CN106904636A - It is a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application - Google Patents
It is a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application Download PDFInfo
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Abstract
The invention discloses a kind of with the molecular sieves of SSZ 13 and its synthetic method of microporous mesoporous multi-stage artery structure and application, synthetic method is as crystallization additive synthesis from long-chain Bis-quaternary Ammonium Salt Surfactant, specific synthesis step include plastic and ageing, crystallization, washing, Template removal and activate, step etc. ion exchange and activation, the molecular sieves of high-crystallinity multi-stage porous SSZ 13 of microporous mesoporous orderly distribution can be obtained.The molecular sieve for obtaining has mesoporous pore size distribution of two kinds of sizes including 2~5nm and 5~15nm scopes, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g, specific surface area>400m2/ g, the yield of crystallization product can reach more than 85%.In addition to micro-pore zeolite advantage, the advantages of be also equipped with mesoporous middle solid tumor, the molecular screen materials of multi-stage porous SSZ 13 are with a wide range of applications the molecular sieves of this SSZ 13 in the field such as MTO reactions and tail gas catalyzed reduction (SCR) reaction.
Description
Technical field
The present invention relates to a kind of multi-stage porous SSZ-13 molecular sieves with micropore-mesopore and its synthetic method, and in particular to
Long-chain Bis-quaternary Ammonium Salt Surfactant ion is introduced in synthesizing Si-Al collosol intermixture as crystallization promoting agent, in crystallization gradually
Form the SSZ-13 molecular sieves of the multi-stage artery structure of micropore-mesopore.
Background technology
The molecular sieve particle diameter that traditional preparation method is obtained has serious limit than larger for the molecular sieve catalytic life-span
System.The introducing of multi-stage pore canal molecular sieve concept shortens molecule diffusion length so that product is easier to expand from active sites
It is scattered to outer surface, it is suppressed that the formation of coking, increased the life-span of catalyst.Multi-stage pore canal molecular sieve synthesis has been obtained for industry
The extensive concern on boundary.
Document (ACS Catalysis.2013,3 (2):Quaternary surfactant 192-195) is used as structure directing
Agent, synthesizes nanoparticle structure BEA, MTW and MRE molecular sieves under conditions of different ratio, and the molecular sieve has micro- simultaneously
Hole and meso-hole structure.
Patent CN201410386943 with eight Bola type quaternary surfactants of different carbon chain lengths as template,
Prepared with hydro-thermal method in alkalescence condition has mesoporous and microcellular structure Beta multi-stage pore zeolite molecular sieves simultaneously.Eight quaternary ammonium salts
Surfactant generates microcellular structure as the structure directing agent of Beta molecular sieves, and the last-of-chain base hydrophobic long aggregation of template is produced
Rubber Shu Ze makes molecular sieve form meso-hole structure, and the multi-stage porous molecular sieve of preparation has mesoporous and crystalline microporous structure.
Patent CN201210287411 using six ammonium cation type quaternary surfactants as template, in alkaline bar
The multi-stage pore zeolite molecular sieve containing mesoporous and Beta zeolite micropores is prepared under part by hydrothermal synthesis method.Six ammonium cation types
Quaternary surfactant generates micropore as Beta zeolite structure directing agents, and the aggregation between the chain alkyl of its hydrophobic is then
Form mesoporous, the multi-stage pore zeolite molecular sieve of preparation has mesoporous and crystalline state micropore simultaneously.
CN201410723282 coordinates polyquaternium surfactant with a small amount of micropore template agent, and synthesis has obtained crystallinity
High, acid strong, the multi-stage porous ZSM-5 molecular sieve of good hydrothermal stability.But the pore-size distribution controlled range that the method is obtained is not
It is enough big.In this synthetic method mesoporous impalpable structure and micro-pore zeolite two-phase point are likely to be obtained using cationic surfactant
From mix products.
Above-mentioned these patents describe the Beta molecular sieves and ZSM-5 molecular sieve synthetic method of hierarchical porous structure, synthesize
Process control condition is harsher, can not be applied to the porous level structure synthesis of aperture SSZ-13 molecular sieves of 8 yuan of rings CHA types.
