CN102371170A - Adhesive-free zeolite catalyst and preparation method thereof - Google Patents
Adhesive-free zeolite catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an adhesive-free zeolite catalyst and a preparation method thereof. The problem of low activity of the conventional catalyst is mainly solved. According to the new adhesive-free zeolite catalyst, the problem is well solved by adopting the technical scheme that the pore volume is 0.1 to 0.3 milliliter per gram, the average aperture is 50 to 70 nanometers, the porosity is 20 to 30 percent, and the content of the adhesive is 0 to 5 percent; the catalyst has the advantage of relatively high activity; the preparation method can be applied to industrial preparation of the adhesive-free catalyst; and the prepared catalyst can be used in the reaction of preparing ethylene and propylene by catalytic pyrolysis of naphtha.
Description
Technical field
The present invention relates to a kind of binder free zeolite catalyst and preparation method thereof.
Background technology
Zeolite molecular sieve has good shape selective catalysis performance and absorption property owing to have evenly regular pore passage structure, bigger specific area and higher heat endurance, is applied in field of petrochemical industry widely.Because molecular sieve in use need add the binding agent moulding, in the catalyst after the moulding, because binding agent parcel molecular sieve; Caused the effective rate of utilization of molecular sieve to descend, caused the specific area of catalyst lower, activity is also lower; Again because binding agent does not have regular pore passage structure; Reaction raw materials and product are in catalyst diffusion difficulty, and carbon deposit has certain influence to life of catalyst easily.Be converted into the active principle molecular sieve to the binding agent in the catalyst and then can overcome above problem, improve activity of such catalysts and diffusion.
The binder free zeolite catalyst is exactly the active principle that changes into the binding agent that is added in the zeolite molecular sieve catalyst forming process in molecular sieve, makes not contain the binding agent composition in the whole catalyst, keeps the good intensity of catalyst simultaneously.Be converted into the molecular sieve composition fully owing to binding agent in the binder free catalyst; So just improved the content of molecular sieve in the per volume of catalyst; Make activity of such catalysts higher, treating capacity is bigger, simultaneously owing to no longer include binding agent in the catalyst; Solved binding agent parcel molecular sieve and reduced the effective rate of utilization of molecular sieve and the problem that binding agent stops up molecular sieve pore passage, the effective rate of utilization of molecular sieve and carbon accumulation resisting ability are improved greatly.
General binder free zeolite molecular sieve catalyst refers in the catalyst binder content smaller or equal to 5%.
General coexisting molecular sieve is to prepare through the synthetic method of hydro-thermal, is Powdered, no intensity; Be prone to run off, even compression molding, intensity also is lower than 20 newton; Can not directly use, need add binding agent when industry or laboratory applications and carry out extrusion or spray shaping.In the general molecular sieve catalyst forming process, the weight that add binding agent is no less than 40% of total catalyst weight, though the moulding rear catalyst has had intensity, the effective rate of utilization of catalyst reduces, active and diffusion variation.
All use organic formwork agent to promote that the commentaries on classics of binding agent is brilliant in the process of prior art for preparing binder free catalyst.
Chinese patent CN101347742 has reported a kind of catalyst that hydrocarbon raw material prepares light aromatics and light paraffins that is used for; Mainly solve the content that binding agent in the bifunctional catalyst of Zeolite support preparation that available technology adopting contains binding agent can reduce active principle; Cause adsorbance to descend; Effective surface area is reduced, and the activity that therefore causes is lower, the technical problem of less stable.The present invention comprises following component through adopting by weight percentage: a) 0.01～0.8% be selected among Pt or the Pd at least a; B) the surplus technical scheme that is selected from least a preparation bifunctional catalyst in modenite, y-type zeolite, Y zeolite, ZSM-5 or the ZSM-11 zeolite of binder free has solved this problem preferably, can be used in the commercial production that hydrocarbon raw material prepares light aromatics and light paraffins.Also used template in the process of wherein prepared binder free y-type zeolite.
