CN101239325A - Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof - Google Patents
Montmorillonite/ZSM-5 molecular sieve composite material and preparation thereof Download PDFInfo
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- CN101239325A CN101239325A CNA2007100103879A CN200710010387A CN101239325A CN 101239325 A CN101239325 A CN 101239325A CN A2007100103879 A CNA2007100103879 A CN A2007100103879A CN 200710010387 A CN200710010387 A CN 200710010387A CN 101239325 A CN101239325 A CN 101239325A
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Abstract
The present invention provides a montmorillonite/ZSM-5 molecular sieve composite material and its preparing method. The montmorillonite/beta molecular sieve composite material is prepared by evenly mixing montmorillonite with ZSM-5 molecular sieve gelatin, then processing home position crystallization, and via filtering, washing and drying. The composite material have structure characteristics of the montmorillonite and the molecular sieve at the same time, the montmorillonite and the molecular sieve are alternative. The synthetic montmorillonite/ZSM-5 molecular sieve have characteristics of small crystal grain molecular sieve by controlling the synthetic course and the conditions. The preparing method is simple, the easily separating, the molecular sieve composite material has better water-heat stability. The composite material are mainly used for all kinds of catalysts and absorption agents, especially the preparing of hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of new catalytic material and preparation method thereof, imvite specifically/ZSM-5 molecular sieves compound material and preparation method thereof.
Background technology
ZSM-5 molecular sieve with small crystal grains has unique topological structure, heat endurance and more acidity preferably, the catalytic reaction good stability has good anti-coking, be widely used in catalytic fields such as PETROLEUM PROCESSING and fine chemistry industry, developed into a kind of novel catalysis material in recent years rapidly.
CN1303816A discloses the method that a kind of legal system that leads is equipped with the small-grain ZSM-5 zeolite, and its characteristics are to prepare a kind of highly active directed agents and replace organic formwork agent, and crystallization process adopts two sections temperature programmings.CN1608990A has introduced the method that a kind of nano-scale contains hetero atom ZSM-5 zeolite, it is characterized in that, under the room temperature with aluminium source or hetero atom source, alkali metal salt, NaOH, template agent and water evenly mix, stir mixed liquor to clarification, in mixed liquor, drip the silicon source, it is even to continue to be stirred to mixed liquor, obtain sial or silicon-hetero atom colloidal sol, with at room temperature still aging 1～2 day of this colloidal sol, change in the polytetrafluoroethylene (PTFE) reactor of stainless steel inner lining, 80～120 ℃ of following crystallization 3～10 days, product was through suction filtration, washing is to neutral, oven dry, at 540 ℃ of roasting 6h, what obtain nano-scale contains hetero atom ZSM-5 molecular sieve.
Though take above method can make the molecular sieve of nano-scale, small crystal grain molecular sieve is easy to take place sintering in separation process and in catalytic reaction process, be gathered into bigger particle, influences its catalysis efficiency.An effective solution directly loads on molecular sieve on the various carriers by original position is synthetic exactly.Existing both at home and abroad at present report about support type ZSM-5 composite, and most of carrier all is to adopt ceramic honey comb material or metal alloy.
CN1269262A discloses a kind of method that original position is synthesized the ZSM-5 molecular sieve on the block honeycomb ceramic carrier of cordierite, at first ceramic honey comb dip-coating one deck is contained Al
2O
3, SiO2 and Na
2The coagulant liquid of O is characterized in that: the carrier after the dip-coating is depressed crystallization at 150～200 ℃ the organic amine and the mixing saturated vapor of water, 3～10 days time, make the ZSM-5 molecular sieve with the mode growth in situ of gas-solid inversion of phases in carrier surface.
CN1059673A discloses the organically NEW TYPE OF COMPOSITE zeolite catalyst of embedding life on vermiculite of a kind of zeolite, its preparation method is that vermiculite, NaOH, sodium aluminate, organic amine and water are mixed under vigorous stirring, in 140-180 ℃ of crystallization, after crystallization finishes after filtration, the washing, the oven dry, the gained powder crystal is after roasting removes amine, exchange with ammonium nitrate solution, more after filtration, washing, oven dry, roasting promptly get composited HZSM-5 zeolite/vermiculite catalyst.
