CN107282102A - A kind of preparation method of metal load type molecular sieve catalyst - Google Patents

A kind of preparation method of metal load type molecular sieve catalyst Download PDF

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CN107282102A
CN107282102A CN201710482565.1A CN201710482565A CN107282102A CN 107282102 A CN107282102 A CN 107282102A CN 201710482565 A CN201710482565 A CN 201710482565A CN 107282102 A CN107282102 A CN 107282102A
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molecular sieve
metal
preparation
sieve catalyst
load type
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CN107282102B (en
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张媛
庄大为
刘�文
杨琦武
王聪
刘新伟
杨克俭
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China Tianchen Engineering Corp
Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
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Tianjin Tianchen Green Energy Resources Engineering Technology and Development Co Ltd
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    • 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
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract

The invention provides a kind of preparation method of metal load type molecular sieve catalyst, comprises the steps：The precursor compound for preparing molecular sieve is mixed with carbon template, presoma xerogel of the carbonization treatment formation containing porous carbon ball；The impregnating metal salting liquid on presoma xerogel, forms the porous carbon ball of carrying active metal and presoma crystallite；Add Molecular Sieves as Template agent, hydro-thermal reaction formation molecular sieve structure；Molecular sieve structure is fired, obtains the molecular sieve catalyst of carried metal.The invention can realize metal active centres being uniformly distributed in molecular sieve pore passage, improve selectivity of light olefin.

Description

A kind of preparation method of metal load type molecular sieve catalyst
Technical field
The present invention relates to molecular sieve catalyst technical field, more particularly to a kind of high selectivity gas low-carbon alkene directly processed The preparation method of the metal load type molecular sieve catalyst of hydrocarbon.
Background technology
It is the base stock of chemical industry, mesh using ethene, propylene as the low-carbon alkene (alkene of carbon atom≤4) of representative Before, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, also alkane, hydrogenated diesel oil, portion Divide mink cell focus etc..From the direct preparing ethylene of synthesis gas (can be converted to by natural gas and coal), the exploitation of propylene technology, not only may be used The dependence to petroleum resources is reduced, and to the chemical industrial expansion important in inhibiting in some rich gas oil starvations area.The process Have technique simple than this degradation pathways, the features such as equipment investment is few substantially belongs to F-T synthetic reactions.F-T synthetic reactions its Purpose is by synthesis gas synthetic fuel liquefied hydrocarbon, although fluidization, the use of ferrum-based catalyst and the addition of auxiliary agent, The yield of low-carbon alkene (C2-C4 alkene) is improved to a certain extent, but yield of light olefins is not still high, only 20~25%. Lot of domestic and foreign scientific research institutions and esbablished corporation have carried out substantial amounts of research to the process, it is believed that the exploitation of effective catalyst, especially It is that the exploitation of the catalyst of high olefin selectivity is the key of the technique.
Metal load type molecular sieve is the important catalyst that synthesis gas directly prepares low-carbon alkene, and it is class reproducibility gold Category is carried in the pore passage structure of molecular sieve, while having the high selectivity catalysis in metal active centres and acid activated centre Agent.It is general in the prior art to be made using infusion process or micro emulsion method combination hydro-thermal method, introduced by active metal inside molecular sieve During, it is in contact due to solid-liquid, the reason such as osmotic pressure, is easily caused metal skewness in molecular sieve pore passage, causes The catalytic performance reduction of catalyst, selectivity of light olefin reduction.
The content of the invention
In view of this, the invention is directed to a kind of preparation method of metal load type molecular sieve catalyst, can Metal active centres being uniformly distributed in molecular sieve pore passage is realized, selectivity of light olefin is improved.
The preparation method for the metal load type molecular sieve catalyst that the invention is provided, comprises the steps：
S1：The precursor compound for preparing molecular sieve is mixed with carbon template, before carbonization treatment formation is containing porous carbon ball Drive soma gel；
S2：The impregnating metal salting liquid on presoma xerogel, forms the porous of carrying active metal and presoma crystallite Carbon ball；
S3：Add Molecular Sieves as Template agent, hydro-thermal reaction formation molecular sieve structure；
S4：Molecular sieve structure is fired, obtains the molecular sieve catalyst of carried metal；
Wherein, the carbon template of the step S1 has following property：(1) it can be carbonized after being heat-treated；(2) after being carbonized Remain reproducibility group (such as aldehyde radical).It is preferred that carbon template be sucrose.