Chinese patent 200510028782 has reported that the present invention of small crystal grain without bonding agent prepare zeolite method is a primary raw material through adopting with diatomite or white carbon; Add the crystal seed directed agents; And with Ludox or sodium metasilicate as the binding agent moulding; Handle the technical scheme that is converted into integrated little crystal grain with organic amine mutually with the water vapour gas-solid then; Mainly solve the zeolite powder and in practical application, have the difficult weakness that reclaims, is prone to inactivation and gathering, and the adding binding agent can cause that effective surface area reduces the problem that influences with diffusion restriction in the forming process.But the preparation process is used organic amine and crystal seed directed agents.
Chinese patent 200510029462 has been reported the preparation method of ZSM-type molecular sieve without binding agent.Through adopting content is the mixture that the former powder of 5～50 weight % binding agent silica and ZSM type molecule forms; In the aqueous solution that contains halogenation organic amine and alkyl diamine or steam; Be converted into the technical scheme of integrated ZSM type molecular sieve through hydrothermal treatment consists, mainly solved and add binding agent in the molecular sieve catalyst forming process and can cause that effective surface area reduces the problem with the diffusion restriction influence.
In the binder free Preparation of catalysts method of existing report, all need add organic amine or crystal seed directed agents as template or directed agents.Adopt the preparation cost of template high, the organic amine of interpolation is poisoned big to human body, and environmental pollution is serious, reclaims difficulty, adopts the method for roasting to remove usually, and required energy consumption is big, and environment is also had pollution; Prepare the method that adds crystal seed or directed agents in the process, building-up process is very complicated comparatively.No template does not have the method that crystal seed directly prepares the binder free catalyst can avoid the problems referred to above, and corresponding optimization synthesis step, has tangible economic worth and social value.At present, the method for not using template to prepare the binder free catalyst is not seen report.
Summary of the invention
One of technical problem to be solved by this invention is that the catalyst of prior art for preparing contains binding agent, the problem that activity of such catalysts is lower; A kind of new binder free zeolite catalyst is provided, and this catalyst has active advantage of higher.
Two of technical problem to be solved by this invention provides the preparation method that a kind of new binder free zeolite catalyst with one of technical solution problem adapts.This method has that the preparation process is simple, and cost is lower, the advantage of environmental protection.
For one of addressing the above problem, the technical scheme that the present invention adopts is following: a kind of binder free zeolite catalyst, it is characterized in that pore volume is 0.1～0.3 a milliliter/gram, and average pore size is 50～70nm, and voidage is 20～30%, and binder content is 0～5%.
In the technique scheme, the preformed catalyst intensity preferable range that makes is 50～200 newton; The binder content preferable range is 0.1～2% in the catalyst that makes.The molecular sieve preferred version is at least a in ZSM-5, ZSM-23, ZSM-11, modenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or the ZSM-5/Y zeolite/modenite.
For address the above problem two, the technical scheme that the present invention adopts is following: a kind of preparation method of binder free zeolite catalyst may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the zeolite 10～80%, 0.1～20% alkaline matter, 0～20% aluminium and 10～80% silica mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, the compound weight content of mixture aluminium is less than the weight content of silica in the mixture I;
B) the mixture I is placed put into water vapour, carry out obtaining binder free zeolite catalyst precursor after crystallization handles 10～300 hours at 100～200 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains the binder free zeolite molecular sieve catalyst through super-dry;
Wherein, alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of periodic table of elements I A or II A element; The compound of aluminium is at least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium, and binder content is 0～5% in the binder free catalyst that makes.
In the technique scheme, I A family element preferred version is at least a in sodium or the potassium; II A family element preferred version is at least a in magnesium or the calcium; The salt of weak acid preferred version is at least a in disulfate, sulphite, bisulfites, phosphate, the hydrophosphate.In the catalyst weight behind the shaping and roasting, the consumption preferable range of molecular sieve is 20～70%; The consumption preferable range of alkaline matter is 0.5～10%; The compound preferred version of aluminium is hydroxide species at least a of hydrous oxide or aluminium of oxide, the aluminium of aluminium salt, aluminium, and the consumption preferable range is 1～15%; The weight percentage preferable range of silica is 30～70%; The crystallization temperature preferable range is 120～200 ℃, and the crystallization time preferable range is 20～100 hours.The binder free catalyst that makes is used in the reaction of naphtha catalytic pyrolysis preparing low-carbon alkene and methanol dehydration producing light olefins.