The method that above-mentioned patent adopted is the same in essence, all is carrier is joined in the molecular sieve gel, and hydrothermal crystallizing forms then.Its difference is that used carrier is different.Obviously also have other material to can be used as the carrier of composite.Imvite itself has higher heat endurance and hydrothermal stability, and the cation of interlayer has interchangeability simultaneously, can regulate the Acidity of Aikalinity of material itself.And owing to distinctive 2: 1 layer structure of imvite supports for it, thereby can form material with mesoporous or macroporous structure.If the ZSM-5 molecular sieve is grown in the imvite, can obtain a kind of novel catalysis material, promptly be supported on the ZSM-5 molecular sieve with small crystal grains on the imvite microballoon.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of imvite/ZSM-5 molecular sieves compound material, and another object of the present invention provides the preparation method of a kind of this imvite/ZSM-5 molecular sieves compound material.
Consisting of of imvite of the present invention/ZSM-5 molecular sieves compound material: the weight with composite is benchmark, and the content of ZSM-5 molecular sieve is 10wt%～70wt%, is preferably 30wt%～50wt%; ZSM-5 zeolite crystal size is 0.1～0.3 μ m, and silica alumina ratio is 10～20, and this composite has the XRD spectra feature of imvite and ZSM-5 molecular sieve simultaneously.SEM (SEM) and X-ray diffraction (XRD) to this composite the analysis showed that, imvite and ZSM-5 molecular sieve alternate in this compound, and imvite is dispersed in the molecular sieve matrix, and zeolite crystal " growth " is around clay.
Characterize on D/max2500 type XRD instrument that the character of composite is produced in Japan company of science (experiment condition is: voltage 40Kv, electric current 80mA, 6 °/min scanning) and the JSM-6301F of company of the NEC awkward silence at a meeting SEM.
The preparation method of imvite of the present invention/ZSM-5 molecular sieves compound material is:
Preparation mole proportioning is (8～20) SiO
2: (TPA)
2O: (1～4) Na
2O: (350～600) H
2The directed agents of O, and according to (20～50) SiO
2: Al
2O
3: (2～5) Na
2O: (800～1200) H
2The mole proportioning of O prepares the ZSM-5 molecular sieve gel, join the directed agents for preparing in the gel and stir, add the imvite microballoon then, after mixing, 160～190 ℃ of following hydrothermal crystallizings 20～60 hours, preferably 24～48 hours, take out above-mentioned product and separate, wash and drying, promptly obtain described imvite/ZSM-5 composite.
The addition of wherein said directed agents accounts for the 2v%～10v% of molecular sieve gel volume, is preferably 4v%～8v%.The weight ratio of imvite microballoon and reaction gel (the mixed gel of molecular sieve gel and directed agents) is (30～60): (70～40) are preferably (40～50): (60～50).
Compared with prior art, the present invention has following characteristics:
1, process is simple.The present invention uses high activity directed agents and imvite effect, grows the little crystal grain of ZSM-5 molecular sieve at the imvite spatial induction.
2, good hydrothermal stability adopts the ZSM-5 molecular sieve of the inventive method preparation to be grown on the imvite microballoon, and the ZSM-5 hydrothermal stability of molecular sieve that this supports is good, easy-sintering not in the catalytic reaction process.
3, separate easily.Because the present invention directly is grown in ZSM-5 molecular sieve with small crystal grains on the imvite microballoon, has solved the problem that industrial large-scale production small crystal grain molecular sieve is difficult to separate.
4, imvite is a kind of lamellar clay, and wide material sources are cheap and easy to get.Be the very big clays of a kind of reserves of China, cost of material is very low.
Description of drawings
Fig. 1 is the XRD spectra of the embodiment of the invention 1 gained sample.
Fig. 2 is the electromicroscopic photograph of the embodiment of the invention 1 gained sample.
Fig. 3 is the electromicroscopic photograph after the embodiment of the invention 1 gained sample water heat treatment.
