CN108435245A - Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application - Google Patents

Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application Download PDF

Info

Publication number
CN108435245A
CN108435245A CN201810357940.4A CN201810357940A CN108435245A CN 108435245 A CN108435245 A CN 108435245A CN 201810357940 A CN201810357940 A CN 201810357940A CN 108435245 A CN108435245 A CN 108435245A
Authority
CN
China
Prior art keywords
sapo
kaolin
catalyst
preparation
crystal grain
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.)
Granted
Application number
CN201810357940.4A
Other languages
Chinese (zh)
Other versions
CN108435245B (en
Inventor
刘海燕
张丽娜
鲍晓军
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.)
China University of Petroleum Beijing
Original Assignee
China University of Petroleum Beijing
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 China University of Petroleum Beijing filed Critical China University of Petroleum Beijing
Priority to CN201810357940.4A priority Critical patent/CN108435245B/en
Publication of CN108435245A publication Critical patent/CN108435245A/en
Application granted granted Critical
Publication of CN108435245B publication Critical patent/CN108435245B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/82Phosphates
    • B01J29/84Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85Silicoaluminophosphates [SAPO compounds]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/633Pore volume less than 0.5 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/638Pore volume more than 1.0 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/82Phosphates
    • C07C2529/84Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85Silicoaluminophosphates (SAPO compounds)
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention provides a kind of 34@kaolin microspheres catalyst of little crystal grain grade hole SAPO and its preparations and application.The preparation method includes the following steps:Kaolin microsphere, the kaolin microsphere activated after fired is prepared;It is mixed with the alukalin microballoon, water, phosphorus source, micropore template agent and mesoporous template to obtain reactant gel;Crystallizing treatment is carried out to the reactant gel, centrifuges, obtains 34@kaolin microsphere composite materials of little crystal grain grade hole SAPO;Calcination process is carried out to 34@kaolin microsphere composite materials of little crystal grain grade hole SAPO, obtains 34@kaolin microsphere catalyst of little crystal grain grade hole SAPO.34 molecular sieve contents of SAPO height, crystal grain are small in the 34@kaolin microsphere catalyst of SAPO, and have grade hole;Compared with the product being not added with obtained by mesoporous template, the yield with higher situ product.