SSZ-13 molecular sieves are that Americanized scholar Zones is synthesized the eighties in 20th century by hydro-thermal method, belong to micropore
In pore zeolite.It has good heat endurance, simultaneously because the tetrahedral presence of AlO4 and SiO4 in skeleton, makes its bone
Frame has cation exchange and acid adjustability, so that SSZ-13 is provided with good catalytic performance, including hydrocarbon
The catalytic cracking of thing, is hydrocracked, and alkene and aromatic hydrocarbons construction reaction.Be condensed-nuclei aromatics blocking with conventional SSZ-13 micropores,
Outer surface to form sharp contrast for carbon deposit is covered, and multi-stage porous SSZ-13 is fully used in duct, possesses faster reaction rate,
Product is easier to be diffused into outer surface from active sites, it is suppressed that the formation of coking, increased the life-span of catalyst.
The content of the invention
It is an object of the invention to provide a kind of hierarchical porous structure SSZ-13 molecular sieves of micropore-mesopore, it is catalyzed as one kind
Agent improves catalytic reaction activity, substantially increases mass transfer rate, significantly suppress the coking deactivation of catalyst, extends catalyst
Life-span.
It is many it is an object of the invention to provide a kind of synthesis by the use of long-chain Bis-quaternary Ammonium Salt Surfactant as crystallization promoting agent
The method of level duct SSZ-13 molecular sieves, the molecular sieve of this pore size distribution structure is conducive to MTO and SCR etc. to react.
The technical solution adopted for the present invention to solve the technical problems is with alkali source, silicon source, Organic structure directing agent, long-chain
Bis-quaternary Ammonium Salt Surfactant and water are raw material heating stirring into colloidal sol, and silicon source is added in then gradually being stirred according to proportioning, are mixed
Conjunction forms Alusil, and after room temperature ageing, being placed in carries out crystallization in crystallizing kettle, by product filtering, Template removal, ion exchange
Multi-stage porous SSZ-13 molecular sieve catalysts are obtained with activation.
The synthetic method of multistage pore canal SSZ-13 molecular sieves of the present invention, it is characterised in that comprise the following steps that：
1) a certain amount of long-chain Bis-quaternary Ammonium Salt Surfactant dissolving is weighed in deionized water according to reaction raw materials proportioning
Solution ＆ stir dispersion is formed, silicon source, alkali source and organic formwork agent is subsequently adding, 5~10 is stirred under the conditions of 30~50 DEG C small
When, obtain silicon source mixed solution；
2) at 30~80 DEG C, in the silicon source solution formed during 1) silicon source solution is added drop-wise to according to reaction raw materials proportioning,
After being stirred vigorously 30~120min, it is stored at room temperature ageing and obtains silicon-aluminum sol in 2~12 hours.
3) the silicon-aluminum sol mixture obtained in 2) is placed in 120~190 DEG C of points of 2 sections of crystallization, second in Hydrothermal Synthesiss kettle
Duan Wendu is higher than first paragraph 20 DEG C, and after 48~168 hours crystallization are complete, centrifugation goes out solid product, then by solid product
With deionized water cyclic washing to neutrality, then dried 12~48 hours under the conditions of 100~130 DEG C, and at 400~600 DEG C
2~10 hours removing organic formwork agents of roasting, obtain multi-stage porous SSZ-13 molecular screen primary powders；
4) by SSZ-13 molecular screen primary powders and NH4 +Solion carries out 400~600 DEG C of roastings after ion exchange, washing, drying
Burning obtains the multi-stage porous SSZ-13 molecular sieve catalysts of H types for 2~10 hours.
Silicon source is with SiO in the Alusil mixture of the crystallization that feeds intake described in synthetic method of the present invention2Meter, silicon source is with Al2O3
Meter, in terms of SDA, in terms of DQA, crystallization feed molar proportioning is long-chain Bis-quaternary Ammonium Salt Surfactant organic formwork agent：
Na2O：SiO2：Al2O3：SDA：DQA：H2O=0.35~0.65：1：0.0025~0.01：0.05~0.5：0.01~0.05：10
~50.