It is strip solid cylindrical, that diameter is 0.5～2mm that shape after the catalyst precarsor mixture I extrusion is generally tangent plane, is broken into every grain length degree after the drying and is 5 millimeters short cylindrical shape catalyst bar, is convenient to change brilliant and handles and examination.Catalyst mechanical strength among the present invention is calculated by this shape measure.Catalyst precarsor mixture I also can be made cellular as required, clover shape, hollow tubular or shape such as spherical, and its strength criterion is meter in addition.
In the characterization method of binder free catalyst, with the contained thing of XRD test mutually and the content of each thing phase, change the pattern of molecular sieve of situation and the generation of crystalline substance with the scanning electron microscopic observation binding agent.Change brilliant back binder content through the XRD thing mutually quantitatively and in the stereoscan photograph content of binding agent confirm.The catalyst silica alumina ratio is confirmed with chemico-analytic method.The strength test method of catalyst is the crushing strength of the catalyst after test roasting on the pressure testing machine; Every of the catalyst of surveying is of a size of 1.5 millimeters of diameters; 5 millimeters of length; Be disposed across on the testing machine, suffered maximum pressure when measuring catalyst breakage is got its mean value after testing 10 catalyst crushing strengths.The mercury injection method test is adopted in catalyst pore volume, average pore size and porosity test.
The present invention is through being crystal seed with the zeolite that adds in the preformed catalyst; Control is suitable for the alkaline environment and the material proportion of zeolite growth, makes binding agent following inducing jointly of zeolite seed crystal and alkali ion, in the environment of water vapour; Can carry out nucleation and growth; Binding agent changes into zeolite active ingredient, obtains the binder free zeolite catalyst, and the preparation process is simple, environmental protection.The content of binding agent can reach below 2% in the binder free type zeolite catalyst that makes; Even do not contain binding agent; Be zeolite all in the catalyst, in the per volume of catalyst, molecular sieve content is higher; So the active site of molecular sieve is also more in the unit volume, so the catalytic activity of catalyst is higher.Because change the staggered growth of the binder free catalyst zeolite crystal grain that obtains behind the crystalline substance, intercrystalline combines closely, so the intensity of catalyst is also higher, can reach 180 newton/more than.The catalyst that makes can be used in the reaction of naphtha catalytic pyrolysis preparing propylene, and the diene weight yield of ethylene, propylene can reach more than 53%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of the adhesiveless ZSM-5 catalyst of embodiment 1 preparation
Fig. 2 is the ESEM picture of the adhesiveless ZSM-5 catalyst of embodiment 1 preparation
Through specific embodiment the present invention being done a nearly step below sets forth.
The specific embodiment
[embodiment 1]
Get silica alumina ratio (molecular proportion, down with) and be 30 ZSM-5 molecular sieve 60 grams, add weight percentage and be 40% Ludox 40 grams, after the mixing and stirring; 10 milliliters of sodium hydroxide solutions that add 1 mol again, mixing and stirring, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours; Put into the moisture autoclave of inner bag bottom then, catalyst does not contact with liquid water, puts into baking oven after the autoclave sealing; 170 ℃ of crystallization were taken out after 60 hours, washed then 2 times, put into 120 ℃ of oven dry of baking oven 3 hours; Putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours make the adhesiveless ZSM-5 catalyst.The XRD figure spectrum of the catalyst that makes is as shown in Figure 1, and it is shown as pure ZSM-5 thing phase.The ESEM picture of the catalyst that makes is as shown in Figure 2, and it is shown as pure ZSM-5 crystal grain, has the binding agent of unformed state hardly.The binder content of unformed state is 0.2%.The withstand voltage broken intensity of detecting catalyst sample be 150 newton/.