Description

Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application
Technical field
The present invention relates to chemical technology fields, and specifically, the present invention relates to a kind of little crystal grain grade hole SAPO-34@high Ridge soil microspherical catalyst and its preparation and application.
Background technology
Ethylene and propylene are the most important basic organic chemical raw materials of chemical industry, and act is played in modern petrochemical field The effect of sufficient weight.In recent years, gradually decreasing with oil amount of storage, oil supply amount is increasingly deficient, is original with naphtha Material production ethylene and the route of propylene will face a severe test, and therefore, seeking to substitute petroleum path, to prepare ethylene and propylene etc. low The process route of carbon olefin becomes inevitable.By the research for many years of researcher, using coal or natural gas as raw material, through methanol or Person's dimethyl ether is the process route for being most hopeful to substitute naphtha route for the route of low-carbon alkene.First industrially at present The catalyst of alcohol alkene (MTO) is the catalyst using SAPO-34 as active component, and building-up process summary is:Chemical reagent closes At micropore SAPO-34 molecular screen primary powders, then by it with matrix (generally kaolin), binder, pore creating material and water etc. mix, Stir, be beaten, being spray dried to 80-100 μm or so of bead, as MTO catalyst.This method is referred to as " semi-synthetic " side Method, there are following two disadvantages for MTO catalyst prepared by this " semi-synthetic " method:First, synthesized SAPO-34 molecular sieves Usually micro porous molecular sieve, molecular sieve bore diameter is smaller, is unfavorable for the diffusion of reactants and products, easily coking and deactivation;Second, it adopts It being unevenly distributed with the catalyst activity component prepared by " semi-synthetic ", binder blocks duct, catalyst duct not unicom, Easily cause catalyst inactivation.
Some researches show that in MTO reactions, reduce the crystallite dimension of SAPO-34 molecular sieves, be conducive to reactants and products Diffusion;On the other hand, mesoporous, SAPO-34 molecular sieve of the synthesis with grade pore passage structure is introduced in micro porous molecular sieve, The diffusion that reactants and products can be improved, to improve catalyst service life and diene (ethylene+propylene) selectivity, simultaneously Reaction depth can effectively be inhibited, carbon deposition rate is reduced and increase and hold carbon ability;Third, using in-situ crystallization method, in matrix Upper growth in situ molecular sieve crystal, catalyst can be prepared to avoid " semi-synthetic " method to be caused Active components distribution unevenness, bonds Agent blocks the problem of duct.
Research about little crystal grain and grade hole SAPO-34 molecular sieves has very much, such as:Liu Hongxing has applied for a series of passes In how the patent of the method for synthesizing small-grain SAPO-34 molecular sieves:CN104445266A, CN103420391A and CN102464338A.Wherein, the method for CN104445266A reports is first to obtain the initial crystallization 1-10h of SAPO-34 defective SAPO-34 crystal seeds, then this defective crystal seed is added in the initial crystallization liquid of SAPO-34, at 140-170 DEG C Hydro-thermal process 0.1-4h dissolves defect crystal seed, then continues the SAPO-34 molecular sieves that heating crystallization obtains little crystal grain;CN The method of 103420391 A reports is to prepare fine grain SAPO-34 by the method for being segmented crystallization, and concrete operations are first in 180- 250 DEG C of crystallization 1-20h, then program be cooled to -160 DEG C of room temperature, at least keep 0.1h, be finally continuously heating to 180-250 DEG C Crystallization 2-24h, obtains fine grain SAPO-34;The method of 102464338 A of CN is similar with 104445266 A of CN, only raw material In add HF solution.
Preparation report about grade hole SAPO-34 is few.106608632 A of CN describe a kind of hierarchical porous structure The preparation method of SAPO-34 molecular sieves is mainly obtained by the method that nano carbon black hard mould agent is added in synthesized gel rubber Multi-stage porous;105858684 A of CN 104525250 A and CN reports the crystal seed by introducing broken crystal seed and Nano lamellite The method for preparing multi-stage porous SAPO-34 molecular sieves;104973608 A of patent CN report poly- by being added in synthesized gel rubber The method of ethylene glycol prepares the SAPO-34 molecular sieves of multi-stage porous;It is more that 107285342 A of CN report a kind of post-processing preparation SAPO-34 molecular sieves and solid acid, i.e., be pulverized and mixed uniformly by the method for grade hole SAPO-34 molecular sieves, anti-at 20-120 DEG C The regular hour is answered to obtain multi-stage porous SAPO-34 molecular sieves;The little crystal grain or more that above-mentioned a series of preparation method obtains Grade hole SAPO-34 molecular sieves all have good reactivity worth, however the synthetic method that gained has been reported for work is entirely that ex situ is closed At using the deficiency for equally existing " semi-synthetic " catalyst.
In conclusion existing literature report changes building-up process and synthesis condition comes mainly by the method for ex situ It prepares little crystal grain or multi-stage porous SAPO-34 molecular sieves, the molecular sieve of gained is required to be prepared into MTO using " semi-synthetic " method Catalyst, therefore, using in-situ synthetic method, exploitation diffusion is good, the high fabricated in situ little crystal grain grade of catalytic performance Hole SAPO-34 molecular sieve catalytic materials and catalyst have great importance.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of little crystal grain grade hole SAPO-34@kaolin The preparation method of microspherical catalyst.Whole sial of SAPO-34 Zeolite synthesis are provided by using kaolin microsphere for raw material Source, and as the matrix of molecular sieve growth, phosphorus source is supplemented, and specific mesoporous template is added in the synthesis process, it is in situ brilliant Change and realizes.
Another object of the present invention is to provide a kind of high yield SAPO-34@kaolin microsphere catalyst.
Another object of the present invention is to provide a kind of methods of methanol-to-olefins.
