CN106554026A - A kind of preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal and its MTO reactivity worth - Google Patents

A kind of preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal and its MTO reactivity worth Download PDF

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CN106554026A
CN106554026A CN201510621707.9A CN201510621707A CN106554026A CN 106554026 A CN106554026 A CN 106554026A CN 201510621707 A CN201510621707 A CN 201510621707A CN 106554026 A CN106554026 A CN 106554026A
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李渊
王文婷
赵飞
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Tianjin Polytechnic University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Abstract

The invention provides a kind of preparation method of the magnesium-modified low silicate molecular sieve material of metal, consisting of：Content of magnesium (being counted with magnesium oxide) is as 0.1-6%；Aluminium content (in terms of aluminium oxide) is：5.36-20%；Silicone content (in terms of silicon oxide) 69-94.5%；As 0.01-5%, this material has the topological structure of CHA types to alkali metal content (being counted with oxide).And this material 630 DEG C calcining 4 hours after specific surface (BET method) not less than 565 meters squared per grams.Its preparation process includes：Template and sodium hydrate aqueous solution are added in alkaline silica sol and are stirred, aluminum sulfate is added, is stirred, add the crystal seed of chabasie crystalline phase, stirring at normal temperature to obtain homogeneous gel in 4 hours；Again through crystallization, roasting, magnesium ion are exchanged and obtain product.The introducing of magnesium ion can also be introduced in one step of sieve synthesis procedure.Molecular screen material according to prepared by the present invention has low silica-alumina ratio, acid site density adjustable, and acid intensity is low, high MTO diolefin selectives and preparation process does not have the advantages that a large amount of ammonium chloride exhausted liquids.