In above process, carbon template can form porous carbon ball by carbonization, and metal salt solution is immersed in containing many During the presoma xerogel of hole carbon ball, due to remaining the metal ion in the reproducibility group such as aldehyde radical, solution in porous carbon ball It is reduced to metal and is supported on carbon ball surface, while forming the presoma crystallite of molecular sieve in porous carbon ball, adds molecule Sieve after template, under hydrothermal conditions, molecular sieve structure is formed and is coated in porous carbon ball, by other post processings such as roasting After processing, porous carbon ball is removed, the molecular sieve catalyst for the carried metal for being uniformly mixed and coating.
Wherein, the precursor compound of molecular sieve includes silicon, aluminium, the precursor compound of phosphorus in the step S1.The precursor of silicon Compound can be the one or more in silica gel, sodium metasilicate, tetraethyl orthosilicate, the precursor compound of aluminium can for Alumina gel, One or more in boehmite, sodium metaaluminate, aluminium isopropoxide, the precursor compound of phosphorus can be phosphoric acid, phosphorous acid It is one or more.The silicon, aluminium, the mol ratio of the precursor compound of phosphorus and carbon template, respectively with SiO2、Al2O3、PO4 3+、C12 Meter, is SiO2：Al2O3：PO4 3+：C12=(0.01~5):1:(0.01~5):(0.5~20), preferably SiO2：Al2O3：PO4 3+： C12=(0.05~2):1:(0.05~2):(1~10).
Wherein, in the step S1 carbonization treatment condition be 160~220 DEG C of carburizing temperature, 2~48h of carbonization time, preferably 4~24h.Suitable Carbonization Conditions contribute to flash carbonization and obtain the porous carbon ball of Suitable porous structure, the hole of porous carbon ball Road structure (hole size, hole wall size etc.) can be controlled by suitably adjusting Carbonization Conditions；Meanwhile, suitable Carbonization Conditions have Beneficial to the formation of molecular sieve precursor xerogel, the nucleation for formation molecular sieve precursor crystallite is ready.
Wherein, metal salt solution can be Cu in the step S22+、Mg2+、Fe3+、Cr3+、Zn2+、Zr4+、Ce3+Nitrate In one or more.The concentration of the metal salt solution, with metal ion, is 0.1~5mol/L, preferably 0.5~3mol/ L.Suitable metal salt solution concentration provides the metal ion for entering porous carbon ball enough and osmotic drive work in dipping process With, metal ion can be rapidly entered in hole under the duct adsorption dual effect of osmotic drive and carbon ball, and by porous carbon ball The reproducibility group on surface is reduced into metal, so as to be evenly affixed to porous carbon ball surface.
Wherein, immersion condition is 10~60 DEG C of dipping temperature, 1~10h of dip time in the step S2.Typically use etc. Volume impregnation crosses volume impregnation.Suitable dipping temperature can accelerate infusing rate, while promoting molecular sieve precursor crystallite Quick formation.
Wherein, in the step S2, the first drying process is also included after dipping, optimum condition is drying temperature 80~160 DEG C, 4~24h of drying time.On the one hand drying process can cross the steeping liq for removing residual, on the other hand be conducive to active metal With stabilization of the presoma crystallite in porous carbon ball.
Wherein, in the step S3 Molecular Sieves as Template agent be organic formwork agent, preferably diethylamine, triethylamine, n-propylamine, One or more in n-butylamine, tetraethyl ammonium hydroxide, TPAOH, TBAH.Organic mould The mol ratio of the precursor compound of plate agent and molecular sieve, respectively with N, SiO2Meter, is N：SiO2=0.2~10, preferably 1~5.
Wherein, hydrothermal reaction condition is 160~210 DEG C in the step S3.
Wherein, roasting condition is 400~800 DEG C of sintering temperature, preferably 450~650 DEG C in the step S4；Roasting time For 2~10h, preferably 4~8h；Calcination atmosphere is the flowing atmosphere that oxygen content is 50~100vol%.Roasting process can be by Porous carbon ball is removed, and obtains the molecular sieve catalyst of uniform load metal active centres.
Wherein, in the step S4, centrifugation washing and the second drying process step is also included before roasting, is respectively used to separate Preparation before molecular sieve structure and roasting containing porous carbon ball.