The long-chain Bis-quaternary Ammonium Salt Surfactant added described in crystallization synthesis of the present invention, it is characterised in that including
[CnH2n+1-N+(CH3)2-(CH2)4-N+(CH3)2-C4H9]X2(it is abbreviated as Cn-4-4X2) and [CmH2m+1-N+(CH3)2-(CH2)6-
N+(CH3)2-C6H13]Y2(it is abbreviated as Cm-6-6Y2), wherein, n=16,18,22；X=Br, Cl, I.M=16,18,22；Y=
Br,Cl,I。
In synthetic method of the present invention involved silicon source be white carbon, active silica, sodium metasilicate, silester or
One kind of methyl silicate；Silicon source is aluminium isopropoxide, sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium hydroxide or intends thin water
One kind of aluminium stone.
Involved organic formwork agent is N, N, N- trimethyl -1- adamantane ammonium hydroxide in synthetic method of the present invention
(TMADa+), any one or two kinds in benzyltrimethylammonium hydroxide (BTMA+).
Crystal pattern described in synthetic method of the present invention is dynamic crystallization or static crystallization, preferably dynamic crystallization mode.
The salting liquid for being related to the ammonium ion that SSZ-13 molecular sieves carry out ion exchange in the present invention is ammonium nitrate, sulfuric acid
The aqueous solution of ammonium, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 0.5~1.5mol/L.
The present invention provides a kind of SSZ-13 molecular sieves of the multistage pore canal that above-mentioned preparation method is obtained, and is characterised by its duct
<2nm, 2~5nm and 5~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>0.35cm3/ g,
Specific surface area>400m2/g。
The present invention provides a kind of above-mentioned SSZ-13 molecular sieves in methanol-to-olefins (MTO) and tail gas catalyzed reduction reaction
(SCR) application in field such as.
Compared with prior art, the present invention has advantages below and beneficial effect：
SSZ-13 molecular sieves prepared by the present invention have micropore and mesoporous simultaneously, it is to avoid the defect in single duct, big
Molecular Adsorption and catalysis aspect have broad application prospects.
In addition to micro-pore zeolite advantage, transgranular meso-hole structure effectively contracts the multi-stage porous SSZ-13 molecular sieves that the present invention is obtained
Short diffusion length, hence it is evident that improve adsorption capacity.By the use of long-chain Bis-quaternary Ammonium Salt Surfactant multistage is obtained as the auxiliary agent of synthesis
Duct SSZ-13 molecular sieves, compared with the head group of single quaternary ammonium salt, two ammonium head groups preferably can lead with structure
The growth of SSZ-13 molecular sieves is formed to have with the multilevel hierarchy hole of micropore-mesopore to agent (SDAs) and advantageously promotes effect.Should
Multi-stage porous SSZ-13 molecular screen materials are with a wide range of applications in fields such as petrochemical industry, Coal Chemical Industry and fine chemistry industries, special
It is not have good application in the field such as methanol-to-olefins (MTO) and tail gas catalyzed reduction reaction (SCR), not only improves catalysis anti-
Answer the service life of activity and the catalyst of extension.
Brief description of the drawings
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
Fig. 1 is the multi-stage porous SSZ-13 molecular sieves SEM figures of sample 1 in embodiments of the invention 1；
Fig. 2 is the multi-stage porous SSZ-13 molecular sieve XRDs of sample 1 in embodiments of the invention 1.
Specific embodiment
Embodiment of the present invention and produced effect are further illustrated by embodiment and comparison example, but it is of the invention
Protection domain is not limited to the content listed by embodiment.
Embodiment 1
According to listed in table 1, reaction raw materials proportioning weighs quantitative long-chain Bis-quaternary Ammonium Salt Surfactant and is dissolved in methyl alcohol
Middle formation solution ＆ stir dispersion, is subsequently adding silicon source, alkali source, is stirred 6 hours under the conditions of 40 DEG C, obtains silicon source mixing molten
Liquid；At 60 DEG C, silicon source solution is added drop-wise in silicon source mixed solution according to reaction raw materials proportioning, it is quiet after being stirred vigorously 90min
Put ageing and obtain mixture gel in 12 hours.Mixture gel is placed in 120~190 DEG C of points of 2 sections of crystallization in Hydrothermal Synthesiss kettle, the
Two sections of temperature are higher than first paragraph 20 DEG C, and after crystallization is complete, centrifugation goes out solid product, then by solid matter with deionized water
Then cyclic washing dries 24 hours to neutrality under the conditions of 120 DEG C, and in 550 DEG C of roastings, 4 hours removing organic formwork agents,
Obtain multi-stage porous SSZ-13 molecular screen primary powders；By SSZ-13 molecular screen primary powders and the NH of 1.0mol/L4 +Solion is according to solid-liquid
Than=1:10 ratio carry out ion exchange 2 hours, washing, 120 DEG C of dryings 24 hours at 90 DEG C after 550 DEG C of roastings 2 hours
To the multi-stage porous SSZ-13 molecular sieve catalysts of H types.Synthesized SSZ-13 molecular screen primary powders sample 1~20#Primogel in
Type of feed and proportioning, crystallization temperature, crystallization time, ammonium ion salt species and products therefrom yield and silica alumina ratio difference
As shown in Table 1 and Table 2.The SSZ-13 zeolite products have the hierarchical porous structure pattern of micropore-mesopore, mesopore orbit size model
Enclose 2~15nm.