Description

A kind of preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal and its MTO reactivity worth
Technical field
The present invention relates to a kind of preparation method of the magnesium-modified low silicon SSZ-13 molecular sieves of metal, and its as methanol-to-olefins (MTO) catalyst Application.
Background technology
Methanol-to-olefins (MTO) are the new technologies that a kind of alternative traditional petroleum path produces low-carbon alkene, in recent years, with petroleum resources In short supply, the technique causes the extensive concern of countries in the world.And the core of MTO techniques is catalyst problem.At present, it is commonly used on market MTO catalyst active component is SAPO-34 molecular sieves.At the same time, people to and SAPO-34 molecular sieves there is the silicon of identical CHA structure The MTO properties of aluminium profiles zeolite molecular sieve have been also carried out in-depth study.
SSZ-13 molecular sieves are invented by Chevron Corporation (Chevron) oil company, are disclosed in patent US4544538.As the patent is closed Into SSZ-13 molecular sieves there is relatively low silica alumina ratio, MTO reacting catalytic performances are unsatisfactory.
In order to improve the MTO diolefin selectives of SSZ-13 molecular sieves, researcher has been focused on synthesizing high-silicon aluminum ratio SSZ-13 molecular sieves, Attempt to reduce the acid site density of SSZ-13 molecular sieves, improve MTO diolefin selectives.However as carrying for SSZ-13 molecular sieve silica alumina ratios Height, molecular sieve product specific surface area are reduced, and degree of crystallinity declines, acid to strengthen.
The content of the invention
Compared with SAPO-34 molecular sieves, SSZ-13 molecular sieves have stronger acid strength, thus during catalysis MTO, hydrogen migration is anti- Should be serious, have impact on the diolefin selective of MTO processes.It can be seen that, the acid strength for reducing SSZ-13 molecular sieves is to improve MTO process diolefins It is selective crucial.In Si-Al molecular sieve, a framework aluminum atom pair answers a sour position, and regular according to Lowenstein, two skeleton aluminium atoms are The structural formula that an oxygen bridge, i.e.-Al-O-Al- can not be shared is that two non-existent therefore closest in molecular sieve aluminium atoms have - Al-O-Si-O-Al structures, i.e. NNN (Next-nearest neighbour) structure.Research finds to use in congeneric elements sieve, dividing with NNN structures Son sieve, its acid strength are minimum.Therefore, by increasing aluminium content, the quantity and size of silicon island are reduced reducing the acid strength of SSZ-13 molecular sieves, It is feasible in theory.However, silica alumina ratio is reduced while molecular sieve acid strength is reduced, improve the acid site density of molecular sieve.Research table The alternative H of bright metal ion+The center of negative charge that neutralizing molecule sieve framework aluminum is produced, so that the acid centre of molecular sieve is reduced.Therefore, in low silicon Appropriate metal ion is introduced on aluminum ratio SSZ-13 molecular sieves can reduce its acid strength and acid site density, and then improve the diolefin of MTO processes Yield.It is an object of the invention to provide a kind of low silica-alumina ratio, exchange without the need for ammonium chloride, the Mg-SSZ-13 molecular sieves that high MTO diolefins are selected Prepare and its apply.
With N, N, N- trimethyl diamantane (obsolete) ammonium hydroxide as template, the Na-SSZ-13 molecular sieves of synthesis are exchanged the present invention without the need for ammonium chloride, acid Property center is less, and acid strength is relatively low.The Mg-SSZ-13 molecular sieves of preparation have superior MTO reactivity worth.
The preparation method of the present invention comprises the steps：
(1) preparation of gel
Alkaline silica sol is added in beaker, room temperature stirring in water bath, adds alkali liquor (aqueous solution of template and sodium hydroxide), stir, Aluminum sulfate is added, adds the molecular sieve of chabasie (CHA) crystalline phase to make crystal seed, stirring at normal temperature 4 hours is obtained homogeneous gel.
Wherein silicon source is with Al2O3Meter, silicon source (alkaline silica sol) is with SiO2Meter, sodium hydroxide is with Na2O count, template in terms of R, instead Material is answered by mol ratio SiO2∶Al2O3∶Na2O∶R∶H2O=(6.8-30): 1: (1-5): (0.5-2): (200-500) synthesize colloid.
The composition of alkaline silica sol as above is as follows：Silicon dioxide (SiO2) mass content 30-60%, sodium oxide (Na2O) quality contains Amount 0.2-0.4%, remaining is water.
The composition of template as above is as follows：N, N, N- trimethyl diamantane (obsolete) ammonium hydroxide mass content 20-30%, remaining is water.
Crystal seed as above is the molecular sieve with chabasie (CHA) crystalline phase, including：SAPO-34 molecular sieves, SSZ-13 molecular sieves, SAPO-34 Type molecular sieve includes template cationic, Hydrogen.SSZ-13 type molecular sieves include sodium form, template cationic, Hydrogen.
(2) crystallization
By Primogel load polytetrafluoro autoclave at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product be washed with deionized to Filtrate is dried 12h in neutrality at 100 DEG C.