Relative to prior art, the present invention can realize molecular sieve carrier by introducing carbon template in preparation process Uniform with metal active constituent is mixed and cladding, and does not produce undesired impurities, and the catalyst catalytic performance of acquisition is good, especially It is applied to the catalytic reaction of the direct producing light olefins of synthesis gas, substantially increases the selectivity of low-carbon alkene.
Embodiment
The schematic description and description of the invention is used to explain the invention, does not constitute to present invention wound The improper restriction made.
Embodiment 1
It is silica gel (30% mass fraction) by mol ratio:Boehmite:Phosphoric acid:Sucrose is 0.2:1:0.1:3 weigh original Material, after mixed at room temperature is uniform, 220 DEG C of carbonization 4h in water heating kettle, naturally cooling to room temperature, to obtain presoma porous carbon ball dry solidifying Glue.Configure mol ratio copper nitrate:Zinc nitrate:Aluminum nitrate is 4.5:4.5:1 metal salt solution, active component accounts for catalyst down payment Category is calculated as 30% (mass ratio), and incipient impregnation is in porous carbon ball xerogel at room temperature, 80 DEG C of dry 24h, obtains containing activity The porous carbon ball of component and presoma crystallite.It is silica gel that porous carbon ball, which is added to mol ratio,:Tetraethyl ammonium hydroxide is 2.4:1 Solution in, 180 DEG C of hydro-thermal process 4d, after centrifugation washing, 100 DEG C of drys 12h, 600 DEG C of pure oxygen atmospheres roasting 4h are catalyzed Agent.
Embodiment 2
It is sodium metasilicate by mol ratio:Aluminum sulfate:Phosphorous acid:Sucrose is 0.6:1:0.4:7 weigh raw material, and mixed at room temperature is uniform Afterwards, 160 DEG C of carbonization 24h in water heating kettle, naturally cool to room temperature and obtain presoma porous carbon ball xerogel.Configure mol ratio nitre Sour iron:Chromic nitrate is 1:1 metal salt solution, 25 DEG C are crossed volume impregnation in porous carbon ball xerogel, and total metal salt solution is dense Spend for 5mol/L, dip time is 10h, 110 DEG C of dry 12h, obtains the porous carbon ball containing active component and presoma crystallite.Will It is sodium metasilicate that porous carbon ball, which is added to mol ratio,:Triethylamine is 1:In 1 solution, 200 DEG C of hydro-thermal process 2d, after centrifugation washing, 120 DEG C of dry 6h, 550 DEG C of 80vol% oxygen atmospheres are calcined 6h, obtain catalyst.
Embodiment 3
It is tetraethyl orthosilicate by mol ratio:Aluminium isopropoxide:Phosphoric acid:Sucrose is 0.2:1:0.5:10 weigh raw material, and room temperature is mixed After closing uniformly, 175 DEG C of carbonization 10h, naturally cool to room temperature and obtain presoma porous carbon ball xerogel in water heating kettle.Configuration rubs You compare zinc nitrate:Chromic nitrate is 1:1 metal salt solution, 25 DEG C are crossed volume impregnation in porous carbon ball xerogel, total metal salt Solution concentration is that 1.5mol/L dip times are 10h, 110 DEG C of dry 12h, obtains porous containing active component and presoma crystallite Carbon ball.It is tetraethyl orthosilicate that porous carbon ball, which is added to mol ratio,:Diethylamine:TPAOH is 1:0.24:0.30 In solution, 190 DEG C of hydro-thermal process 3d, after centrifugation washing, 110 DEG C of dry 10h, 650 DEG C of 50vol% oxygen atmospheres are calcined 4h, obtain Catalyst.
Embodiment 4
It is Ludox (mass fraction 30%) by mol ratio:Alumina gel:Phosphorous acid:Sucrose is 1.5:1:0.3:20 weigh original Material, after mixed at room temperature is uniform, 180 DEG C of carbonization 10h in water heating kettle, naturally cooling to room temperature, to obtain presoma porous carbon ball dry solidifying Glue.Configure mol ratio ferric nitrate:Magnesium nitrate is 1:1 metal salt solution, 40 DEG C are crossed volume impregnation in porous carbon ball xerogel, Total metal salt solution concentration is 2.5mol/L, and dip time is 6h, 95 DEG C of dry 20h, obtains micro- containing active component and presoma Brilliant porous carbon ball.It is Ludox that porous carbon ball, which is added to mol ratio,:N-butylamine:Tetraethyl ammonium hydroxide is 1:0.20: In 0.20 solution, 195 DEG C of hydro-thermal process 2d, after centrifugation washing, 110 DEG C of dry 10h, 450 DEG C of 50vol% oxygen atmospheres roastings 8h, obtains catalyst.