[embodiment 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve.Get ZSM-5/ β zeolite 60 grams, the adding weight percentage is 40% Ludox 40 grams, after the mixing and stirring, adds 2 gram magnesia again; Mixing and stirring, agent bar moulding then, preformed catalyst was 80 ℃ of oven dry 3 hours; Put into the moisture autoclave of inner bag bottom then, catalyst does not contact with liquid water, puts into baking oven after the autoclave sealing; 165 ℃ of crystallization were taken out after 80 hours, washed then 2 times, put into 120 ℃ of oven dry of baking oven 3 hours; Putting into the 400 ℃ of roastings 2 hours that heat up of Muffle furnace internal program, 550 ℃ of roastings 3 hours, it is as shown in table 1 to make adhesiveless ZSM-5/beta-zeolite catalyst.The thing that the XRD figure of the catalyst that makes spectrum is shown as ZSM-5 and beta zeolite coexisting mutually.The ESEM picture of the catalyst that makes is shown as cuboidal ZSM-5 molecular sieve thing phase, and there is the binding agent of unformed state hardly in spherical β zeolite thing phase.The withstand voltage broken intensity of detecting catalyst sample be 160 newton/.The binder content of unformed state is 0.5%.
[embodiment 3～16]
Get silica alumina ratio respectively and be 20 modenite, silica alumina ratio and be 10 Y zeolite 60 grams, silica alumina ratio and be 40 MCM-22 molecular sieve, silica alumina ratio and be 20 ZSM-5/ mercerization zeolite symbiosis molecular screen, silica alumina ratio and be 40 ZSM-5/ β zeolite/Y zeolite coexisting molecular sieve, silica alumina ratio and be 20 ZSM-5/Y zeolite/mercerization zeolite symbiosis molecular screen, silica alumina ratio and be 20 ZSM-23, silica alumina ratio and be 30 ZSM-11, silica alumina ratio and be 40 MCM-49, silica alumina ratio and be 60 MCM-56, silica alumina ratio and be 20 ZSM-5/Y coexisting molecular sieve, silica alumina ratio and be 40 MCM-22/ modenite, silica alumina ratio and be 200 ZSM-5/Magadiite, silica alumina ratio and be ZSM-5/ β zeolite/modenite of 30; Proportioning raw materials such as table 1; Method according to embodiment 1; Make the binder free mordenite catalyst, as shown in table 3.
[embodiment 17～22]
Select the used molecular sieve of embodiment 3～8 respectively, according to the method for embodiment 1, other condition is constant; In forming process, add expanding agents such as 2.0 gram sesbania powder, methylcellulose, soluble starch, polyvinyl alcohol, it is as shown in table 2 that raw material is formed proportioning, mixing and stirring; Extrusion, moulding; Press the method for embodiment 1 again, process the binder free zeolite catalyst, the result is as shown in table 3.
[embodiment 23]
Method according to embodiment 1 makes the binder free catalyst; Use concentration is 5% ammonium nitrate solution; It in the solid-to-liquid ratio of catalyst and ammonium nitrate solution 1: 10 ratio; 90 ℃ of exchanges three times, 550 ℃ of roastings made the adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst of Hydrogen after 3 hours then.The component that adopts Shanghai Gaoqiao petro-chemical corporation to produce is C
4～C
10Light oil be raw material (the raw material physical index is seen table 4), the examination activity of such catalysts, using diameter is 12 millimeters fixed bed reactors normal pressure examination down, range of reaction temperature is 650 ℃, reaction pressure is 0.02MPa, weight space velocity is 1 hour
-1, water/feedstock oil weight ratio is 1: 1, the reaction half an hour after, products distribution is seen table 5, obtaining the weight ethylene yield is 28%, the propylene weight yield is 27%, diene weight total recovery is 55%.
[embodiment 24]
Get the binder free catalyst that embodiment 8 makes; Using concentration is 5% ammonium nitrate solution, is 1: 10 ratio in the solid-to-liquid ratio of catalyst and ammonium nitrate solution, exchanges three times at 90 ℃; 550 ℃ of roastings made the Adhesive-free Molecular Sieve catalyst of Hydrogen after 3 hours then.With methyl alcohol is raw material, and the use diameter is 12 millimeters fixed bed reactors, at 450 ℃, weight space velocity 1h
-1, water/methyl alcohol weight ratio 1: 1, pressure is to check and rate under the condition of 0.02MPa, the weight ethylene yield reaches 25%, the propylene weight yield reaches 45%.