In order to achieve the above objectives, the present invention provides a kind of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst Preparation method, wherein this method comprises the following steps:
(1) kaolin microsphere, the kaolin microsphere activated after fired is prepared;
(2) kaolin microsphere, water of the activation for obtaining step (1), phosphorus source, micropore template agent and the mixing of mesoporous template Reactant gel is prepared, each component molar ratio meets following condition:
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2 +R3):(100-300)H2O, wherein R1 is micropore template agent, and R2 and R3 are mesoporous template, and silicon source and silicon source are all from kaolinite Native microballoon;
(3) Crystallizing treatment is carried out to the reactant gel that step (2) obtains, is then centrifuged for detaching, obtains little crystal grain grade Hole SAPO-34@kaolin microsphere composite materials;
(4) calcination process is carried out to the composite material that step (3) obtains, obtains little crystal grain grade hole SAPO-34@high Ridge soil microspherical catalyst.
Preparation method provided by the present invention using in kaolin silicon, aluminium species are as synthesis SAPO-34 molecular sieves One of raw material supplements phosphorus source, and using specific template is introduced, induces the SAPO-34@kaolin in synthesizing small-grain grade hole Microspherical catalyst.Method using the present invention is using the sial component in kaolin as the raw material of synthesis SAPO-34 molecular sieves, energy It is enough largely to reduce synthesis cost, synthesized SAPO-34 small, step hole feature structures with crystal grain, and have Very high yield, while being conducive to the raising of MTO reactivity worth.
In the present invention, silicon, the aluminium species (i.e. silicon source, silicon source) of kaolin offer refer in kaolin microsphere by roasting After processing, it can be extracted by hydrochloric acid or sodium hydroxide solution, into reactant gel, the sial object as Zeolite synthesis Kind.
In the preparation process in accordance with the present invention, the kaolin microsphere of step (1) can be carried out according to prior art conventional method It prepares, step (1) can be that it is micro- to prepare kaolin using the method for spray drying after mixing kaolin with water and binder Ball.Specifically, first kaolin can be crushed, screening, is then mixed again with water and binder.
In the preparation process in accordance with the present invention, in step (1), the mass ratio of kaolin and binder is preferably 2.5-3:1.
In the preparation process in accordance with the present invention, in step (1), binder is preferably in waterglass, Aluminum sol and Ludox One or more mixtures.
In the preparation process in accordance with the present invention, it is preferable that in step (1), the temperature of roasting is 700-900 DEG C, more preferably It is 800 DEG C;The time of roasting is 1-6h, more preferably 3-4h.
In the preparation process in accordance with the present invention, in step (1), kaolin microsphere can be according to prior art conventional kaolin Prepared by Microsphere Size, it is preferable that the grain size of kaolin microsphere is 80-110 μm.
In the preparation process in accordance with the present invention, the charging sequence in step (2) can be:Water-phosphoric acid-micropore template agent-height The aqueous solution of the mesoporous template R3 of ridge soil microballoon-mesoporous template R2-.Mesoporous template is first added when mesoporous template is added Mesoporous template R3 is added in R2 afterwards.Mesoporous template R3 needs thoroughly to be dissolved with a certain amount of deionized water before addition.
In the preparation process in accordance with the present invention, it is preferable that step (2) includes:First mesoporous template R3 is mixed with part water, It is stirred overnight, so that mesoporous template R3 is fully dissolved, obtain solution A;Phosphorus source is uniformly mixed with part water, micropore is then added Template R1 is added the kaolin microsphere for the activation that step (1) obtains, mesoporous template R2 is then added, stirs after mixing It mixes after so that it is sufficiently mixed, the solution A is added.
In the preparation process in accordance with the present invention, it is preferable that in step (2), the molar ratio of each component preferably satisfies following item Part:(0.2-0.27)SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9)R1:(0.13-0.61)(R2+R3): (114-300)H2O。
In the preparation process in accordance with the present invention, it is preferable that in step (2), mesoporous template R2 is added and carries out aging later Processing, the temperature of the burin-in process may be controlled to 40-90 DEG C, preferably 70 DEG C.
In the preparation process in accordance with the present invention, it is preferable that in step (2), the solution A containing mesoporous template R3 is to add It is added after entering mesoporous template R2 and aging 0-5h;It is added after preferably burin-in process 3.5h.
In the preparation process in accordance with the present invention, it is preferable that the micropore template agent is triethylamine.
In the preparation process in accordance with the present invention, it is preferable that phosphorus source is orthophosphoric acid.
In the preparation process in accordance with the present invention, it is preferable that the mesoporous template R2 is selected from cationic surfactant 16 One kind in alkyl trimethyl ammonium bromide, tetradecyltrimethylammonium bromide and dodecyl trimethyl ammonium bromide etc..
In the preparation process in accordance with the present invention, it is preferable that the mesoporous template R3 is selected from organosilan dimethyl hexadecyl One kind in base [3- trimethoxy silicon propyl] ammonium chloride and dimethyl stearyl [3- trimethoxy silicon propyl] ammonium chloride etc..
In the preparation process in accordance with the present invention, it is preferable that in step (3), the temperature of Crystallizing treatment is 180-220 DEG C, excellent It is selected as 200 DEG C;The time of Crystallizing treatment is 24-72h, preferably 48h.
In the preparation process in accordance with the present invention, it is preferable that step (3), by standing sedimentation, is centrifuged, washed after crystallization It washs and obtains little crystal grain grade hole SAPO-34@kaolin microsphere composite materials with drying and other steps.The standing sedimentation time can control For 2-15min.Dry temperature may be controlled to 100-120 DEG C, be carried out in air atmosphere, and drying time can be 4-12h.