Embodiment 5
It is sodium metasilicate by mol ratio:Aluminium isopropoxide:Phosphoric acid:Sucrose is 0.4:1:0.4:1 weighs raw material, and mixed at room temperature is uniform Afterwards, 170 DEG C of carbonization 24h in water heating kettle, naturally cool to room temperature and obtain presoma porous carbon ball xerogel.Configure mol ratio nitre Sour iron:Cerous nitrate is 8:1 metal salt solution, 30 DEG C are crossed volume impregnation in porous carbon ball xerogel, and total metal salt solution is dense Spend for 1.0mol/L, dip time is 9h, 100 DEG C of dry 20h, obtains the porous carbon ball containing active component and presoma crystallite. It is sodium metasilicate that porous carbon ball, which is added to mol ratio,:Triethylamine:Tetraethyl ammonium hydroxide is 1:0.35:In 0.20 solution, 160 DEG C hydro-thermal process 5d, after centrifugation washing, 100 DEG C of drys 24h, 580 DEG C of 70vol% oxygen atmospheres roasting 5h obtain catalyst.
Embodiment 6
It is tetraethyl orthosilicate by mol ratio:Sodium metaaluminate:Phosphorous acid:Sucrose is 0.7:1:0.5:5 weigh raw material, and room temperature is mixed After closing uniformly, 185 DEG C of carbonization 7h, naturally cool to room temperature and obtain presoma porous carbon ball xerogel in water heating kettle.Configuration rubs You compare zinc nitrate:Zirconium nitrate is 3:1 metal salt solution, active component accounts for catalyst and is calculated as 24% (mass ratio), room by metal Warm volumetric is immersed in porous carbon ball xerogel, and leaching obtains the porous carbon ball containing active component and presoma crystallite.To be many It is tetraethyl orthosilicate that hole carbon ball, which is added to mol ratio,:N-butylamine:TPAOH is 1:0.18:In 0.24 solution, 210 DEG C hydro-thermal process 1d, after centrifugation washing, 90 DEG C of drys 20h, 500 DEG C of 80vol% oxygen atmospheres roasting 8h obtain catalyst.
Embodiment 7
It is Ludox by mol ratio:Aluminium isopropoxide:Phosphoric acid:Sucrose is 0.3:1:0.5:9 weigh raw material, and mixed at room temperature is uniform Afterwards, 210 DEG C of carbonization 3h in water heating kettle, naturally cool to room temperature and obtain presoma porous carbon ball xerogel.Configure mol ratio nitre Sour zinc:Cerous nitrate:Zirconium nitrate is 1:2:2 metal salt solution, 60 DEG C are crossed volume impregnation in porous carbon ball xerogel, total metal Concentration of salt solution is 2mol/L, and dip time is 2h, 120 DEG C of dry 6h, obtains porous containing active component and presoma crystallite Carbon ball.It is Ludox that porous carbon ball, which is added to mol ratio,:N-propylamine:TBAH is 1:0.50:0.30 solution In, 200 DEG C of hydro-thermal process 3d, after centrifugation washing, 120 DEG C of dry 6h, 600 DEG C of 60vol% oxygen atmospheres are calcined 5h, are catalyzed Agent.
Comparative example 1
Cu-Zn-Al oxide catalysts and SAPO-34 molecular sieves are uniformly mixed according to the proportioning of embodiment 1, miniature Required granularity is sized to after 15Hz on ball mill, 30min ball milling, catalyst is obtained.
Comparative example 2
Zn-Cr oxide catalysts and SAPO-34 molecular sieves are uniformly mixed according to the proportioning of embodiment 3,10% is added The Alumina gel (mass fraction 20%) of mass ratio mist projection granulating afterwards, obtains catalyst.
