CN102730712A - Preparation method of nano GaZSM-5 molecular sieve - Google Patents
Preparation method of nano GaZSM-5 molecular sieve Download PDFInfo
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- CN102730712A CN102730712A CN2012102564654A CN201210256465A CN102730712A CN 102730712 A CN102730712 A CN 102730712A CN 2012102564654 A CN2012102564654 A CN 2012102564654A CN 201210256465 A CN201210256465 A CN 201210256465A CN 102730712 A CN102730712 A CN 102730712A
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Abstract
The invention relates to a preparation method of a nano molecular sieve, particularly a preparation method of a nano GaZSM-5 molecular sieve. The invention aims to solve the problems of high cost and high toxicity in the existing method which uses abundant organic amine compounds as the template agent. The method comprises the following steps: 1. preparing a precrystallized crystal seed; 2. preparing a Ga(OH)3 alkali solution; 3. adding silicasol into the solution of the step 2 to prepare a mixed gel; and 4. adding the precrystallized crystal seed prepared in the step 1 into the gel in the step 3 to obtain the nano GaZSM-5 molecular sieve. The invention uses a small amount of template agent in the precrystallized crystal seed synthesis process, and the consumption of the template agent is only 1/20-1/50 of other synthesis methods as compared with other synthesized GaZSM-5 molecular sieves; and the invention solves the problems of higher molecular sieve production cost, environmental pollution and the like caused by the high price and high toxicity of the organic template agent. The method can be used for synthesizing nano molecular sieves.
Description
Technical field
The invention belongs to the preparation field of zeolite [molecular sieve, be specifically related to the preparation method of nano molecular sieve.
Background technology
But the ZSM-5 molecular sieve is one of present most important molecular sieve catalytic material because of acid site with suitable pore passage structure modulation, good thermostability and hydrothermal stability and outstanding shape selective catalysis effect, is widely used in catalytic fields such as refining of petroleum, petrochemical complex, Coal Chemical Industry and fine chemistry industry.Nano-ZSM-5 molecular sieve is compared with micron order ZSM-5 molecular sieve; Owing to have the intracrystalline rate of diffusion of bigger outer surface area and Geng Gao; The duct is short and have a large amount of intracrystalline pore (secondary pore); Improving the utilization ratio of catalyzer, strengthening the macromole conversion capability, reducing deep reaction, improving aspects such as selectivity and all show more superior performance; In some hydro carbons catalytic conversion reactions, show better activity, selectivity and strong anti-coking deactivation ability and sulfur poisoning-resistant ability, therefore, the ZSM-5 molecular sieve synthetic of relevant nanoscale research in recent years seems quite active.
But because nanometer sial ZSM-5 molecular sieve has very strong B acidity, for aromizing, alkylation etc. have improved production of by-products.Through isomorphous substitution trivalent metal Ga ion is inserted in the skeleton; Not only can reduce the distribution that strength of acid changes acidic site; Reduce the generation of carbon distribution; And can the modulation aperture size, make diffusion improve and the acidity of original position synthetic nanometer GaZSM-5 can be controlled through the ZSM-5 of synthetic Different Silicon gallium ratio, satisfied the requirement of various catalyzed reactions greatly.Adopt the existing report of method of the synthetic GaZSM-5 molecular sieve of template, but be to use a large amount of organic amine compounds as template, not only cost height but also toxicity are big, and synthetic is the micron order molecular sieve.
Summary of the invention
The present invention will solve existing cost height and the toxicity that exists with the method for the synthetic GaZSM-5 molecular sieve of template to reach the big technical problem of molecular sieve particle diameter greatly, thereby a kind of preparation method of nanometer GaZSM-5 molecular sieve is provided.
