter 50mm, high 110cm Fluid bed in, compare 1 using alcohol water quality：1 methanol aqueous solution charging, 460-500 DEG C of temperature of reactor, methanol quality air speed 1h-1, reaction pressure 0.1MPa, using gas chromatographic detection using product obtained in these catalyst reactions composition.Measure first To the composition of product, alcohol conversion 100%, constantly detects that concrete products distribution is shown in Table 2 in the course of reaction of 200h.
Products distribution of the 1# catalyst of 2 present invention of table in methanol to olefins reaction（Mass percent）
Time/h CH4 C2H4 C3H6 C4 C5
10 0.48 9.44 46.79 23.72 13.32
50 0.41 8.66 46.95 24.16 12.76
100 0.58 8.62 49.16 24.89 12.80
150 0.84 9.66 46.54 23.14 12.43
200 1.20 9.14 46.01 23.51 12.30
Can be seen by upper table 2, the catalyst of the present invention is used afterwards still can be effectively more than 200 hours Its catalysis activity and selectivity are kept, gratifying service life is shown.
Embodiment 8
Abrasion index test is carried out to 3# and 0# catalyst using vertical abrasion index tester, standard is adopted for ASTM- D5757-00, is control sample using Chang Ling FCC poising agents, and Chang Ling FCC poising agents abrasion index is 2.5%, 3# catalyst abrasions Index is 1.7%, and 0# catalyst abrasions index is 5.8%.As can be seen here, compared with the catalyst of prior art, the present invention Catalyst there is the wear resistance that significantly improves.

Claims (10)

1. a kind of method for preparing catalyst, the catalyst is the catalysis for alkene is prepared by methanol in fluid bed Agent, the method comprising the steps of：
(1) ZSM-5 molecular sieve, host material, binding agent and water are mixed, is configured to aqueous slurry, with the aqueous slurry Gross weight on the basis of count, wherein the total content of component in addition to water is 20-50 weight %, with the serosity except water On the basis of the gross weight of component in addition count, in the serosity content of ZSM-5 molecular sieve be 20-55 weight %, the ZSM-5 The silica alumina ratio of molecular sieve is Si/Al=20-400, is counted, institute on the basis of the gross weight of the component in the serosity in addition to water The content for stating host material described in serosity is 20-59 weight %, and the particle diameter of the host material is less than 2 microns, selected from following One or more in material：Kaolin, calcined kaolin, kieselguhr, boehmite, montmorillonite, to remove in the serosity Count on the basis of the gross weight of the component beyond water, the content of binding agent described in the serosity is 20-50 weight %, it is described viscous Knot agent is acidic silicasol and Alumina gel, and also comprising dispersant, the dispersant is n-octyl alcohol to the serosity, with the serosity Count on the basis of the gross weight of component in addition to water, in the serosity, the content of dispersant is 0.01-1 weight %；
(2) serosity obtained in step (1) is spray-dried, graininess intermediate product is obtained；
(3) roasting is carried out to graininess intermediate product obtained in step (2), be obtained for alkene being prepared by methanol in fluid bed The catalyst of hydrocarbon.
2. the method for claim 1, it is characterised in that the gross weight with the component in the serosity in addition to water is Benchmark meter, in the serosity, the content of ZSM-5 molecular sieve is 20-55 weight %, and the silica alumina ratio of the ZSM-5 molecular sieve is Si/ Al=200-400.
3. the method for claim 1, it is characterised in that the serosity also includes pore creating material.
4. method as claimed in claim 3, it is characterised in that one or more in following material of the pore creating material： Sesbania powder, polyvinyl alcohol, methylcellulose, are counted on the basis of the gross weight of the component in the serosity in addition to water, described The content of pore creating material described in serosity is 0.01-1 weight %.
5. the method as any one of claim 1-4, it is characterised in that in the step (2), using atomizer Exsiccator or press spray exsiccator are spray-dried, and the inlet temperature of spray dryer is 250-300 DEG C, outlet temperature For 150-200 DEG C, it is 100-500ml/min that serosity is input into the feed rate of the spray dryer.
6. the method as any one of claim 1-4, it is characterised in that in the step (3), at 400-600 DEG C At a temperature of the roasting of 3-6 hours is carried out to the graininess intermediate product.
7. the method as any one of claim 1-4, it is characterised in that in the step (3), in 550 DEG C of temperature The roasting of 4 hours is carried out under degree to the graininess intermediate product.
8. the catalyst that prepared by a kind of method by any one of claim 1-4, with the gross weight of the catalyst On the basis of count, the catalyst comprising 25-60 weight % ZSM-5 molecular sieve, 20-50 weight % from the host material Component and 10-45 weight % the component from the binding agent, the particle diameter of the catalyst is 50-110 microns.
9. catalyst as claimed in claim 8, it is characterised in that ZSM-5 molecule of the catalyst comprising 25-40 weight % Sieve, the component from the binding agent of the component and 25-40 weight % from the host material of 30-45 weight %, The particle diameter of the catalyst is 50-110 microns.
10. a kind of method for preparing alkene by methanol, the method include, is being sufficient so that methanol and is converted into the reaction condition of alkene Under, it is in a fluidized bed reactor so that the aqueous solution of methanol or methanol is contacted with the catalyst described in claim 8, described anti- The condition is answered to be：Methanol quality air speed 0.5-5h-1, reaction temperature 430-550 DEG C, reaction pressure 0-1MPa.
CN201310040880.0A 2013-01-31 2013-01-31 It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed Expired - Fee Related CN103962169B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201310040880.0A CN103962169B (en) 2013-01-31 2013-01-31 It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed
PCT/CN2014/071737 WO2014117735A1 (en) 2013-01-31 2014-01-29 Catalyst for preparing olefin from methanol in fluidized bed and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310040880.0A CN103962169B (en) 2013-01-31 2013-01-31 It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed

Publications (2)

Publication Number Publication Date
CN103962169A CN103962169A (en) 2014-08-06
CN103962169B true CN103962169B (en) 2017-04-05

Family

ID=51232455

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310040880.0A Expired - Fee Related CN103962169B (en) 2013-01-31 2013-01-31 It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed

Country Status (2)

Country Link
CN (1) CN103962169B (en)
WO (1) WO2014117735A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211086B (en) * 2014-09-22 2016-04-13 湖南理工学院 ZSM-5 zeolite molecular sieve and preparation method thereof
CN108262069B (en) * 2017-01-04 2021-06-22 中国石油化工股份有限公司 Method for producing a fluidized bed catalyst, catalyst produced and use thereof
CN109721447A (en) * 2017-10-27 2019-05-07 上海碧科清洁能源技术有限公司 A method of olefin product is prepared using ciculation fluidized bed reaction technique
CN108404970B (en) * 2018-03-05 2020-02-18 中国科学院山西煤炭化学研究所 Apple-shaped hollow molecular sieve microsphere and preparation method and application thereof
CN109225235B (en) * 2018-10-10 2021-07-20 上海兖矿能源科技研发有限公司 High-efficiency wear-resistant iron-based catalyst for Fischer-Tropsch synthesis in slurry bed and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274283A (en) * 2008-04-11 2008-10-01 中国石油化工股份有限公司 Method for preparing olefin hydrocarbon catalyst from oxygen-containing compounds

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040064008A1 (en) * 2002-09-30 2004-04-01 Torsten Maurer Molecular sieve catalyst composition
CN102371168B (en) * 2010-08-23 2013-12-04 中国石油化工股份有限公司 Preparation method of fluid catalyst
CN102372534B (en) * 2010-08-23 2014-07-02 中国石油化工股份有限公司 Method for preparing light olefins through conversion of oxygen-containing compounds
CN102059138A (en) * 2010-11-18 2011-05-18 大唐国际化工技术研究院有限公司 ZSM-5 zeolite catalyst for preparing propylene by methanol dehydration as well as preparation method and application thereof
CN102527445B (en) * 2011-12-21 2014-01-08 陕西煤化工技术工程中心有限公司 Preparation method of low-abrasion fluidized bed microspherical catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101274283A (en) * 2008-04-11 2008-10-01 中国石油化工股份有限公司 Method for preparing olefin hydrocarbon catalyst from oxygen-containing compounds

Also Published As

Publication number Publication date
WO2014117735A1 (en) 2014-08-07
CN103962169A (en) 2014-08-06

Similar Documents

Publication Publication Date Title
CN103962169B (en) It is a kind of for preparing catalyst of alkene and preparation method thereof by methanol in fluid bed
KR101083844B1 (en) Process for production of propylene
CN101481122B (en) Process for producing composite silicophosphoaluminate molecular sieve by in situ synthesis
CN102648051B (en) Produce the method for Si bonding fluid catalyst
WO2014166372A1 (en) Mixed molecular sieve catalyst and preparation method and use thereof
CN103447070A (en) FCC (Fluid Cracking Catalyst) catalyst containing silicon binder and preparation method thereof
CN106890672B (en) A kind of methanol conversion light olefin catalyst processed and its preparation method and application
CN102371167A (en) Fluidized bed catalyst and its preparation method
Ebrahimi et al. Effect of calcination temperature and composition on the spray-dried microencapsulated nanostructured SAPO-34 with kaolin for methanol conversion to ethylene and propylene in fluidized bed reactor
CN102371168B (en) Preparation method of fluid catalyst
CN102886275A (en) Method for preparing dual-molecular-sieve-containing cracking catalyst by using in-situ crystallization
CN102464548B (en) Method for preparing propylene by disproportionating fluidized bed olefin
CN109789392A (en) Peptization for can fluidized catalyst aluminium oxide method
CN100413586C (en) Molecular screen microspherical catalyst
CN100475756C (en) Method for producing propylene and ethene by using catalytic cracking olefin through fluid bed
CN102372553B (en) Method for producing olefin by catalytically cracking
JP4394992B2 (en) Catalyst composition for increasing gasoline octane number and / or lower olefin and fluid catalytic cracking process of hydrocarbons using the same
CN115999629A (en) Heterogeneous catalyst for preparing aldehyde by hydroformylation of alpha-olefin, preparation method and application thereof
CN103962170A (en) Methanol-to-olefin catalyst with high C4 olefin selectivity and preparation method thereof
CN102372551B (en) Method for producing light olefin by catalytically cracking
CN102371183B (en) Preparation method for adhesive-free fluidized bed catalyst
CN109721447A (en) A method of olefin product is prepared using ciculation fluidized bed reaction technique
CN104822455A (en) Catalytic cracking of organic compounds, using modified y zeolite
CN111822033A (en) Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof
CN109701633A (en) Fluid catalyst, preparation method and its usage

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170405

Termination date: 20220131