(3) roasting
Temperature programming in 4 hours, to 500-600 DEG C, is incubated roasting in 4 hours to the sample of drying in air atmosphere.
(4) magnesium nitrate is exchanged
Sample after roasting is added in magnesium ion aqueous solution (0.01M) (sample is 1: 100 with the mass ratio of water), 60-80 DEG C of insulation is heated to Stirring 1-2 hours complete exchange of the magnesium ion to part sodium ion, and the mixed system is carried out sucking filtration, wash to filtrate in neutrality, then in 100 DEG C drying, completes magnesium ion and exchanges, repeat above-mentioned magnesium ion exchange process twice, complete three magnesium ions and exchange, in air atmosphere in In Muffle furnace, temperature programming in 4 hours is incubated roasting in 4 hours to 500-600 DEG C.
Template R as above is N, N, N- trimethyl diamantane (obsolete) ammonium hydroxide.
Silicon source is aluminum sulfate as mentioned above.
It is magnesium nitrate or magnesium acetate that magnesium ion exchanges reagent as mentioned above.
Magnesium ion in Mg-SSZ-13 molecular sieves can also be introduced in the preparation process of gel, and one-step synthesis Mg-SSZ-13 saves magnesium ion Ion exchange process.
The application of magnesium-modified low silica-alumina ratio SSZ-13 molecular sieves prepared by the present invention comprises the steps：With first alcohol and water compounding methanol mass concentration it is The methanol solution of 50-96% be raw material, the methanol quality air speed of reaction：2-20h-1, reaction temperature：400-500 DEG C, reaction pressure：Normal pressure is low Pressure.
The present invention has the advantage that as follows compared with prior art：
Exchange without the need for ammonium chloride
With acid site density lower under silica alumina ratio
Excellent MTO reactivities, the average diolefin selectives of MTO are more than 82%
Description of the drawings
Fig. 1 is the x-ray diffractogram of powder (XRD) of the product described in the embodiment of the present invention 1
Fig. 2 is the electromicroscopic photograph (SEM) of the product described in the embodiment of the present invention 1
Fig. 3 is the MTO ACTIVITY CHANGE OF FT figures of the product described in the embodiment of the present invention 1 and comparative example product
Fig. 4 is the MTO diolefin selective variation diagrams of the product described in the embodiment of the present invention 1 and comparative example product
Specific embodiment
Comparative example 1：The preparation of low silicon H-SSZ-13 molecular sieves
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
Prepare gel：13.05g Ludox is added in beaker, room temperature stirring in water bath, adds alkali liquor, stir, add 3.25g aluminum sulfate, Stir, add the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, stirring at normal temperature 4 hours is obtained homogeneous gel.
Crystallization：By Primogel load polytetrafluoro autoclave at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：Temperature programming in 4 hours, to 600 DEG C, is incubated roasting in 4 hours to the sample of drying in air atmosphere.
Ammonium is exchanged：The above-mentioned baked samples of 3g are taken, in adding 100ml beakers, the solution for adding 0.9g ammonium chloride and 30g deionized waters to be made into, It is warming up to 70 DEG C of insulated and stirred 2 hours, sucking filtration completes an ammonium and exchanges.Repeat above-mentioned ammonium exchange process twice, after the completion of three ammonium exchanges, 30g 70 DEG C of deionized water insulated and stirred 2 hours, sucking filtration is added to complete once to wash, 100 DEG C of drying samples, the sample of drying is in air atmosphere Lower temperature programming in 4 hours is incubated roasting in 4 hours, obtains low silicon H-SSZ-13 sieve samples to 600 DEG C.
Comparative example 2：The preparation of low silicon Na-SSZ-13 molecular sieves
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
Prepare gel：13.05g Ludox is added in beaker, room temperature stirring in water bath, adds alkali liquor, stir, add 3.25g aluminum sulfate, Stir, add the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, stirring at normal temperature 4 hours is obtained homogeneous gel.
Crystallization：By Primogel load polytetrafluoro autoclave at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：The sample of drying is warming up to 600 DEG C for 4 hours in air atmosphere, is incubated roasting in 4 hours, and Na-SSZ-13 molecular sieves are obtained.
Embodiment 1：Using magnesium nitrate exchange system for Mg-SSZ-13
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
Prepare gel：13.05g Ludox is added in reactor, room temperature stirring in water bath is subsequently adding alkali liquor, stirs, adds 3.25g Aluminum sulfate, stirs, and adds the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, and stirring at normal temperature 4 hours is obtained homogeneous gel.
Crystallization：By Primogel load polytetrafluoro autoclave at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：Temperature programming in 4 hours, to 600 DEG C, is incubated roasting in 4 hours to the sample of drying in air atmosphere.