The preparation method of a kind of nanometer GaZSM-5 molecular sieve of the present invention realizes according to the following steps:
One, takes by weighing 1 part aluminum isopropylate, 42 ~ 108 parts tetrapropyl oxyammonia, 2 ~ 4 parts of deionized waters, 31 ~ 78 parts tetraethoxy, 1 part of Gallium trioxide, 3.2 ~ 8 parts of NaOH, 99 ~ 247 parts deionized water and 64 ~ 159 parts SiO by weight
2Mass content be 30% silicon sol;
Two, in advance the preparation of crystallization crystal seed: a, aluminum isopropylate is joined in the mixing solutions of TPAOH and deionized water, low whipping speed is to stir 20 ~ 50min under the condition of 300 ~ 600r/min, makes A solution; B, low whipping speed are under the condition of 300 ~ 700r/min, tetraethoxy are dropwise joined in the A solution of step a, and after adding, low whipping speed is to stir 3 hours under the condition of 100 ~ 300r/min, processes mixed gel B; C, the mixed gel B that step b is prepared place the stainless closed reactor that has the polytetrafluoroethyllining lining pad; In crystallization under 130 ~ 160 ℃ the temperature condition after 3 ~ 24 hours; Be cooled to 25 ℃, the solid formation washing that filtration is obtained, dry, obtain preparatory crystallization crystal seed;
Three, in Gallium trioxide, add NaOH and deionized water, place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, under 150 ~ 180 ℃ temperature condition, dissolve 1 ~ 3 hour postcooling to 25 ℃, promptly be mixed with solution C;
Four, low whipping speed is in the solution C that step 3 obtains, to add SiO under the condition of 300 ~ 700r/min
2Mass content be 30% silicon sol, add continued and stir 10min, process mixed gel D;
Five, the preparatory crystallization crystal seed that in the mixed gel D that step 4 obtains, adds the step 2 preparation; Low whipping speed is after stirring 10 ~ 20min under the condition of 300 ~ 800r/min; Place the stainless closed reactor that has the polytetrafluoroethyllining lining pad; 160 ~ 185 ℃ of following crystallization 2 ~ 24 hours, be cooled to 25 ℃, after centrifugal, filtration, washing, drying, obtain nanometer GaZSM-5 molecular sieve then;
Wherein, the preparatory crystallization crystal seed in the step 5 accounts for 1% ~ 5% of mixed gel D gross weight;
Centrifugal condition in the step 5 is the centrifugal 5 ~ 10min of 3000 ~ 5000r/min, and wash conditions is with the secondary deionized water washing, washs 3 ~ 5 times, and drying conditions is 100 ~ 120 ℃ of dry 12h.
The present invention uses the template of minute quantity in synthetic preparatory crystallization seed crystal process; Compare with other synthetic GaZSM-5 molecular sieve; The template consumption is 1/20 ~ 1/50 of other compound method; Not only solved higher because of the organic formwork agent price, that toxicity is brought more greatly molecular sieve production cost improve, to problems such as environment pollute, and the synthetic nanometer GaZSM-5 of institute molecular sieve is gentleer more than the acidity of AlZSM-5.The silicon gallium ratio of the present invention's preparation is 60 ~ 150 nanometer GaZSM-5 molecular sieve; Do not need to add again the organic amine template; Simplified ageing process; And shortened the time that crystallization time and roasting crystallization product are removed template, not only can reduce production costs significantly, reduce environmental pollution, and avoid crystallization product to lose the problem of nano material characteristic because of long-time roasting is grown up zeolite crystal effectively.What particularly point out is that employing this patent method can design synthetic silicon gallium than the nanometer GaZSM-5 acidic zeolite catalyzer that in relative broad range, changes, and has prior application prospect in fields such as petrochemical complex, fine chemistry industries than AlZSM-5 molecular sieve.
Description of drawings
Fig. 1 is the XRD spectra of sample GaZSM-5 (150) in the test one;
Fig. 2 is the SEM spectrogram of sample GaZSM-5 (150) in the test one;
Fig. 3 is the XRD spectra of sample GaZSM-5 (100) in the test two;
Fig. 4 is the SEM spectrogram of sample GaZSM-5 (100) in the test two;
Fig. 5 is the XRD spectra of sample GaZSM-5 (60) in the test three;
Fig. 6 is the SEM spectrogram of sample GaZSM-5 (60) in the test three.
Embodiment
Embodiment one: a kind of preparation method of nanometer GaZSM-5 molecular sieve is realized by following step in this embodiment:
One, takes by weighing 1 part aluminum isopropylate, 42 ~ 108 parts tetrapropyl oxyammonia, 2 ~ 4 parts of deionized waters, 31 ~ 78 parts tetraethoxy, 1 part of Gallium trioxide, 3.2 ~ 8 parts of NaOH, 99 ~ 247 parts deionized water and 64 ~ 159 parts SiO by weight
2Mass content be 30% silicon sol;
Two, in advance the preparation of crystallization crystal seed: a, aluminum isopropylate is joined in the mixing solutions of tetrapropyl oxyammonia and deionized water, low whipping speed is to stir 20 ~ 50min under the condition of 300 ~ 600r/min, makes A solution; B, low whipping speed are under the condition of 300 ~ 700r/min, tetraethoxy are dropwise joined in the A solution of step a, and after adding, low whipping speed is to stir 3 hours under the condition of 100 ~ 300r/min, processes mixed gel B; C, the mixed gel B that step b is prepared place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, after 3 ~ 24 hours, are cooled to 25 ℃ in crystallization under 130 ~ 160 ℃ the temperature condition, obtain preparatory crystallization crystal seed;
Three, in Gallium trioxide, add NaOH and deionized water, place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, under 150 ~ 180 ℃ temperature condition, dissolve 1 ~ 3 hour postcooling to 25 ℃, promptly be mixed with solution C;
Four, low whipping speed is in the solution C that step 3 obtains, to add SiO under the condition of 300 ~ 700r/min
2Mass content be 30% silicon sol, add continued and stir 10min, process mixed gel D;
Five, the preparatory crystallization crystal seed that in the mixed gel D that step 4 obtains, adds the step 2 preparation; Low whipping speed is after stirring 10 ~ 20min under the condition of 300 ~ 800r/min; Place the stainless closed reactor that has the polytetrafluoroethyllining lining pad; 160 ~ 185 ℃ of following crystallization 2 ~ 24 hours, be cooled to 25 ℃, after centrifugal, filtration, washing, drying, obtain nanometer GaZSM-5 molecular sieve then;
Wherein, the preparatory crystallization crystal seed in the step 5 accounts for 1% ~ 5% of mixed gel D gross weight;
Centrifugal condition in the step 5 is the centrifugal 5 ~ 10min of 3000 ~ 5000r/min, and wash conditions is with the secondary deionized water washing, washs 3 ~ 5 times, and drying conditions is 100 ~ 120 ℃ of dry 12h.