Table 1
Table 2
Embodiment 2
To SSZ-13 sieve samples 1~20 synthesized in embodiment 1 using the types of Micromeritics ASAP 2020
Nitrogen physisorption instrument carries out phenetic analysis.The preprocess method of sample is as follows before analysis：At normal temperatures by sieve sample
Vacuumize process, after vacuum condition is reached, 2h is processed at 130 DEG C；Afterwards 2h is processed at 350 DEG C.Nitrogen physisorption result
Show, the micropore size of sample 1~20 is 0.3~0.5nm, contains meso-hole structure, mesoporous pore size distribution, mesoporous average pore size,
Mesopore volume and specific surface area are as shown in table 3.
Table 3
Embodiment 3
XRD is carried out to sample 1~20 prepared in embodiment 1 to characterize to confirm as SSZ-13 molecular sieves.Used instrument
Device is PANalytical X ' Pert type X-ray diffractometers, and copper target, K α radiation source instrument operating voltage is 40kv, operating current
It is 40mA.The XRD spectra of resulting sample 1~20 is consistent with the feature spectrogram of standard SSZ-13 molecular sieves.Typical XRD
Spectrum (such as Fig. 2) is with sample 1 as representative, and 2 θ are as shown in table 4 in 5 °~50 ° main diffraction peak positions and peak intensity.Other sample numbers
According to result compared with sample 1, diffraction maximum location and shape are identical, according to the change relative peak intensities of synthesis condition in ± 5% scope
Interior fluctuation, shows that synthetic product has the feature of SSZ-13 molecular sieve structures.
Table 4
| Characteristic peak sequence number | 2Theta(°) | Relative intensity % |
| 9.4 | 100.0% | |
| 12.78 | 16.6% | |
| 15.88 | 9.0% | |
| 17.52 | 13.9% | |
| 20.44 | 62.6% | |
| 22.22 | 5.3% | |
| 22.84 | 27.1% | |
| 24.6 | 23.2% | |
| 25.72 | 5.7% | |
| 27.44 | 4.1% | |
| 27.8 | 8.1% | |
| 30.38 | 43.1% | |
| 30.7 | 36.9% | |
| 35.58 | 14.7% | |
| 43.06 | 6.0% | |
| 43.66 | 3.4% |
Embodiment 4
The evaluation of catalyst：1~8 catalyst raw powder resulting in embodiment 1 is carried out into compressing tablet, 20~40 are crushed to
Mesh.Weigh 0.3g samples and load fixed bed reactors, carry out MTO evaluations.Lead to nitrogen activation 1.5 hours at 500 DEG C, then drop
Temperature is to 450 DEG C.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 15ml/min, methanol weight air speed 4.0h-1.Resulting product by
Online gas-chromatography (Agilent7890) is analyzed, and the results are shown in Table 5.From which it can be seen that 8 samples be respectively provided with it is high
Catalytic life, while the total recovery of ethene and propylene has exceeded 83.0%.
Table 5
t50：Conversion ratio was reduced to for 50% time experienced from 100%；t98：Conversion ratio is reduced to 98% institute from 100%
The time of experience.
As can be seen from Table 5, multi-stage porous SSZ-13 molecular sieve catalysts prepared by the method that the present invention is provided react in MTO
In, with low-carbon alkene (C higher2 =+C3 =) selectivity is up to 84.5%, and conversion ratio drops to the conversion life-span before 50%
More than 13 hours, illustrate that there is the multi-stage porous SSZ-13 molecular sieve catalysts MTO to react the good life-span.