In the preparation process in accordance with the present invention, it is preferable that in step (4), the temperature of the roasting is 500-650 DEG C, institute The time for stating roasting is 3-6h.
It is excellent the present invention also provides the little crystal grain grade hole SAPO-34@kaolin microspheres that above-mentioned preparation method is prepared Selection of land, in terms of relative crystallinity, the relative amount of SAPO-34 molecular sieves is 15-35wt.%.
Specific embodiment according to the present invention, yield in situ=(situ product quality after roasting)/(feed intake middle kaolin The quality of the corresponding phosphorus pentoxide of microballoon+phosphoric acid), little crystal grain grade hole SAPO-34@kaolin microspheres prepared by the present invention are urged The yield of agent is 55-70wt.%.
The present invention also provides a kind of methods of methanol-to-olefins, wherein this method is with the methanol of a concentration of 95wt.% Aqueous solution is raw material, using above-mentioned little crystal grain grade hole SAPO-34 kaolin microspheres as catalyst, in normal pressure, reaction temperature 450 DEG C, mass space velocity 2.5h-1Under conditions of prepare alkene.
Technical scheme of the present invention has the following advantages that:
The present invention, simultaneously as matrix and part material, provides synthesis SAPO-34 molecular sieves institute using kaolin microsphere Whole silicon and aluminum sources needed, and specific mesoporous template is added in the synthesis process, obtained SAPO-34 molecular sieve contents it is high, The small SAPO-34@kaolin microsphere catalyst with grade hole of crystal grain;Compared with the product being not added with obtained by mesoporous template, Yield with higher situ product.
The little crystal grain grade hole SAPO-34@kaolin microspheres catalyst can be reacted directly as MTO catalyst for MTO Device, this can not only greatly shorten the preparation path of catalyst, reduce catalyst preparation cost, and can be closed by modulation Come the grain size of modulation SAPO-34 and mesoporous content, and then the architectural characteristic of modulation composite material at condition, avoids " semi-synthetic " side The drawbacks of method matrix or binder block molecular sieve pore passage, can also avoid the generation of a large amount of ex situ products, play small crystalline substance The synergistic effect of grain and grade pore structure, to improve MTO reaction service life and diene (ethylene+propylene) selectivity.
Description of the drawings
Fig. 1 is the XRD spectra of 1 obtained catalyst of embodiment.
Fig. 2 a and Fig. 2 b are the Flied emission scanning that 1 obtained composite material of embodiment amplifies 400 times and 10000 times respectively Electronic Speculum (FESEM) photo.
Fig. 3 is the XRD spectra of 2 obtained catalyst of embodiment.
Fig. 4 a and Fig. 4 b are the FESEM photos that 2 obtained composite material of embodiment amplifies 800 times and 10000 times respectively.
Fig. 5 is the XRD spectra of 3 obtained catalyst of embodiment.
Fig. 6 a and Fig. 6 b are the FESEM photos that 3 obtained composite material of embodiment amplifies 500 times and 10000 times respectively.
Fig. 7 is the XRD spectra of 4 obtained catalyst of embodiment.
Fig. 8 a and Fig. 8 b are the FESEM photographs that 4 obtained composite material of embodiment amplifies 2000 times and 10000 times respectively Piece.
Fig. 9 is the XRD spectra of 5 obtained catalyst of embodiment.
Figure 10 a and Figure 10 b are the FESEM photographs that 5 obtained composite material of embodiment amplifies 500 times and 20000 times respectively Piece.
Figure 11 is the XRD spectra of 6 obtained catalyst of embodiment.
Figure 12 a and Figure 12 b are the FESEM photographs that 6 obtained composite material of embodiment amplifies 2000 times and 20000 times respectively Piece.
Figure 13 is the XRD spectra of 7 obtained catalyst of embodiment.
Figure 14 a and Figure 14 b are that 7 obtained composite material of embodiment amplifies 700 times and 50000 times of FESEM photos respectively.
Figure 15 is the XRD spectra of 1 obtained catalyst of comparative example.
Figure 16 a and Figure 16 b are the FESEM photographs that 1 obtained composite material of comparative example amplifies 1500 times and 20000 times respectively Piece.
Figure 17 is the XRD spectra of 2 obtained catalyst of comparative example.
Figure 18 a and Figure 18 b are the FESEM photographs that 2 obtained composite material of comparative example amplifies 1500 times and 20000 times respectively Piece.
Figure 19 is the XRD spectra of 3 obtained catalyst of comparative example.
Figure 20 a and Figure 20 b are the FESEM photographs that 3 obtained composite material of comparative example amplifies 2400 times and 20000 times respectively Piece.
The N of sample in Figure 212Adsorption/desorption curve.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
The present invention uses the crystal phase structure of XRD determining sample;Using the crystalline form crystalline substance looks of FESEM determination samples;It is inhaled using N2- The texture property of attached desorption determination sample.
The content of SAPO-34 molecular sieves in the SAPO-34@kaolin microsphere catalyst of little crystal grain step provided by the invention hole Calculated with relative crystallinity data.Relative crystallinity refers to that the characteristic peak of each molecular sieve in in-situ crystallization product is corresponding The area of the characteristic peak of molecular sieve standard specimen and the ratio between, the characteristic peaks of SAPO-34 molecular sieves be 2 θ=9.5 °, 16.0 °, 20.5 °, Peak at 31 °.Standard specimen molecular sieve is the conventional micropore SAPO-34 molecular sieves of Nankai's catalyst plant production, by its crystallinity It is set to 100%.
Original position yield and ex situ relative productivity provided by the invention are calculated by following equation:Yield=roasting in situ The quality of SAPO-34@kaolin microsphere catalyst after burning Template removal/(quality for the kaolin microsphere that feeds intake+feed intake phosphoric acid correspondence Phosphorus pentoxide quality), ex situ relative productivity=ex situ product quality/SAPO-34@kaolin microsphere catalyst Quality.
Embodiment 1
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 700 DEG C by ridge soil microballoon, spare.
0.5g dimethyl stearyls [3- trimethoxy silicon propyl] ammonium chloride (TPOAC) is weighed to pour into equipped with 15g water In beaker, 12h is stirred, so that it is fully dissolved, obtains solution A.