The specific embodiment
The concrete preparation method of imvite of the present invention/ZSM-5 molecular sieves compound material is as follows:
(1) preparation of directed agents: with silicon source, template agent, NaOH and water according to (8～20) SiO
2: (TPA)
2O: (1～4) Na
2O: (350～600) H
2The mole proportioning of O is mixed under room temperature and mechanical agitation condition, continues to stir to mix until raw material, changes over to then in the synthetic bullet, in 90～110 ℃ of general heating 10～20 hours, preferably 16～20 hours, makes directed agents under the airtight condition.Wherein said silicon source is white carbon, Ludox or silicic acid; Said template agent is a TPAOH.
(2) preparation of ZSM-5 molecular sieve gel: with silicon source, aluminium source, NaOH and water according to (20～50) SiO
2: Al
2O
3: (2～5) Na
2O: (800～1200) H
2The mole proportioning of O is mixed under room temperature and mechanical agitation condition, continues to stir to mix until raw material, obtains Alusil; Described silicon source is white carbon, Ludox, silicic acid, ethyl orthosilicate or silica gel; Described aluminium source is sodium metaaluminate, aluminium hydroxide or aluminium isopropoxide.
(3) directed agents that step (1) is obtained joins in the gel that step (2) makes and stirs, and obtains reaction gel; The addition of directed agents is the 2v%～10v% of gel volume, is preferably 4v%～8v%.
(4) add the imvite microballoon, wherein the weight ratio of imvite and reaction gel is (30～60): (70～40), preferably (40～50): (60～50), stirring at room 0.5～2 hour, then 160～190 ℃ of following hydrothermal crystallizings 20～60 hours, be preferably 40～45 hours, take out above-mentioned product and separate, wash and drying, obtain imvite/ZSM-5 molecular sieves compound material.
The described separation of step (4), washing and drying condition are the state of the art.Separation as described can adopt centrifugation or suction filtration to separate, and described washing is meant and spends deionised water 1～6 time that described drying is meant at 50～180 ℃ to descend dry 10～30 hours, is Powdered until composite.
Compounding ingredients imvite among the present invention is generally the refining imvite after natural montmorillonite or the flotation.Described method for floating is: get natural calcium base or sodium-based montmorillonite, by weight 1: (5～20) add deionized water and are mixed with slurries, stirred 30 minutes～24 hours down in room temperature～95 ℃ then, sedimentation 30 minutes～24 hours, get supernatant liquid, add flocculant, isolate the redistilled calcium base montmorillonite, ℃ following drying for standby in room temperature～150.
Preferably by the following method imvite is carried out after the modification as compounding ingredients:
The sodium modification: get natural calcium base or redistilled calcium base montmorillonite, add deionized water and sodium agent and be mixed with slurries, ℃ following the stirring 30 minutes～24 hours in room temperature～95 isolated the refining sodium-base imvite, ℃ following drying for standby in room temperature～150 then.Sodium agent commonly used comprises NaCl, NaNO
3, NaSO
4Deng reagent, calcium-base montmorillonite: sodium agent: the ratio of deionized water weight is 1: (0.1～0.6): (5～20).
The acid modification: imvite, deionized water and ammonium salt (or acid) are with weight ratio 1: (0.1～0.6): (5～20) make slurries, ℃ stir 30 minutes～24 hours down in room temperature～95, separate, and washing, ℃ dry down in room temperature～150.Wherein ammonium salt comprises NH
4Cl, NH
4NO
3, (NH
4)
2SO
4Deng, acid is hydrochloric acid, sulfuric acid, nitric acid etc.If what add is ammonium salt, need be standby after 1～5 hour 300～700 ℃ of following roastings
Organically-modified: with imvite, quaternary ammonium salt and deionized water with weight ratio 1: (0.1～0.6): (5～20) make slurries, ℃ stir 30 minutes～24 hours down in room temperature～95, separate washing, ℃ following drying for standby in room temperature～150.Wherein organic ammonium salt comprises softex kw, OTAC etc.
Pillared modification: with between bigger inorganic hydroxyl cation and cheating engaging layer as Na
+, K
+And Ca
+Exchange, these hydroxyl species are the polymerization that formed by Al, Zr, Cr, Ca, Si, Ti, Fe and their hybrid metal salt hydrolysis or oligomeric hydroxy metal cation, sample after the exchange reaction passes through careful heat treatment again, make it dehydrogenation and dehydration, form stable metal oxide post, thereby lamella is strutted, form two-dimentional duct with an opening.