The embodiment only technology design and feature to illustrate the invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (9)
1. a kind of synthetic method of the SSZ-13 molecular sieves with micropore-mesopore multi-stage artery structure, it is characterised in that including such as
Lower step：
1) a certain amount of long-chain Bis-quaternary Ammonium Salt Surfactant is weighed according to reaction raw materials proportioning to be dissolved in water to form solution simultaneously
Dispersed with stirring, is subsequently adding silicon source, alkali source and organic formwork agent, is stirred 5~10 hours under the conditions of 30~50 DEG C, obtains silicon source
Mixed solution；
2) at 30~80 DEG C, in the silicon source solution formed during 1) silicon source solution is added drop-wise to according to reaction raw materials proportioning, acutely
After 30~120min of stirring, it is stored at room temperature ageing and obtains silicon-aluminum sol in 2~12 hours；
3) silicon-aluminum sol obtained in 2) is placed in 120~190 DEG C of points of 2 sections of crystallization in Hydrothermal Synthesiss kettle, second segment temperature compares
One section high 20 DEG C, after 48~168 hours crystallization are complete, centrifugation goes out solid product, then by solid matter with deionized water
Then cyclic washing dries 12~48 hours to neutrality under the conditions of 100~130 DEG C, and small in 400~600 DEG C of roastings 2~10
When remove organic formwork agent, obtain multi-stage porous SSZ-13 molecular screen primary powders；
4) by SSZ-13 molecular screen primary powders and NH4 +Solion carries out 400~600 DEG C of roastings 2 after ion exchange, washing, drying
Obtain within~10 hours the multi-stage porous SSZ-13 molecular sieve catalysts of H types；
Wherein, silicon source is with SiO in the silicon-aluminum sol of the crystallization that feeds intake2Meter, silicon source is with Al2O3Meter, organic formwork agent in terms of SDA, long-chain
In terms of DQA, crystallization feed molar proportioning is bi-quaternary ammonium salt：Na2O：SiO2：Al2O3：SDA：DQA：H2O=0.35~0.65：
1：0.0025~0.01：0.05~0.5：0.01~0.05：10~50.
2. synthetic method according to claim 1, it is characterised in that：The long-chain Bis-quaternary Ammonium Salt Surfactant formula is
[CnH2n+1-N+(CH3)2-(CH2)4-N+(CH3)2-C4H9]X2Or [CmH2m+1-N+(CH3)2-(CH2)6-N+(CH3)2-C6H13]Y2, its
Middle n is selected from 16,18,22；M is selected from 16,18,22；X is selected from Br, Cl, I；Y is selected from Br, Cl, I.
3. synthetic method according to claim 1, it is characterised in that：Silicon source is white carbon, active silica, silicic acid
One kind of sodium, silester or methyl silicate.
4. synthetic method according to claim 1, it is characterised in that：Silicon source be aluminium isopropoxide, sodium metaaluminate, aluminum nitrate,
One kind of aluminum sulfate, aluminium chloride, aluminium hydroxide or boehmite.
5. synthetic method according to claim 1, it is characterised in that：Organic formwork agent is N, N, N- front three in step (1)
Any one or two kinds in base -1- adamantane ammonium hydroxide, benzyltrimethylammonium hydroxide.
6. synthetic method according to claim 1, it is characterised in that：Crystal pattern is dynamic crystallization or quiet in step (1)
State crystallization.
7. synthetic method according to claim 1, it is characterised in that：NH in step (4)4 +Solion is the salt of ammonium ion
Solution, selected from the aqueous solution of ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 0.5~1.5mol/L.
8. the SSZ-13 molecular sieves of the multistage pore canal that the synthetic method as described in claim 1~7 any one is obtained, the molecule
Sieve aperture road exists<2nm, 2~5nm and 5~15nm scopes have pore-size distribution, micro pore volume>0.20cm3/ g, mesopore volume>
0.35cm3/ g, specific surface area>400m2/g。
9. application of the molecular sieve as claimed in claim 8 in methanol-to-olefins or tail gas catalyzed reduction reaction.