It weighs 4g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.1g cetyl trimethylammonium bromides (CTAB) is added, and 70 DEG C of water-baths stand 1h, add Enter solution A, obtain reactant gel, each component molar ratio meets in the gel of preparation:0.20SiO2:1Al2O3:1.7P2O5: 3.9R1:0.13(R2+R3):170H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 40h in baking oven is rotated at 180 DEG C.
Product is taken out, standing sedimentation 2min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 4h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 15% in product, and situ product yield is 55%, the XRD diffraction patterns of microspherical catalyst are as shown in Figure 1, FESEM photos are as shown in Figure 2 a and 2 b, SAPO-34 grain sizes About 380nm.
Embodiment 2
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Ludox 35g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 0.7g TPOAC to pour into the beaker equipped with 10g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 4g phosphoric acid to mix with 10g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.3g CTAB is added, and 75 DEG C of water-baths stand 2h, solution A is added, and it is solidifying to obtain reactant Glue, each component molar ratio meets in the gel of preparation:0.25SiO2:1.17Al2O3:1.7P2O5:3.9R1:0.22(R2+R3): 114H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 5min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 6h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 20% in product, and yield in situ is 57%, micro- The XRD diffraction patterns of sphere catalyst as shown in figure 3, FESEM photos as shown in figures 4 a and 4b, SAPO-34 grain sizes are about 360nm。
Embodiment 3
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 850 DEG C by ridge soil microballoon, spare.
0.17g dimethyl hexadecyls base [3- trimethoxy silicon propyl] ammonium chloride (TPHAC) is weighed to pour into equipped with 10g water In beaker, 12h is stirred, so that it is fully dissolved, obtains solution A.
It weighs 5g phosphoric acid to mix with 10g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.5g dodecyl trimethyl ammonium bromide (DTAB) is added, and 70 DEG C of water-baths stand 2.5h, Solution A is added, obtains reactant gel, each component molar ratio meets in the gel of preparation:0.26SiO2:1.20Al2O3: 2.16P2O5:5.0R1:0.196(R2+R3):115H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 6min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 100 DEG C of dry 8h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 22% in product, and yield in situ is 65%, micro- The XRD diffraction patterns of sphere catalyst as shown in figure 5, FESEM photos as shown in figures 6 a and 6b, SAPO-34 grain sizes are about 350nm。
Embodiment 4
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and waterglass 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 3h at 900 DEG C by ridge soil microballoon, spare.
It weighs 0.8g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.8g tetradecyltrimethylammonium bromide (TTAB) is added, and 70 DEG C of water-baths stand 3h, add Enter solution A, obtain reactant gel, each component molar ratio meets in the gel of preparation:0.27SiO2:1.25Al2O3: 2.16P2O5:5.0R1:0.40(R2+R3):292H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 8min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 10h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 25% in product, and yield in situ is 56%, micro- The XRD diffraction patterns of sphere catalyst as shown in fig. 7, FESEM photos as figures 8 a and 8 b show, SAPO-34 grain sizes are about 470nm。
Embodiment 5
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 4g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 4g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, obtains reactant Gel, each component molar ratio meets in the gel of preparation:0.25SiO2:1.17Al2O3:1.73P2O5:3.9R1:0.42(R2+ R3):170H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 34% in product, and yield in situ is 68%, micro- The XRD diffraction patterns of sphere catalyst as shown in figure 9, FESEM photos as as-shown-in figures 10 a and 10b, SAPO-34 grain sizes are about 600nm。
Embodiment 6
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.7g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 6g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 6g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 1g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, and it is solidifying to obtain reactant Glue, each component molar ratio meets in the gel of preparation:0.25SiO2:1.17Al2O3:2.6P2O5:5.9R1:0.61(R2+R3): 300H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 30% in product, and yield in situ is 62%.It is micro- The XRD diffraction patterns of sphere catalyst are as shown in figure 11, and as depicted in figs. 12 a and 12b, SAPO-34 grain sizes are about FESEM photos 550nm。
Embodiment 7
A kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst is present embodiments provided, is wrapped Include following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h, solution A is added, obtains reactant Gel, each component molar ratio meets in the gel of preparation:0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.42(R2+ R3):292H2O。
Above-mentioned reactant gel is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains little crystal grain grade hole SAPO-34@kaolin microspheres then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h Catalyst.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 35% in product, and yield in situ is 70%, micro- The XRD diffraction patterns of sphere catalyst are as shown in figure 13, and as shown in Figure 14 a and Figure 14 b, SAPO-34 grain sizes are about FESEM photos 260nm。
Comparative example 1
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
It weighs 1.0g TPOAC to pour into the beaker equipped with 15g water, stirs 12h, so that it is fully dissolved, obtain solution A.
It weighs 5g phosphoric acid to mix with 15g water phases, 30min is stirred under 40 DEG C of water bath conditions, tri- second of 5g is added under stirring condition Amine continues to stir, and 5g kaolin microspheres are added, and 70 DEG C of water-baths stand 3.5h;Solution A is added, in the gel of preparation respectively at centimorgan You are than meeting:0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.20R3:292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 19% in product, and yield in situ is 70.2%, The XRD diffraction patterns of microspherical catalyst are as shown in figure 15, and as shown in fig 16 a and fig 16b, SAPO-34 grain sizes are about for FESEM photos It is 1 μm.
Comparative example 2