[comparative example 1]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; Then mixed crystal molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
[comparative example 2]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5/ β zeolite mixed crystal molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
[comparative example 3]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5 molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; Then ZSM-5 molecular sieve direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
[comparative example 4]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 23 is processed hydrogen type molecular sieve; Then β zeolite direct tablet compressing, break into pieces, sieve, do not contained 20～40 purpose catalyst granules of binding agent, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
Table 3
Table 4
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.2 |
| Cycloalkane % (weight %) | 28.4 |
| Alkene % (weight %) | 0.2 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
Table 5
| Products distribution | Product weight yield (%) |
| Methane | 5.2 |
| Ethane | 6.1 |
| Ethene | 28.0 |
| Propane | 6.5 |
| Propylene | 27.0 |
| Butane | 8.7 |
| Butylene | 7.6 |
| Carbon five above cuts | 8.8 |
| Other | 2.1 |
[comparative example 5]
The silica alumina ratio that Oil of Shanghai Petrochemical Company research institute produces is 40 ZSM-5 molecular sieve; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5 molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
[comparative example 6]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 β zeolite; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the beta zeolite coexisting molecular sieve catalyst of binding agent according to the method extruded moulding of embodiment 1, put into fixed bed reactors; Press the method examination of embodiment 23, the result sees table 6.
[comparative example 7]
The silica alumina ratio of getting the production of Oil of Shanghai Petrochemical Company research institute is 40 ZSM-5, and silica alumina ratio is 40 β zeolite, is mixed into mechanical impurity at 1: 1 according to weight ratio; Method by embodiment 23 is processed hydrogen type molecular sieve; And then, obtain containing the ZSM-5 of binding agent and the catalyst of β zeolite mechanical impurity according to the method extruded moulding of embodiment 23, put into fixed bed reactors; Press the method examination of embodiment 23 again, the result sees table 6.
[comparative example 8]
Preparing silica alumina ratio by the method for Chinese patent CN101428233A is 40 ZSM-5/ β zeolite mixed crystal molecular sieve.Get ZSM-5/ β zeolite 60 grams, the adding weight percentage is 40% Ludox 40 grams, after the mixing and stirring; After pressing the method extrusion, moulding, oven dry of embodiment 2; Put into then the inner bag bottom moisture with the tetraethylammonium bromide mass ratio be 200 milliliters autoclave of 1: 1 mixed solution 40 gram, catalyst does not contact with liquid water, autoclave is put into baking oven after sealing; Press the method for embodiment 2 again and change brilliant processing; Make adhesiveless ZSM-5/beta zeolite coexisting molecular sieve catalyst, the withstand voltage broken intensity of detecting catalyst sample be 150 newton/, the binder content of unformed state is 0.7%.Method by embodiment 23 is processed hydrogen type molecular sieve, puts into fixed bed reactors, presses the method examination of embodiment 23 again, and the result sees table 6.
Table 6
Claims (8)
1. a binder free zeolite catalyst is characterized in that pore volume is 0.1～0.3 a milliliter/gram, and average pore size is 50～70nm, and porosity is 20～30%, and binder content is 0～5%.
2. binder free zeolite catalyst according to claim 1 is characterized in that preformed catalyst intensity is 60～200 newton, and binder content is 0.1～2%.
3. the preparation method of binder free zeolite catalyst according to claim 1 is characterized in that zeolite in the said binder free zeolite catalyst comprises at least a in ZSM-5, ZSM-23, ZSM-11, modenite, Y zeolite, β zeolite, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or the ZSM-5/Y zeolite/modenite.
4. the preparation method of the described binder free zeolite catalyst of claim 1 may further comprise the steps:
A) in the catalyst weight behind the shaping and roasting; After the compound of the zeolite molecular sieve 10～80%, 0.1～20% alkaline matter, 0～20% aluminium and 10～80% silica mixing, moulding, the drying; Obtain preformed catalyst precursor mixture I, the compound weight content of mixture aluminium is less than the weight content of silica in the mixture I;
B) the mixture I is placed put into water vapour, carry out obtaining binder free zeolite catalyst precursor after crystallization handles 10～300 hours at 100～200 ℃;
C) catalyst precarsor 400～700 ℃ of following roastings 1～10 hour, obtains the Adhesive-free Molecular Sieve catalyst through super-dry;
Wherein, alkaline matter is selected from least a in oxide, hydroxide or its salt of weak acid of periodic table of elements I A or II A element; The compound of aluminium is at least a in the hydroxide of hydrous oxide or aluminium of oxide, aluminium of aluminium salt, aluminium, and binder content is 0～5% in the binder free catalyst that makes.