Magnesium nitrate is exchanged：Sample after roasting is added in 300ml magnesium nitrate aqueous solutions (0.01M) by sample 3g, 80 DEG C of insulations are heated to Stirring carries out ion exchange in 1 hour, completes exchange of the magnesium ion to part sodium ion, the mixed system is carried out sucking filtration, washs, then in 100 DEG C drying, completes magnesium and exchanges, repeat above-mentioned magnesium exchange process twice, completes after three magnesium ions exchange, to add 30g deionized waters 70 DEG C insulated and stirred 2 hours, sucking filtration completes once to wash, in air atmosphere in Muffle furnace, temperature programming in 4 hours to 600 DEG C, insulation 4 Hour roasting.
Compounding methanol solution：Methanol quality concentration 80%, moisture 20%.Using micro fixed-bed reactor in WHSV=5h-1, at 450 DEG C Carry out MTO active testings, the average diolefin selectives 82.12% of MTO, compared to Na-SSZ-13 molecular sieves (79.91%) and H-SSZ-13 Molecular sieve (68.94%) MTO diolefin selectives improve a lot.Methyl alcohol process 5.48g, compared to Na-SSZ-13 molecular sieves (4.98g) Improve a lot with H-SSZ-13 molecular sieves (3.25g) MTO methyl alcohol process amounts.Test result is shown in 3 accompanying drawing 4 of accompanying drawing.
Embodiment 2：Using magnesium acetate exchange system for Mg-SSZ-13
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
Prepare gel：13.05g Ludox is added in beaker, room temperature stirring in water bath, adds alkali liquor, stir, add 3.25g aluminum sulfate, Stir and add the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, stirring at normal temperature 4 hours is obtained homogeneous gel.
Crystallization：By Primogel load polytetrafluoro high-pressure reactor at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：The sample of drying is warming up to 600 DEG C in 4 hours under air atmosphere, is incubated roasting in 4 hours.
Magnesium acetate is exchanged：Sample after roasting is added in 300ml magnesium acetate aqueous solutions (0.01M) by sample 3g, 80 DEG C of insulations are heated to Stirring carries out ion exchange in 1 hour, completes exchange of the magnesium ion to part sodium ion, the mixed system is carried out sucking filtration, washs, then in 100 DEG C drying, completes magnesium and exchanges, repeat above-mentioned magnesium exchange process twice, completes after three magnesium ions exchange, to add 30g deionized waters 70 DEG C insulated and stirred 2 hours, sucking filtration completes once to wash, and in air atmosphere in Muffle furnace, is warming up within 4 hours 600 DEG C, is incubated 4 hours Roasting.
Case study on implementation 3：Using magnesium nitrate one-step synthesis Mg-SSZ-13
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
Prepare gel：13.05g Ludox is added in beaker, room temperature stirring in water bath is subsequently adding alkali liquor, stirs, adds 3.25g sulfur Sour aluminum, stirs, and adds 1.47g magnesium nitrates, adds the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, stirring at normal temperature 4 hours, Homogeneous gel is obtained.
Crystallization：By Primogel load polytetrafluoro high-pressure reactor at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：The sample of drying is warming up to 600 DEG C in 4 hours under air atmosphere, is incubated roasting in 4 hours.
Case study on implementation 4：Using magnesium acetate one-step synthesis Mg-SSZ-13
Prepare alkali liquor：0.83g sodium hydroxide is added in 18g water, is stirred to sodium hydroxide and is dissolved, add 3.43g N, N, N- trimethyl Buddha's warrior attendants Alkane ammonium hydroxide (template), stirs to uniform solution.
It is prepared by gel：13.05g Ludox is added in reactor, room temperature stirring in water bath is subsequently adding alkali liquor, stirs, adds 3.25g Aluminum sulfate, stirs, and adds 1.23g magnesium acetates, adds the molecular sieve of 0.16g chabasies (CHA) crystalline phase to make crystal seed, and stirring at normal temperature 4 is little When, homogeneous gel is obtained.
Crystallization：By Primogel load polytetrafluoro high-pressure reactor at 165 DEG C crystallization 2-4 days, after the completion of crystallization, by product deionized water Wash to filtrate in neutrality, 12h is dried at 100 DEG C.
Roasting：The sample of drying is warming up to 600 DEG C in 4 hours under air atmosphere, is incubated roasting in 4 hours.
Material testing art
The material phase analysis of target product are determined using the Rigaku D/max2550 types X-ray diffractometer of Rigaku company, method of testing：Cu k α targets, scanning voltage 40KV, sweep current 150mA, 5 °/min of scanning speed, 2theta are 5～50 °, test result Origin Software is processed.
The crystal morphology of target product is tested by FDAC (Hitachi) company field emission scanning electron microscope S-4800.
The present invention discloses and proposes a kind of preparation and its MTO reactivity worth of the magnesium-modified low silicon SSZ-13 molecular sieves of metal, by embodiment Son is described, and person skilled substantially can be entered to device as herein described and processing method in without departing from present invention, spirit and scope Row is corresponding to be changed or suitably changes and combine, and realizes the technology of the present invention.Specifically, all similar replacements and change are to ability It is it will be apparent that they are considered as being included in spirit of the invention, scope and content for field technique personnel.