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
Weigh 5g phosphoric acid to mix with 15g water phases, stir 30min under 40 DEG C of water bath conditions, be added under stirring condition 15g water and 5g triethylamines continue to stir, and 5g kaolin microspheres, 0.8g CTAB is added, and 70 DEG C of water-baths stand 3.5h;It is each in the gel of preparation Component molar ratio meets:0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0.22R2:292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 110 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 33% in product, and yield in situ is 64.9%, The XRD diffraction patterns of microspherical catalyst are as shown in figure 17, and FESEM photos are as shown in Figure 18 a and Figure 18 b, and SAPO-34 grain sizes are about For 800nm.
Comparative example 3
This comparative example provides a kind of preparation method of SAPO-34@kaolin microsphere catalyst comprising following steps:
Add water 350g and Aluminum sol 40g to be uniformly mixed kaolin 100g, be spray-dried, screening obtains 80-110 μm of height Kaolin microsphere is roasted 4h at 800 DEG C by ridge soil microballoon, spare.
Weigh 5g phosphoric acid to mix with 15g water phases, stir 30min under 40 DEG C of water bath conditions, be added under stirring condition 15g water and 5g triethylamines continue to stir, and 5g kaolin microspheres are added, and 70 DEG C of water-baths stand 3.5h;Each component molar ratio in the gel of preparation Meet:0.25SiO2:1.17Al2O3:2.16P2O5:4.95R1:0(R2+R3):292H2O。
Mixed liquor obtained above is transferred in closed high pressure crystallizing kettle, crystallization 48h in baking oven is rotated at 200 DEG C.
Product is taken out, standing sedimentation 15min, remove the ex situ product of upper liquid, by precipitation situ product centrifugation point From washing obtains SAPO-34@kaolin microsphere catalyst then at 600 DEG C of roasting 6h three times, in 120 DEG C of dry 12h.
By XRD quantitative analyses, the mass content of SAPO-34 molecular sieves is 11.2% in product, and yield in situ is 54.2%, the XRD diffraction patterns of microspherical catalyst are as shown in figure 19, and for FESEM photos as shown in Figure 20 a and Figure 20 b, SAPO-34 is brilliant Grain size is about 2 μm.
Experimental example:The texture property and catalytic performance of fine grain SAPO-34@kaolin microsphere catalyst
Texture property is tested using the full-automatic specific surfaces of Kang Ta and Porosimetry (Autosorb-iQ3-XR), is inhaled Attached gas is nitrogen, (is denoted as S@to the little crystal grain grade hole SAPO-34@kaolin microspheres catalyst prepared by embodiment 7 respectively KCT), the SAPO-34@kaolin microspheres catalyst (being denoted as S@KT) prepared by comparative example 1, the SAPO- prepared by comparative example 2 SAPO-34@kaolin microspheres catalyst prepared by 34@kaolin microspheres catalyst (being denoted as S@KC) and comparative example 3 (is denoted as S@ K N) is carried out2Adsorption/desorption characterizes, N2Adsorption/desorption curve is as shown in figure 21, and texture property is as shown in table 1.As shown in Table 1, single The mesoporous template R2, that is, cetyl trimethylammonium bromide of pure introducing, the mesoporous influence on product are not very big, but from it FESEM photos can see, kaolin microsphere surface distribution little crystal grain SAPO-34 molecular sieves, illustrate, the introducing of CTAB Contribute to the generation of little crystal grain;Occurs a large amount of mesoporous knot if the mesoporous template R3, that is, TPOAC of simple introducing, in product Structure, mesoporous and micropore volume ratio be up to 3.2, however from its FESEM photo it is found that the SAPO-34 on kaolin microsphere surface Grain diameter is larger.And if CTAB and TPOAC is added simultaneously, what can be will be apparent that sees, synthetic product has had both simple introducing Advantage when two kinds of mesoporous templates, i.e., existing a large amount of mesoporous generation, and there is the SAPO-34 of little crystal grain to generate, to success Obtain little crystal grain grade hole SAPO-34@kaolin microsphere catalyst.
The texture property of 1 sample of table
MTO is carried out to aforementioned four catalyst S@K, S@KC, S@KT and S@KCT and is catalyzed reaction evaluating, wherein evaluation raw material For the methanol aqueous solution of 95wt.%, evaluation condition is:450 DEG C of reaction temperature, mass space velocity 2.5h-1, flow rate of carrier gas 20ml/ min.Product after reaction is analyzed using offline gas-chromatography, divides 3420A gas chromatographs using north, HP PLOT-Q columns, Fid detector is detected.When methanol conversion is less than 98wt.%, you can think that catalyst has inactivated, stop at this time real It tests, and using the time point as catalyst life.Selectivity of product result takes in methanol-to-olefins reaction process in sample point Maximum value.Evaluation result is as shown in table 2.
The data provided from table 2 are prepared into merely little crystal grain it is found that for simple introducing meso-hole structure SAPO-34@kaolin microspheres have more preferably MTO reactivity worth, wherein compared with the catalyst S@K for being not added with mesoporous template, Fine grain SAPO-34@kaolin microsphere catalyst S@KC have relatively high diene selective and react the service life, and grade hole The diene selective of SAPO-34@kaolin microsphere catalyst S@KT is suitable with S@K, but its catalytic life slightly extends.And lead to The double mesoporous templates of addition are crossed, obtained little crystal grain grade hole SAPO-34@kaolin microsphere catalyst has optimal MTO anti- Performance is answered, not only catalytic life greatly extends, and close to 200min, while diene selective is also up to 81%, illustrates little crystal grain The effect of collaboration has been played with step hole.
2 methanol-to-olefins catalytic performance test result of table
It is above-mentioned the experimental results showed that, method through the invention can be prepared that zeolite crystal is small, molecular sieve content High, situ product yield height and the fine grain SAPO-34@kaolin microsphere catalyst with grade pore structure;Meanwhile Ke Yitong Cross modulation synthesis condition, the grain size of modulation SAPO-34 and mesoporous content;And it is prepared compared to mesoporous template is not added with SAPO-34@kaolin microsphere catalyst, the obtained product of the present invention has better activity stability, catalyst life Long, about 200min, diene selective is up to 81%, has good prospects for commercial application.