The modification of porous isomery: get acidity or organo montmorillonite, add organic amine, behind the vigorous stirring reaction 30min, add TEOS, stirring reaction 2～8h under the room temperature separates, drying, and 300～700 ℃ of roasting 3～8h remove organic matter, obtain the imvite of porous isomery.Wherein imvite: organic amine: the TEOS mol ratio is 1: 50: (50～200).
Imvite provided by the invention/ZSM-5 molecular sieves compound material is mainly used in all kinds of catalyst and adsorbent, especially the catalyst of hydrogenation aspect.
Set forth technical scheme of the present invention below in conjunction with embodiment, but be not limited to the present invention.
Embodiment 1
(1) preparation directed agents:
1. take by weighing 13.8g NaOH, be dissolved in the 710.3g distilled water, add the 117.0g TPAOH aqueous solution then, the electromagnetic agitation mixing.2. get 158.9g silicic acid and join in the solution, electromagnetic agitation is even.3. above-mentioned solution magnetic agitation was packed in the synthetic bullet after 0.5 hour, 100 ℃ of following ageings 16 hours, made directed agents.
(2) the synthetic and growth on the imvite microballoon of ZSM-5 molecular sieve.
1. take by weighing 867.8g distilled water, dissolving 10.2g NaOH and 10.3g sodium aluminate stir.2. 124g silicic acid progressively adds in the solution under fully stirring, and at room temperature fiercely stirs.3. the 30ml directed agents is joined in the above-mentioned solution, add 60g imvite microballoon again, stirring at room 0.5 hour.180 ℃ of following hydrothermal crystallizings 35 hours.
(3) take out that above-mentioned product separates, suction filtration, washing, drying, obtain imvite/ZSM-5 molecular sieves compound material.
The XRD spectra of this composite and sem photograph are as shown in Figure 1, 2.As can be seen from Figure 1, the characteristic peak of imvite and ZSM-5 molecular sieve is quite obvious in this composite.As can be seen from Figure 2, ZSM-5 zeolite crystal " growth " is around montmorillonite particle.The mechanical dimension of ZSM-5 molecular sieve concentrates on about 100nm mostly, belongs to the ZSM-5 molecular sieve with small crystal grains category.Therefore, by control, can synthesize imvite/ZSM-5 molecular sieve with small crystal grains composite to building-up process and condition.By the XRD quantitative analysis as can be known, the content of ZSM-5 molecular sieve in composite is approximately 35%.By calculate cell parameter as can be known in the composite silica alumina ratio of ZSM-5 molecular sieve be 14.Fig. 3 is a composite through 600 ℃ of hydrothermal treatment consists resulting XRD spectra after 2 hours.Comparison diagram 1 as can be seen, the XRD characteristic peak of composite changes not quite before and after the hydrothermal treatment consists, the good hydrothermal stability of composite is described, not easy-sintering.
Embodiment 2
(1) preparation directed agents:
1. take by weighing 13.8g NaOH, be dissolved in the 710.3g distilled water, add the 117.0g 25% TPAOH aqueous solution then, the electromagnetic agitation mixing.2. take by weighing 158.9g silicic acid and join in the solution, electromagnetic agitation is even.3. above-mentioned solution magnetic agitation was packed in the synthetic bullet after 0.5 hour, 100 ℃ of following ageings 16 hours, made directed agents.
(2) the synthetic and growth on the imvite microballoon of ZSM-5 molecular sieve.
1. take by weighing 867.8g distilled water, dissolving 8.8g NaOH and 10.3g sodium aluminate stir.2. 113.1g silicic acid is progressively added in the solution under fully stirring, and at room temperature fiercely stir.3. the 30ml directed agents is joined in the above-mentioned solution, add 40g imvite microballoon again, stirring at room 0.5 hour.180 ℃ of following hydrothermal crystallizings 40 hours.
(3) take out that above-mentioned product separates, suction filtration, washing, drying, obtain imvite/ZSM-5 molecular sieves compound material.The content of ZSM-5 molecular sieve in composite is approximately 45%.By calculate cell parameter as can be known in the composite silica alumina ratio of ZSM-5 molecular sieve be 12.5.
Embodiment 3
(1) preparation directed agents:
1. take by weighing 13.8g NaOH, be dissolved in the 710.3g distilled water, add the 117.0g 25% TPAOH aqueous solution then, the electromagnetic agitation mixing.2. take by weighing 158.9g silicic acid and join in the solution, electromagnetic agitation is even.3. above-mentioned solution magnetic agitation was packed in the synthetic bullet after 0.5 hour, 100 ℃ of following ageings 16 hours, made directed agents.
(2) the synthetic and growth on the imvite microballoon of ZSM-5 molecular sieve.
1. take by weighing 867.8g distilled water, dissolving 8.8g NaOH and 10.3g sodium aluminate stir.2. 113.1g silicic acid is progressively added in the solution under fully stirring, and at room temperature fiercely stir.3. the 30ml directed agents is joined in the above-mentioned solution, add 60g imvite microballoon again, stirring at room 0.5 hour was 180 ℃ of following hydrothermal crystallizings 40 hours.
(3) take out that above-mentioned product separates, suction filtration, washing, drying, obtain imvite/ZSM-5 molecular sieves compound material.The content of ZSM-5 molecular sieve in composite is approximately 33wt%.By calculate cell parameter as can be known in the composite silica alumina ratio of ZSM-5 molecular sieve be 13.
Embodiment 4
(1) preparation directed agents:
1. take by weighing 13.8g NaOH, be dissolved in the 710.3g distilled water, add the 117.0g TPAOH aqueous solution then, the electromagnetic agitation mixing.2. take by weighing 158.9g silicic acid and join in the solution, electromagnetic agitation is even.3. above-mentioned solution magnetic agitation was packed in the synthetic bullet after 0.5 hour, 100 ℃ of following ageings 16 hours, made directed agents.
(2) the synthetic and growth on the imvite microballoon of ZSM-5 molecular sieve.
1. take by weighing 810.8g distilled water, dissolving 8.4g NaOH and 9.3g sodium aluminate stir.2. 103.1g silicic acid is progressively added in the solution under fully stirring, and at room temperature fiercely stir.3. the 30ml directed agents is joined in the above-mentioned solution, add 40g imvite microballoon again, stirring at room 0.5 hour was 180 ℃ of following hydrothermal crystallizings 35 hours.The content of ZSM-5 molecular sieve in composite is approximately 48%.By calculate cell parameter as can be known in the composite silica alumina ratio of ZSM-5 molecular sieve be 12.
(1) preparation directed agents:
1. take by weighing 13.8g NaOH, be dissolved in the 710.3g distilled water, add the 117.0g TPAOH aqueous solution then, the electromagnetic agitation mixing.2. take by weighing 158.9g silicic acid and join in the solution, electromagnetic agitation is even.3. above-mentioned solution magnetic agitation was packed in the synthetic bullet after 0.5 hour, 100 ℃ of following ageings 16 hours, made directed agents.
(2) the synthetic and growth on the imvite microballoon of ZSM-5 molecular sieve.
1. take by weighing 610.8g distilled water, dissolving 6.4g NaOH and 8.3g sodium aluminate stir.2. 93.1g silicic acid is progressively added in the solution under fully stirring, and at room temperature fiercely stir.3. the 30ml directed agents is joined in the above-mentioned solution, add 40g imvite microballoon again, stirring at room 0.5 hour was 180 ℃ of following hydrothermal crystallizings 40 hours.The content of ZSM-5 molecular sieve in composite is approximately 44%.By calculate cell parameter as can be known in the composite silica alumina ratio of ZSM-5 molecular sieve be 11.5.
Claims (10)
1. imvite/ZSM-5 molecular sieves compound material, it is characterized in that, weight with composite is benchmark, the content of ZSM-5 molecular sieve is 10wt%～70wt%, the grain size of ZSM-5 molecular sieve is 0.1～0.3 μ m, silica alumina ratio is 10～20, and this composite has the XRD spectra feature of imvite and ZSM-5 molecular sieve simultaneously.
2. according to the described composite of claim 1, it is characterized in that the content of described ZSM-5 molecular sieve is 30wt%～50wt%.
3. the preparation method of the described imvite of claim 1/ZSM-5 molecular sieves compound material, at first preparation mole proportioning is (8～20) SiO
2: (TPA)
2O: (1～4) Na
2O: (350～600) H
2The directed agents of O, and according to (20～50) SiO
2: Al
2O
3: (2～5) Na
2O: (800～1200) H
2The mole proportioning of O prepares the ZSM-5 molecular sieve gel, the directed agents for preparing is joined in the gel, stir and obtain reaction gel, add the imvite microballoon then, after mixing, 160～190 ℃ of following hydrothermal crystallizings 20～60 hours, take out above-mentioned product and separate, wash and dry, promptly obtain described imvite/ZSM-5 composite.
4. according to the described preparation method of claim 3, it is characterized in that the addition of described directed agents accounts for the 2v%～10v% of molecular sieve gel volume, the weight ratio of imvite microballoon and reaction gel is (60～30): (40～70).
5. according to the described preparation method of claim 3, it is characterized in that the addition of described directed agents is 4v%～8v%.
6. according to the described preparation method of claim 3, it is characterized in that the preparation method of described directed agents is: with silicon source, template agent, NaOH and water according to (8～20) SiO
2: (TPA)
2O: (1～4) Na
2O: (350～600) H
2The mole proportioning of O is mixed under room temperature and mechanical agitation condition, continues to stir to mix until raw material, changes over to then in the synthetic bullet, makes directed agents in 10～20 hours in 90～110 ℃ of heating under the airtight condition.
7. according to the described preparation method of claim 6, it is characterized in that described silicon source is white carbon, Ludox or silicic acid, said template agent is a TPAOH.
8. according to the described preparation method of claim 3, it is characterized in that the preparation method of described ZSM-5 molecular sieve gel is: with silicon source, aluminium source, NaOH and water according to (20～50) SiO
2: Al
2O
3: (2～5) Na
2O: (800～1200) H
2The mole proportioning of O is mixed under room temperature and mechanical agitation condition, continues to stir to mix until raw material, obtains molecular sieve gel.
9. according to the described preparation method of claim 8, it is characterized in that described silicon source is white carbon, Ludox, silicic acid, ethyl orthosilicate or silica gel; Described aluminium source is sodium metaaluminate, aluminium hydroxide or aluminium isopropoxide.
10. according to the described preparation method of claim 3, it is following dry 10～30 hours to it is characterized in that described drying is meant at 50～180 ℃.
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| CN103041847A (en) * | 2012-12-25 | 2013-04-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
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| CN112427010A (en) * | 2020-11-06 | 2021-03-02 | 盐城工学院 | HZSM-5 molecular sieve gas adsorbent synthesized by using attapulgite, and preparation method and application thereof |
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| CN1160154C (en) * | 1999-04-07 | 2004-08-04 | 中国科学院大连化学物理研究所 | In-site molecular sieve synthesizing process on lumpy honeycomb cordierite ceramic carrier |
| CN1100005C (en) * | 2000-06-28 | 2003-01-29 | 中国科学院山西煤炭化学研究所 | Method for quickly synthesizing small crystal grain ZSM-5 molecular sieve by using guide agent method |
| CN100389067C (en) * | 2005-12-30 | 2008-05-21 | 中国石油大学(北京) | ZSM-5 type molecular sieve and method for preparing the same |
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| CN103041847B (en) * | 2012-12-25 | 2015-06-17 | 辽宁师范大学 | In-situ synthesized catalyst by polyoxometallate and silicon-containing molecular sieve, as well as preparation method and application of same |
| CN107519921A (en) * | 2016-06-21 | 2017-12-29 | 中国石油天然气股份有限公司 | Y/Sm2O3ZSM-22/ZSM-5/ASA composite material and preparation method thereof |
| CN107519921B (en) * | 2016-06-21 | 2019-10-11 | 中国石油天然气股份有限公司 | Y/Sm2O3ZSM-22/ZSM-5/ASA composite material and preparation method thereof |
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| CN112427010B (en) * | 2020-11-06 | 2023-05-23 | 盐城工学院 | HZSM-5 molecular sieve gas adsorbent synthesized by attapulgite, and preparation method and application thereof |
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