Claims (7)

1. magnesium-modified low silicon SSZ-13 molecular screen materials of a kind of metal, consisting of：Content of magnesium is calculated as 0.1-6% with magnesium oxide；Aluminium content is with aluminium oxide It is calculated as：5.36-20%；Silicone content is calculated as with silicon oxide：69-94.5%；Alkali metal content is calculated as 0.01-5% with oxide；This material has CHA The topological structure of type.And the specific surface that this material is obtained using BET method side after 4 hours in 630 DEG C of calcinings is not less than 565 meters squared per grams.
2. material as claimed in claim 1 is constituted, and the preparation method of the magnesium-modified low silicon SSZ-13 molecular sieves of metal is comprised the following steps：
(1) preparation of gel
Alkaline silica sol of the silicon dioxide quality concentration for 30%-60% is added in reactor, room temperature stirring in water bath is subsequently adding template and hydrogen-oxygen Change the aqueous solution of sodium, stir, then sequentially add aluminum sulfate, as the molecular sieve with chabasie crystalline phase of crystal seed, stirring at normal temperature 4 hours, Homogeneous gel is obtained
Wherein silicon source is with Al2O3Meter, silicon source is with SiO2Meter, sodium hydroxide is with Na2O is counted, and in terms of R, reaction mass presses mol ratio SiO to template2∶ Al2O3∶Na2O∶R∶H2O=6.8-30: 1: 1-5: 0.5-2: 200-500 synthesis colloid
(2) crystallization
By Primogel load polytetrafluoro high-pressure reactor at 165 DEG C crystallization two days, after the completion of crystallization, product is washed with deionized, 100 12h is dried at DEG C
(3) roasting
The sample of drying is warming up to 500-600 DEG C in 4 hours under air atmosphere, is incubated roasting in 4 hours
(4) magnesium ion is exchanged
Sample after roasting is added to into the magnesium ion aqueous solution of 0.01M by sample, wherein sample and the mass ratio of water are 1: 100, are heated to 60-80 DEG C of guarantor Temperature stirring 1-2 hours carry out ion exchange, complete exchange of the magnesium ion to part sodium ion, the mixed system is carried out sucking filtration, wash, Ran Houyu 100 DEG C of drying, complete a magnesium and exchange, and the above-mentioned magnesium exchange process of repetition 3 times completes three magnesium ions and exchanges, in air atmosphere in Muffle furnace In, it is warming up to 500-600 DEG C within 4 hours, is incubated roasting in 4 hours.
3., such as material preparation method according to claim 2, the introducing of magnesium ion can be introduced directly in gel preparation course, without carry out it is secondary from Son is exchanged.
4. a kind of preparation of the low silicon SSZ-13 molecular sieve magnesium-modified by the metal described in claim 2, it is characterised in that described crystal seed is with chabasie The molecular sieve of crystalline phase, including：SAPO-34 molecular sieves, SSZ-13 molecular sieves, SAPO-34 type molecular sieves include template cationic, Hydrogen. SSZ-13 type molecular sieves include sodium form, template cationic, Hydrogen.
5. the preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal as claimed in claim 2, it is characterised in that preparation process does not have substantial amounts of ammonium salt and gives up Liquid.
6. the preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal as claimed in claim 2, it is characterised in that the magnesium exchange reagent be magnesium nitrate or Magnesium acetate.
7. the application of the magnesium-modified low silicon SSZ-13 molecular screen materials of a kind of metal as claimed in claim 1, it is characterised in which is applied to methanol conversion system Standby low carbon olefin hydrocarbon, wherein methanol quality concentration are 50-96%, the mass space velocity of reaction：1-20h-1, reaction temperature：400-500℃.
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CN114890435A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof
CN114890434A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) SAPO-34 molecular sieve rich in mesopores prepared from MTO waste catalyst and preparation method thereof

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CN111646483A (en) * 2020-06-12 2020-09-11 浙江浙能技术研究院有限公司 Ru-SSZ-13 molecular sieve and preparation method thereof
CN114890435A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof
CN114890434A (en) * 2022-06-22 2022-08-12 中国石油大学(华东) SAPO-34 molecular sieve rich in mesopores prepared from MTO waste catalyst and preparation method thereof
CN114890434B (en) * 2022-06-22 2023-08-25 中国石油大学(华东) Mesoporous-enriched SAPO-34 molecular sieve prepared from MTO (methyl thiazolyl tetrazolium) spent catalyst and preparation method thereof
CN114890435B (en) * 2022-06-22 2023-08-25 中国石油大学(华东) Hollow-structure SAPO-34 molecular sieve prepared by MTO spent catalyst, and preparation method and application thereof

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