Above-mentioned catalyst is subjected to the direct producing light olefins catalytic reaction checking of synthesis gas.By taking fixed bed reaction as an example, but It is also applied for fluid bed, moving-burden bed reactor.Catalyst in embodiment or comparative example is sized to 20~40 mesh, weighed 1.6g, uses quality for 1:8 quartz sand dilution, is loaded in fixed bed reactors, with 300~350 DEG C of the pure hydrogen of normal pressure also Former 3h.Switching and merging gas (H after cooling in nitrogen atmosphere2/ CO=2/1, N210vol%) reacted.Reaction effluent point Do not collected by hot trap, cold-trap.Reaction condition is 260-450 DEG C of reaction temperature, air speed 1000h-1, reaction pressure 2.5MPa.Product There is on-line chromatograph detection and analysis.The result of reaction evaluating is listed in table 1.As a result show, be catalyzed using made from the inventive method Agent is greatly improved in the selectivity of low-carbon alkene.
Table 1
The preferred embodiment of the invention is the foregoing is only, creation is not intended to limit the invention, it is all at this Within the spirit and principle of innovation and creation, any modification, equivalent substitution and improvements made etc. should be included in the invention Protection domain within.

Claims (10)

1. a kind of preparation method of metal load type molecular sieve catalyst, comprises the steps：
S1：The precursor compound for preparing molecular sieve is mixed with carbon template, presoma of the carbonization treatment formation containing porous carbon ball Xerogel；
S2：The impregnating metal salting liquid on presoma xerogel, forms the porous carbon ball of carrying active metal and presoma crystallite；
S3：Add Molecular Sieves as Template agent, hydro-thermal reaction formation molecular sieve structure；
S4：Molecular sieve structure is fired, obtains the molecular sieve catalyst of carried metal；
Wherein, the carbon template of the step S1 has following property：(1) it can be carbonized after being heat-treated；(2) remained after being carbonized There is reproducibility group (such as aldehyde radical).It is preferred that carbon template be sucrose.
2. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step The precursor compound of molecular sieve includes silicon, aluminium, the precursor compound of phosphorus in S1.The precursor compound of silicon can be silica gel, silicic acid One or more in sodium, tetraethyl orthosilicate, the precursor compound of aluminium can be Alumina gel, boehmite, sodium metaaluminate, different One or more in aluminium propoxide, the precursor compound of phosphorus can be phosphoric acid, the one or more of phosphorous acid.The silicon, aluminium, phosphorus Precursor compound and carbon template mol ratio, respectively with SiO2、Al2O3、PO4 3+、C12Meter, is SiO2：Al2O3：PO4 3+：C12 =(0.01~5):1:(0.01~5):(0.5~20), preferably SiO2：Al2O3：PO4 3+：C12=(0.05~2):1:(0.05 ~2):(1~10).
3. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Carbonization treatment condition is 160~220 DEG C of carburizing temperature, preferably 2~48h of carbonization time, 4~24h in S1.
4. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Metal salt solution can be Cu in S22+、Mg2+、Fe3+、Cr3+、Zn2+、Zr4+、Ce3+One or more in nitrate.The gold Belong to the concentration of salting liquid with metal ion, be 0.1~5mol/L, preferably 0.5~3mol/L.
5. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Immersion condition is 10~60 DEG C of dipping temperature, 1~10h of dip time in S2.
6. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step In S2, the first drying process is also included after dipping, optimum condition is 80~160 DEG C of drying temperature, 4~24h of drying time.
7. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Molecular Sieves as Template agent is organic formwork agent, preferably diethylamine, triethylamine, n-propylamine, n-butylamine, tetraethyl hydroxide in S3 One or more in ammonium, TPAOH, TBAH.The organic formwork agent and molecular sieve it is precursor The mol ratio of compound, respectively with N, SiO2Meter, is N：SiO2=0.2~10, preferably 1~5.
8. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Hydrothermal reaction condition is 160~210 DEG C in S3.
9. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step Roasting condition is 400~800 DEG C of sintering temperature, preferably 450~650 DEG C in S4；Roasting time is 2~10h, preferably 4~8h；Roasting It is the flowing atmosphere that oxygen content is 50~100vol% to burn atmosphere.
10. the preparation method of metal load type molecular sieve catalyst according to claim 1, it is characterised in that the step In rapid S4, centrifugation washing and the second drying process step are also included before roasting.
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