Claims (10)

1. a kind of preparation method of little crystal grain grade hole SAPO-34@kaolin microsphere catalyst, wherein this method includes as follows Step:
(1) kaolin microsphere, the kaolin microsphere activated after fired is prepared;
(2) kaolin microsphere of the activation, water, phosphorus source, micropore template agent and mesoporous template are mixed with and are reacted Object gel, each component molar ratio meet following condition:
(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(1.5-3.1)P2O5:(3.5-6.5)R1:(0.1-0.7)(R2+ R3):(100-300)H2O;Wherein, R1 is micropore template agent, and R2 and R3 are mesoporous template, and silicon source and silicon source are all from kaolinite Native microballoon;
(3) Crystallizing treatment is carried out to the reactant gel, centrifuges, it is micro- obtains little crystal grain grade hole SAPO-34@kaolin Ball composite material;
(4) calcination process is carried out to little crystal grain grade hole SAPO-34@kaolin microsphere composite materials, obtains the small crystalline substance Grain grade hole SAPO-34@kaolin microsphere catalyst.
2. preparation method according to claim 1, wherein the step (1) includes following operation:By kaolin, bonding Agent and water mixing, kaolin microsphere, the fired kaolin microsphere activated are prepared by spray drying;
Preferably, the mass ratio of the kaolin and binder is 2.5-3:1;
Preferably, the binder is one or more mixtures in waterglass, Aluminum sol and Ludox;
Preferably, the temperature of the roasting is 700-900 DEG C, and more preferably 800 DEG C, the time of the roasting is 1-6h, more excellent It is selected as 3-4h;
Preferably, the grain size of the kaolin microsphere is 80-110 μm.
3. preparation method according to claim 1, wherein the step (2) includes:
Mesoporous template R3 is mixed with part water first, is stirred overnight, so that mesoporous template R3 is fully dissolved, obtains solution A;
Phosphorus source is uniformly mixed with part water, micropore template agent R1 is then added, the work that step (1) obtains is added after mixing The kaolin microsphere of change is then added mesoporous template R2 and the solution A is added, is prepared after stirring makes it be sufficiently mixed Reactant gel;
Preferably, each component molar ratio is (0.2-0.27) SiO2:(1-1.25)Al2O3:(1.7-2.6)P2O5:(3.9-5.9) R1:(0.13-0.61)(R2+R3):(114-300)H2O;
Preferably, mesoporous template R2 is added and carries out burin-in process later, it is highly preferred that the temperature of the burin-in process is 40-90 DEG C, further preferably 70 DEG C;
Preferably, the solution A is added after burin-in process 0-5h, is preferably added after burin-in process 3.5h.
4. preparation method according to claim 1 or 3, wherein the micropore template agent is triethylamine.
5. preparation method according to claim 1 or 3, wherein phosphorus source is orthophosphoric acid.
6. preparation method according to claim 1 or 3, wherein the mesoporous template R2 is selected from cation surface activating One kind in agent cetyl trimethylammonium bromide, tetradecyltrimethylammonium bromide and dodecyl trimethyl ammonium bromide.
7. preparation method according to claim 1 or 3, wherein the mesoporous template R3 is selected from organosilan dimethyl In cetyl [3- trimethoxy silicon propyl] ammonium chloride and dimethyl stearyl [3- trimethoxy silicon propyl] ammonium chloride It is a kind of.
8. preparation method according to claim 1, wherein in step (3), the temperature of the Crystallizing treatment is 180- 220 DEG C, preferably 200 DEG C;The time of the Crystallizing treatment is 24-72h, preferably 48h;
In step (4), the temperature of the roasting is 500-650 DEG C, and the time of the roasting is 3-6h.
9. the little crystal grain grade hole SAPO-34@kaolin microspheres that claim 1-8 any one of them preparation methods are prepared Catalyst, it is preferable that in terms of relative crystallinity, the relative amount of SAPO-34 molecular sieves is 15-35wt.%, situ product yield For 55-70wt.%.
10. a kind of method of methanol-to-olefins, wherein this method be using the methanol aqueous solution of a concentration of 95wt.% as raw material, with Little crystal grain grade hole SAPO-34@kaolin microsphere catalyst described in claim 9 is catalyst, in normal pressure, reaction temperature 450 DEG C, mass space velocity 2.5h-1Under conditions of prepare alkene.
CN201810357940.4A 2018-04-20 2018-04-20 Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof Active CN108435245B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810357940.4A CN108435245B (en) 2018-04-20 2018-04-20 Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810357940.4A CN108435245B (en) 2018-04-20 2018-04-20 Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN108435245A true CN108435245A (en) 2018-08-24
CN108435245B CN108435245B (en) 2020-05-22