5. the preparation method of binder free zeolite catalyst according to claim 4 is characterized in that I A element is selected from least a in sodium or the potassium; II A element is selected from least a in magnesium or the calcium; Salt of weak acid is selected from least a in disulfate, sulphite, bisulfites, phosphate or the hydrophosphate.
6. the preparation method of binder free zeolite catalyst according to claim 4; It is characterized in that in the catalyst weight behind the shaping and roasting; The consumption of zeolite molecular sieve is 20～70%, the consumption of alkaline matter is 0.5%～10%; The compound amount of aluminium is 1～15%, and the consumption of silica is 30～70%.
7. the preparation method of binder free zeolite catalyst according to claim 4 is characterized in that crystallization temperature is 120～200 ℃, and crystallization time is 20～200 hours.
8. the preparation method of binder free zeolite catalyst according to claim 4; It is characterized in that in the catalyst weight behind the shaping and roasting, also contain 0.1～2% the expanding agent at least a in sesbania powder, methylcellulose or the soluble starch that is selected from the preformed catalyst precursor mixture I.
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| CN2010102618937A CN102371170B (en) | 2010-08-23 | 2010-08-23 | Adhesive-free zeolite catalyst and preparation method thereof |
| RU2013112852/04A RU2565599C2 (en) | 2010-08-23 | 2011-08-23 | Binder-free molecular sieve-based catalyst and method for production thereof |
| SG2013012976A SG187927A1 (en) | 2010-08-23 | 2011-08-23 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| BR112013004126-9A BR112013004126B1 (en) | 2010-08-23 | 2011-08-23 | BAND-FREE MOLECULAR SIECE CATALYST AND METHOD FOR PREPARING THE SAME |
| PCT/CN2011/001408 WO2012024896A1 (en) | 2010-08-23 | 2011-08-23 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| US13/818,295 US9861969B2 (en) | 2010-08-23 | 2011-08-23 | Binderless molecular sieve catalyst and a preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124611A (en) * | 2019-02-12 | 2019-08-16 | 大连理工大学 | A kind of -11 molecular sieve preparation method of binderless ZSM-5 and its application in oil product absorption desulfurization |
| WO2022083564A1 (en) | 2020-10-20 | 2022-04-28 | 中国石油化工股份有限公司 | Catalyst including molecular sieve having topological pore structure, preparation method therefor and use thereof |
| CN114433037A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413244A (en) * | 1999-12-21 | 2003-04-23 | 美孚石油公司 | Catalytic cracking process using modified mesoporous aluminophosphate material |
| US20090326299A1 (en) * | 2006-08-08 | 2009-12-31 | Sud-Chemie Ag | Use of a Catalyst Based on Zeolites in the Conversion of Oxygenates to Lower Olefins, and Associated Method |
| CN101808955A (en) * | 2007-08-28 | 2010-08-18 | 康宁股份有限公司 | Method with making porous ceramic articles with fugitive pore former |
-
2010
- 2010-08-23 CN CN2010102618937A patent/CN102371170B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413244A (en) * | 1999-12-21 | 2003-04-23 | 美孚石油公司 | Catalytic cracking process using modified mesoporous aluminophosphate material |
| US20090326299A1 (en) * | 2006-08-08 | 2009-12-31 | Sud-Chemie Ag | Use of a Catalyst Based on Zeolites in the Conversion of Oxygenates to Lower Olefins, and Associated Method |
| CN101808955A (en) * | 2007-08-28 | 2010-08-18 | 康宁股份有限公司 | Method with making porous ceramic articles with fugitive pore former |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110124611A (en) * | 2019-02-12 | 2019-08-16 | 大连理工大学 | A kind of -11 molecular sieve preparation method of binderless ZSM-5 and its application in oil product absorption desulfurization |
| WO2022083564A1 (en) | 2020-10-20 | 2022-04-28 | 中国石油化工股份有限公司 | Catalyst including molecular sieve having topological pore structure, preparation method therefor and use thereof |
| CN114433037A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
| CN114433037B (en) * | 2020-10-20 | 2024-01-26 | 中国石油化工股份有限公司 | Preparation method of M41S mesoporous material adsorbent, M41S mesoporous material adsorbent and application |
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