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| CN201710160763.6A CN106904636B (en) | 2017-03-17 | 2017-03-17 | The SSZ-13 molecular sieve and its synthetic method of a kind of multi-stage artery structure with micropore-mesopore and application |
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| CN106745036A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | With the microporous mesoporous molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN106745035A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | A kind of molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN108059172A (en) * | 2017-12-13 | 2018-05-22 | 山东齐鲁华信高科有限公司 | The preparation method of H-SSZ-13 molecular sieves |
| CN109231232A (en) * | 2018-11-07 | 2019-01-18 | 太原理工大学 | Micro--meso-hole structure Beta molecular sieve, micro--mesoporous Beta molecular sieve catalyst of Ni base and preparation method thereof |
| CN109985663A (en) * | 2017-12-29 | 2019-07-09 | 华中科技大学 | The method that the Cu-SSZ-13 molecular sieve of a kind of pair of one kettle way fabricated in situ is post-processed |
| CN110395744A (en) * | 2019-07-11 | 2019-11-01 | 内蒙古工业大学 | A kind of method of the lower preparation octahedron 4A molecular sieve of external electric field factor effect |
| CN110665538A (en) * | 2019-12-06 | 2020-01-10 | 山东国瓷功能材料股份有限公司 | Modified CHA type molecular sieve and preparation method and application thereof |
| CN111233002A (en) * | 2020-02-20 | 2020-06-05 | 山东齐鲁华信高科有限公司 | Method for preparing SSZ-13 molecular sieve from Beta molecular sieve |
| CN111302353A (en) * | 2020-02-11 | 2020-06-19 | 中科催化新技术(大连)股份有限公司 | SAPO-34 molecular sieve with composite meso-microporous structure and synthesis method thereof |
| CN111960434A (en) * | 2020-08-10 | 2020-11-20 | 中触媒新材料股份有限公司 | CHA-type chabazite molecular sieve and synthesis method and application thereof |
| CN112978749A (en) * | 2019-12-02 | 2021-06-18 | 中国石油天然气股份有限公司 | Preparation method and application of multi-stage-hole SSZ-13 molecular sieve and method for preparing olefin from methanol |
| CN115181035A (en) * | 2021-03-17 | 2022-10-14 | 天津师范大学 | Hierarchical pore TS-1 molecular sieve with intra-crystal micropore-ultramicropore-mesopore and preparation method and application thereof |
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| CN106745035A (en) * | 2017-03-17 | 2017-05-31 | 中触媒新材料股份有限公司 | A kind of molecular sieves of multi-stage porous SSZ 13 and its synthetic method and application |
| CN106745035B (en) * | 2017-03-17 | 2019-04-05 | 中触媒新材料股份有限公司 | A kind of multi-stage porous SSZ-13 molecular sieve and its synthetic method and application |
| CN106745036B (en) * | 2017-03-17 | 2019-08-06 | 中触媒新材料股份有限公司 | Multi-stage porous SSZ-13 molecular sieve and its synthetic method and application with micropore-mesopore |
| CN108059172A (en) * | 2017-12-13 | 2018-05-22 | 山东齐鲁华信高科有限公司 | The preparation method of H-SSZ-13 molecular sieves |
| CN108059172B (en) * | 2017-12-13 | 2020-07-10 | 山东齐鲁华信高科有限公司 | Preparation method of H-SSZ-13 molecular sieve |
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| CN112978749B (en) * | 2019-12-02 | 2022-11-04 | 中国石油天然气股份有限公司 | Preparation method and application of multi-stage-hole SSZ-13 molecular sieve and method for preparing olefin from methanol |
| CN112978749A (en) * | 2019-12-02 | 2021-06-18 | 中国石油天然气股份有限公司 | Preparation method and application of multi-stage-hole SSZ-13 molecular sieve and method for preparing olefin from methanol |
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| CN115181035A (en) * | 2021-03-17 | 2022-10-14 | 天津师范大学 | Hierarchical pore TS-1 molecular sieve with intra-crystal micropore-ultramicropore-mesopore and preparation method and application thereof |
| CN115181035B (en) * | 2021-03-17 | 2024-02-23 | 天津师范大学 | Hierarchical pore TS-1 molecular sieve with micropores, polar micropores and mesopores in crystal, and preparation method and application thereof |
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