Family

ID=63201071

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810357940.4A Active CN108435245B (en) 2018-04-20 2018-04-20 Small-grain-grade-pore SAPO-34@ kaolin microsphere catalyst and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN108435245B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113751067A (en) * 2021-09-17 2021-12-07 李加平 Hierarchical pore titanium silicalite molecular sieve coating, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582804A (en) * 2015-10-20 2017-04-26 中国石油大学(北京) Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582804A (en) * 2015-10-20 2017-04-26 中国石油大学(北京) Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HASSAN SHARIFI PAJAIE ET AL.: "Methanol conversion to light olefins over surfactant-modified nanosized SAPO-34", 《REAC KINET MECH CAT》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113751067A (en) * 2021-09-17 2021-12-07 李加平 Hierarchical pore titanium silicalite molecular sieve coating, preparation method and application thereof

Also Published As

Publication number Publication date
CN108435245B (en) 2020-05-22

Similar Documents

Publication Publication Date Title
CN110422856A (en) Sial type AEI/CHA coexisting molecular sieve method for preparing catalyst and its application being catalyzed in SCR
US10758894B2 (en) SAPO-34/ZSM-5@ kaolin microsphere composite catalytic material and its preparation and use
CN101935050B (en) Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor
CN108658093A (en) A kind of preparation method and applications of multi-stage porous ZSM-5 molecular sieve
CN110270360A (en) The method for preparing oligomerisation catalyst
CN103842079A (en) Use of a catalyst comprising a phosphorus modified zeolite in an alcohol dehydration process
CN104056653B (en) A kind of catalyst for producing propylene with methanol
WO2011049301A2 (en) High-strength sapo-34 microsphere catalyst, method for preparing same, and method for preparing light olefins using same
CN110270337A (en) Catalyst containing Ni for olefin oligomerization
CN106582804A (en) Hierarchical porous SAPO-34/kaolin composite material and preparation method thereof
CN110615444A (en) Mordenite molecular sieve, and preparation method and application thereof
CN101857244B (en) Silicoaluminophosphate molecular sieve and preparation method and application thereof
CN104923284B (en) A kind of molded molecular sieve catalyst and its preparation method and application
CN101503201B (en) Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst
Rodrıguez-Castellón et al. Textural and structural properties and surface acidity characterization of mesoporous silica-zirconia molecular sieves
CN106032282A (en) Preparation method and applications of mordenite having mesopores and micropores
CN104971768B (en) A kind of SAPO-34/ natural clay composite material and preparation method and application
CN105645428B (en) The preparation method of the molecular sieves of SSZ 32 with mesoporous micropore graded structure
CN106185982B (en) SAPO5/SAPO34 composite molecular screen, preparation method and its application that a kind of SAPO-5 content is 70%-90%
CN110467194A (en) A kind of low silicon SAPO-34 molecular sieve and its preparation method and application
CN108435245A (en) Little crystal grain grade hole SAPO-34@kaolin microspheres catalyst and its preparation and application
CN105642342B (en) SAPO-5/SAPO-34 composite molecular screens, and preparation method thereof, and its application
CN106608803A (en) Method for preparing propylene through methanol conversion
CN102530989A (en) Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product
CN105271302B (en) A kind of 18 molecular sieves of SAPO and its synthetic method and a kind of method of methanol-to-olefins

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant