CN102259884A - Organic template-free synthesis method for beta molecular sieve through hydro-thermal treatment - Google Patents
Organic template-free synthesis method for beta molecular sieve through hydro-thermal treatment Download PDFInfo
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- CN102259884A CN102259884A CN 201110154663 CN201110154663A CN102259884A CN 102259884 A CN102259884 A CN 102259884A CN 201110154663 CN201110154663 CN 201110154663 CN 201110154663 A CN201110154663 A CN 201110154663A CN 102259884 A CN102259884 A CN 102259884A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000010335 hydrothermal treatment Methods 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title abstract 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 23
- 239000010457 zeolite Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 238000009415 formwork Methods 0.000 claims description 24
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000000571 coke Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000007233 catalytic pyrolysis Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012374 filter flush Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to preparation of crystalline aluminosilicate zeolite, and aims to provide an organic template-free synthesis method for a beta molecular sieve through hydro-thermal treatment. The method comprises the following steps of: (1) exchanging most of Na<+> in a sodium beta molecular sieve obtained by the organic template-free synthesis method by using NH4<+>; and (2) washing and filtering the molecular sieve subjected to NH4<+> exchange, pressing a filter cake, putting into a crucible, and roasting at the temperature of between 500 and 900 DEG C in 100-percent water vapor atmosphere. The silicon-aluminum ratio of the beta molecular sieve synthesized without an organic template through the hydro-thermal treatment is improved to a certain extent, and crystallinity is basically not reduced along with the formation of mesopores; in vacuum gas oil (VGO) catalytic pyrolysis reaction, the molecular sieve effectively reduces cokes, and improves the yield of a product with high added value simultaneously; and the molecular sieve can be directly prepared into a catalytic cracking catalyst, can be subjected to ammonium exchange to further reduce the amount of Na2O and then is prepared into the catalytic cracking catalyst, and can be combined with a chemical aluminum extracting and silicon supplementing method to be prepared into a catalyst with higher performance.
Description
Technical field
The present invention relates to the crystalline aluminosilicate prepare zeolite, belong to inorganic chemistry, physical chemistry, materials chemistry, catalytic chemistry and field of chemical engineering, particularly hydrothermal treatment consists does not have the method for organic formwork synthetic Beta molecular sieve.
Background technology
The catalytic cracking of petroleum hydrocarbon is the main means of producing gasoline, diesel oil.The normal activity of such catalysts component of using of catalytic cracking reaction is exactly the overtemperature Y zeolite that Y molecular sieve obtains after treatment on the current industrial; Because of it has satisfied the requirement of mixing refining residual oil and energy voluminous stop bracket gasoline of people to catalyzer more, and extensive studies and application have been arrived.
With respect to the Y zeolite molecular sieve, the Beta zeolite is unique molecular sieve with three-dimensional, twelve-ring aperture structure in the high-silica zeolite, have and the close adsorptive poweies of large pore molecular sieve such as X, Y type, have higher silica alumina ratio than faujusite, be used as a very important catalyzer and be applied in petroleum refining and chemical field.Known to though the technology of preparing of USY is familiar with by people already, traditional B eta molecular sieve after high-temperature water vapor is handled, degree of crystallinity obviously reduces even becomes amorphous, therefore the report of handling traditional B eta molecular sieve about high-temperature water vapor does not almost have.
People such as Xiao Fengshou successfully synthesize Beta zeolite molecular sieve (Chinese invention patent publication number 101249968A) under the organic-free template condition.Compare with traditional B eta molecular sieve, this Beta molecular sieve has hydrothermal stability height, characteristics that silica alumina ratio is low.Though the low silica-alumina ratio characteristics of the Beta molecular sieve that this method is prepared make it have more acidic site, also easily cause the generation of more coke, cause the easy inactivation of catalyzer, have limited its application in catalyzed reaction.
Therefore, hydrothermal treatment consists does not have organic formwork synthetic Beta molecular sieve, not only can improve silica alumina ratio, and is produced simultaneously mesoporous, reduces the generation of coke, and can change the products distribution of catalyzed reaction; These all are must consider in the actual industrial.Yet patent and document about this face are not also reported.
Summary of the invention
The objective of the invention is to, provide a kind of hydrothermal treatment consists not have the method for template synthetic Beta zeolite, solve its defective such as low silica-alumina ratio, poor stabilities etc. on some are used,, it is had better use widely so that improve no organic formwork synthetic Beta product quality.
The no organic formwork synthetic Beta molecular sieve that the present invention is directed to, the content that its synthetic method is disclosed referring to Chinese invention patent publication number 101249968A, the present invention repeats no more this.
Method of the present invention comprises step:
(1) will use the NH in ammonium salt or the organic ammonium solution by the sodium type BETA molecular sieve of organic-free template synthetic method acquisition
4 +The Na of 80～98wt% in the molecular sieve is fallen in exchange
+The condition of this ion exchange process is:
According to molecular sieve: (ammonium salt or organic ammonium solution): water=1: (0.5～4.5): the weight ratio of (5～60), with molecular sieve, ammonium salt or the making beating of organic ammonium solution with water evenly, and 60～100 ℃ of exchanges 0.3～6 hour down.
(2) washing, filtration are through NH
4 +Molecular sieve after the exchange compresses filter cake and place crucible then, is placed in the retort furnace, rises to 500～900 ℃ through 1 hour, roasting 1～9 hour, and the water vapour that utilizes filter cake to carry carries out hydrothermal treatment consists; Perhaps zeolite is entered in the stoving oven, roasting is 1～9 hour under 500～900 ℃, 100% water vapour atmosphere condition.
In the step of the present invention (1), be used to provide NH
4 +Ammonium salt be in ammonium chloride, ammonium sulfate or the ammonium nitrate any one, described organic ammonium solution is NH
4Ac.
In the step of the present invention (1), described ion exchange process carries out twice at least, makes the Na in the molecular sieve
2O≤5w%.
The invention has the beneficial effects as follows:
Hydrothermal treatment consists does not have organic formwork synthetic Beta molecular sieve, and not only silica alumina ratio increases, the formation that simultaneous is mesoporous, and also degree of crystallinity does not have to reduce substantially.In the VGO catalytic cracking reaction, the molecular sieve of this invention effectively reduces the generation of coke, has improved the yield of high added value product simultaneously.
Molecular sieve by the present invention's preparation can directly prepare catalytic cracking catalyst, also can carry out the ammonium exchange and further reduce Na
2Prepare catalytic cracking catalyst after the amount of O, also can combine the more excellent catalyzer of processability with chemical aluminium-eliminating and silicon-replenishing method.
Description of drawings
Fig. 1 is the XRD comparison diagram that hydrothermal treatment consists does not have organic formwork synthetic Bcta zeolite front and back in the example 3.
Among the figure, curve 1 is the XRD spectra of no organic formwork synthetic Beta, and curve 2 is the XRD spectra of the no organic formwork synthetic Beta of Hydrogen, and curve 3 is the XRD spectra after 760 ℃ of hydrothermal treatment consists do not have organic formwork synthetic Beta filter cake.
Fig. 2 is the front and back XRD comparison diagram that high-temperature water vapor atmosphere is handled no organic formwork synthetic Bcta zeolite in the example 7.
Among the figure, curve 1 is the XRD spectra before the zeolite treatment, and curve 2 is the XRD figure after 750 ℃ in zeolite, 100% steam-treated.
Fig. 3 is that a kind of hydrothermal treatment consists of the present invention does not have organic formwork synthetic Bcta ZEOLITE BY INFRARED.
Among the figure, curve 1 is industrial Beta ZEOLITE BY INFRARED, and curve 2 does not have infrared spectra behind the organic formwork synthetic Beta for hydrothermal treatment consists, and curve 3 does not have infrared spectra before the organic formwork synthetic Beta for hydrothermal treatment consists.
Fig. 4 is the N after a kind of hydrothermal treatment consists of the present invention does not have organic formwork synthetic Bcta zeolite
2Absorption result.
Fig. 5 is that no organic formwork synthetic Bcta zeolite and former powder respectively account for XRD figure after 50% mechanically mixing after a kind of hydrothermal treatment consists of the present invention.
Embodiment
Below in conjunction with drawings and Examples embodiment of the present invention are further specified, but the present invention is not limited to listed embodiment.Also should be included in interior other any known change of scope that the present invention protects.
Embodiment 1:
(1) 1.0g is not had organic formwork synthetic Beta molecular sieve (by butt) with the aqueous solution that 15g contains the 3.0g inorganic ammonium salt,, contain 1.0g (NH with 15g again after the filtration 100 ℃ of following exchanges 20 minutes
4)
2SO
4Aqueous solution exchange once, filter, SO is removed in washing
4 2-, in 100 ℃ of dryings.
(2) roasting in the middle of: the sample after (1) exchange is positioned in the retort furnace, is warming up to 510 ℃ under the room temperature, constant temperature 3 hours.
(3) baked zeolite is contained 3.0g (NH with 60g
4)
2SO
4The aqueous solution, 100 ℃ of down exchanges 30 minutes, filter the back repeated exchanged once, filter flush away SO
4 2-Ion.
(4) above-mentioned filter cake is compressed, place crucible, be placed in the retort furnace, rose under 560 ℃, 650, the 760 ℃ parts roasting through 1 hour 4 hours.
Embodiment 2:
(1) 1.0g is not had organic formwork synthetic Beta (by butt) with the aqueous solution that 15g contains the 3.0g inorganic ammonium salt,, contain 1.0g (NH with 15g again after the filtration 100 ℃ of following exchanges 20 minutes
4)
2SO
4Aqueous solution exchange once, filter, SO is removed in washing
4 2-, in 100 ℃ of dryings.
(2) roasting in the middle of: the sample after (1) exchange is positioned in the retort furnace, is warming up to 510 ℃ under the room temperature, constant temperature 3 hours.
(3) baked zeolite is contained 3.0g (NH with 60g
4)
2SO
4The aqueous solution, 100 ℃ of down exchanges 30 minutes, filter the back repeated exchanged once, filter flush away SO
4 2-Ion.
(4) zeolite after will exchanging enters in the stoving oven at 560,650,750 and 800 ℃, and roasting is 3～8 hours under the 100% water vapour atmosphere condition.
Embodiment 3:
1.0g is not had organic formwork synthetic Beta (by butt) contain the aqueous solution of 4.0g ammonium nitrate,, use the deionized water filtration washing, after the oven dry, be positioned in the retort furnace, be warming up to 500 ℃ of roastings 3 hours 80 ℃ of exchanges 2 hours down with 50g.Repeat above-mentioned steps once, obtain to contain sodium hydrogen type molecular sieve seldom.
The sample of system contains the aqueous solution of 4.0g ammonium nitrate again with 50g, exchange 1 hour down at 80 ℃, and wet sample is placed in the stoving oven, 800 ℃, handles 1 hour under the 100% water vapour atmosphere condition.
Embodiment 4:
1.0g is not had organic formwork synthetic Beta (by butt) contain the aqueous solution of 4.0g ammonium nitrate,, use the deionized water filtration washing, after the oven dry, be positioned in the retort furnace, be warming up to 500 ℃ of roastings 3 hours 80 ℃ of exchanges 2 hours down with 50g.Repeat above-mentioned steps once, obtain to contain sodium hydrogen type molecular sieve seldom.
The sample of system contains the aqueous solution of 4.0g ammonium nitrate again with 50g, exchange 1 hour down at 80 ℃, and wet sample is placed in the stoving oven, 800 ℃, handles 3 hours under the 100% water vapour atmosphere condition.
Embodiment 5:
1.0g is not had organic formwork synthetic Beta (by butt) contain the aqueous solution of 4.0g ammonium nitrate,, use the deionized water filtration washing, after the oven dry, be positioned in the retort furnace, be warming up to 500 ℃ of roastings 3 hours 80 ℃ of exchanges 2 hours down with 50g.Repeat above-mentioned steps once, obtain to contain sodium hydrogen type molecular sieve seldom.
The sample of system contains the aqueous solution of 4.0g ammonium nitrate again with 50g, exchange 1 hour down at 80 ℃, and wet sample is placed in the stoving oven, 800 ℃, handles 9 hours under the 100% water vapour atmosphere condition.
Example 6～10:
With the no organic formwork synthetic sodium type Beta molecular sieve of degree of crystallinity 〉=85% according to Beta: ammonium salt: water=1: (0.5～4.5): the weight ratio of (5～60) will not have organic formwork synthetic Beta molecular sieve and the making beating of ammonium salt water evenly, and under 60～100 ℃, exchanging 0.3～6 hour, most of Na is fallen in exchange
+Ion (is meant the Na that exchanges 80～98wt% in the molecular sieve
+).Be used to provide NH
4 +Ammonium salt be ammonium chloride, ammonium sulfate, ammonium nitrate, perhaps organic ammonium solution such as NH
4Ac etc.Through NH
4 +Zeolite after the exchange, wash out decon after, zeolite was entered in the stoving oven under 500～900 ℃, 100% water vapour atmosphere condition roasting 1～9 hour.Specific examples sees the following form.
Claims (3)
1. hydrothermal treatment consists does not have the method for organic formwork synthetic Beta molecular sieve, it is characterized in that, comprises step:
(1) will use the NH in ammonium salt or the organic ammonium solution by the sodium type BETA molecular sieve of organic-free template synthetic method acquisition
4 +The Na of 80～98wt% in the molecular sieve is fallen in exchange
+The condition of this ion exchange process is:
According to molecular sieve: (ammonium salt or organic ammonium solution): water=1: (0.5～4.5): the weight ratio of (5～60), with molecular sieve, ammonium salt or the making beating of organic ammonium solution with water evenly, and 60～100 ℃ of exchanges 0.3～6 hour down.
(2) washing, filtration are through NH
4 +Molecular sieve after the exchange compresses filter cake and place crucible then, is placed in the retort furnace, rises to 500～900 ℃ through 1 hour, roasting 1～9 hour, and the water vapour that utilizes filter cake to carry carries out hydrothermal treatment consists; Perhaps zeolite is entered in the stoving oven, roasting is 1～9 hour under 500～900 ℃, 100% water vapour atmosphere condition.
2. method according to claim 1 is characterized in that, in the described step (1), is used to provide NH
4 +Ammonium salt be in ammonium chloride, ammonium sulfate or the ammonium nitrate any one, described organic ammonium solution is NH
4Ac.
3. method according to claim 1 is characterized in that, in the described step (1), described ion exchange process carries out twice at least, makes the Na in the molecular sieve
2O≤5w%.
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|---|---|---|---|
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ID=45006759
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649296A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Preparation method of H beta molecular sieve capable of improving silicon-aluminum ratio |
| CN107324354A (en) * | 2017-05-27 | 2017-11-07 | 江苏有容催化技术研究所有限公司 | A kind of method that hydro-thermal process synthesizes Beta molecular sieves |
| CN113325042A (en) * | 2021-06-11 | 2021-08-31 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256392A (en) * | 1989-06-23 | 1993-10-26 | Fina Technology, Inc. | Modified zeolite beta method of preparation |
| CN1105646A (en) * | 1994-06-29 | 1995-07-26 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
| CN1179994A (en) * | 1996-10-11 | 1998-04-29 | 中国石油化工总公司 | Beta zeolite modification method |
| CN1350981A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | High-silicon beta zeolite and its preparing process |
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
-
2011
- 2011-06-09 CN CN 201110154663 patent/CN102259884A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256392A (en) * | 1989-06-23 | 1993-10-26 | Fina Technology, Inc. | Modified zeolite beta method of preparation |
| CN1105646A (en) * | 1994-06-29 | 1995-07-26 | 中国石油化工总公司抚顺石油化工研究院 | Beta zeolite and preparing method thereof |
| CN1179994A (en) * | 1996-10-11 | 1998-04-29 | 中国石油化工总公司 | Beta zeolite modification method |
| CN1350981A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | High-silicon beta zeolite and its preparing process |
| CN101249968A (en) * | 2008-03-10 | 2008-08-27 | 吉林大学 | Method for synthesizing Beta molecular sieve by organic-free template |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104649296A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Preparation method of H beta molecular sieve capable of improving silicon-aluminum ratio |
| CN107324354A (en) * | 2017-05-27 | 2017-11-07 | 江苏有容催化技术研究所有限公司 | A kind of method that hydro-thermal process synthesizes Beta molecular sieves |
| CN113325042A (en) * | 2021-06-11 | 2021-08-31 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
| CN113325042B (en) * | 2021-06-11 | 2022-11-15 | 吉林大学 | Sodium MTW molecular sieve, preparation method and application thereof, ammonia gas sensor, preparation method and application thereof |
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Application publication date: 20111130 |