The present invention uses the template of minute quantity in synthetic preparatory crystallization seed crystal process; Compare with other synthetic GaZSM-5 molecular sieve; The template consumption is 1/20 ~ 1/50 of other compound method; Not only solved higher because of the organic formwork agent price, that toxicity is brought more greatly molecular sieve production cost improve, to problems such as environment pollute, and the synthetic nanometer GaZSM-5 of institute molecular sieve is gentleer more than the acidity of AlZSM-5.The silicon gallium ratio of the present invention's preparation is 60 ~ 150 nanometer GaZSM-5 molecular sieves; Do not need to add again the organic amine template; Simplified ageing process; And shortened the time that crystallization time and roasting crystallization product are removed template, not only can reduce production costs significantly, reduce environmental pollution, and avoid crystallization product to lose the problem of nano material characteristic because of long-time roasting is grown up zeolite crystal effectively.What particularly point out is that employing this patent method can design synthetic silicon gallium than the nanometer GaZSM-5 acidic zeolite catalyzer that in relative broad range, changes, and has prior application prospect in fields such as petrochemical complex, fine chemistry industries than AlZSM-5 molecular sieve.
Embodiment two: what this embodiment and embodiment one were different is: crystallization temperature is 135 ~ 155 ℃ in the c step of step 2, and crystallization time is 5 ~ 24 hours.Other step and parameter are identical with embodiment one.
Embodiment three: what this embodiment was different with embodiment one or two is: crystallization temperature is 140 ℃ in the c step of step 2, and crystallization time is 24 hours.Other step and parameter are identical with embodiment one or two.
Embodiment four: what this embodiment was different with one of embodiment one to three is: solvent temperature is 155 ~ 175 ℃ in the step 3, and dissolution time is 1.5 ~ 2.5 hours.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: what this embodiment was different with one of embodiment one to four is: solvent temperature is 168 ℃ in the step 3, and dissolution time is 2 hours.Other step and parameter are identical with one of embodiment one to four.
Embodiment six: what this embodiment was different with one of embodiment one to five is: crystallization temperature is 165 ~ 180 ℃ in the step 5, and crystallization time is 5 ~ 24 hours.Other step and parameter are identical with one of embodiment one to five.
Embodiment seven: what this embodiment was different with one of embodiment one to six is: crystallization temperature is 170 ℃ in the step 5, and crystallization time is 24 hours.Other step and parameter are identical with one of embodiment one to six.
Through following verification experimental verification beneficial effect of the present invention:
Test one: the preparation method of a kind of nanometer GaZSM-5 molecular sieve of this test realizes according to the following steps:
One, (a) adds the aluminum isopropylate of 0.0465g and the tetrapropyl oxyammonia of 5g in the deionized water of 0.2075g, and 350r/min stirs 30min, makes A solution; (b) teos solution of 3.65g is stirred at 500r/min be added to lentamente down among the step a in the A solution, stir 3 hours formation mixed gel B; (c) the described mixed gel B of step b is placed be sealed in the stainless steel cauldron that has the polytetrafluoroethyllining lining pad, take out after 24 hours in crystallization under 140 ℃ the temperature condition and be cooled to 25 ℃, obtain preparatory crystallization crystal seed;
Two, the deionized water of adding 0.75g NaOH and 23.22g is placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad in the Gallium trioxide of 0.094g, dissolves 2h down at 160 ℃, is cooled to 25 ℃, promptly is mixed with solution C;
Three, the silicon sol that adds 15g in the solution C that under the rotating speed of 500r/min, in step 2, prepares adds and stirs 10min, processes mixed gel D;
Four, in the described mixed gel D of step 3, add the preparatory crystallization crystal seed that step 1 prepares; The crystallization crystal seed accounts for 5% of mixed gel D gross weight in advance; 1000r/min stirs 10min and is placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 170 ℃ of following crystallization 24 hours, is cooled to 25 ℃; With product centrifuging, washing, drying, roasting; Obtain the silicon gallium than the nanometer GaZSM-5 molecular sieve that is 150, be designated as GaZSM-5 (150), its XRD spectra and SEM photo are seen Fig. 1 and Fig. 2 respectively;
Wherein, the middle mixed gel B of step 1 (b) is in molar ratio by 1 mole of Al
2O
3, 150 moles of SiO
2, 53.6 moles of TPAOH and 1625 moles of H
2O forms;
The SiO of silicon sol in the step 3
2Mass content be 30%;
Mixed gel D is by 1 mole of Ga in the step 3
2O
3, 150 moles of SiO
2, 18 moles of Na
2O and 3750 moles of H
2O forms;
The XRD spectra of the nanometer GaZSM-5 molecular sieve of this test one preparation is as shown in Figure 1, can know by figure, and be 22.92 ° at 2 θ, 23.78 ° and 24.24 ° of characteristic diffraction peaks of locating all to have the ZSM-5 molecular sieve do not have other stray crystal;
The SEM photo of the nanometer GaZSM-5 molecular sieve of this test one preparation is as shown in Figure 2, can be known by Fig. 2, and the nanometer GaZSM-5 molecular sieve that this test makes is to be master, accumulative crystal highly with regular cubic structure, and each grain-size is about 30nm.
Test two: the preparation method of a kind of nanometer GaZSM-5 molecular sieve of this test realizes according to the following steps:
The preparation of the preparatory crystallization crystal seed of the step 1 of this test is identical with test one;
Two, the deionized water of adding 0.75g NaOH and 23.22g is placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad in the Gallium trioxide of 0.14g, dissolves 2h down at 160 ℃, is cooled to 25 ℃, promptly is mixed with solution C;
Three, the silicon sol that adds 15g in the solution C that under the rotating speed of 500r/min, in step 2, prepares adds and stirs 10min, processes mixed gel D;
Four, the preparatory crystallization crystal seed that in the described mixed gel D of step 3, adds the step 1 preparation; The crystallization crystal seed accounts for 5% of mixed gel D gross weight in advance; 1000r/min stirs 10min and is placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 170 ℃ of following crystallization 24 hours, is cooled to 25 ℃; With product centrifuging, washing, drying, roasting; Obtain the silicon gallium than the nanometer GaZSM-5 molecular sieve that is 100, be designated as GaZSM-5 (100), its XRD spectra and SEM photo are seen Fig. 3 and Fig. 4 respectively;
Wherein, the middle mixed gel B of step 1 (b) is in molar ratio by 1 mole of Ga
2O
3, 100 moles of SiO
2, 35.7 moles of TPAOH and 1100 moles of H
2O forms;
SiO in the step 3 in the silicon sol
2Mass content be 30%;
Mixed gel D is in molar ratio by 1 mole of Ga in the step 3
2O
3, 100 moles of SiO
2, 12 moles of Na
2O and 2500 moles of H
2The mixed gel D that O forms;
The XRD spectra of the nanometer GaZSM-5 molecular sieve of this test two preparations is as shown in Figure 3, can know by Fig. 3, and be 22.92 ° at 2 θ, 23.78 ° and 24.24 ° of characteristic diffraction peaks of locating all to have the ZSM-5 molecular sieve do not have other stray crystal;
The SEM photo of the nanometer GaZSM-5 molecular sieve of this test two preparations is as shown in Figure 4, can be known by Fig. 4, and the nanometer GaZSM-5 molecular sieve that this test makes is to be the crystal of master, height accumulative nanoscale with regular cubic structure.
Test three: the preparation method of a kind of nanometer GaZSM-5 molecular sieve of this test realizes according to the following steps:
The preparation of the preparatory crystallization crystal seed of the step 1 of this test is identical with test one;
Two, the silicon sol 0.75g NaOH of adding 15g and the deionized water of 23.22g are placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad in the Gallium trioxide of 0.234g; Dissolve 2h down at 160 ℃; Be cooled to 25 ℃, promptly be mixed with solution C;
Three, the silicon sol that adds 15g in the solution C that under the rotating speed of 500r/min, in step 2, prepares adds and stirs 10min, processes mixed gel D;
Four, the preparatory crystallization crystal seed that in the described mixed gel D of step 3, adds the step 1 preparation; The crystallization crystal seed accounts for 5% of mixed gel D gross weight in advance; 1000r/min stirs 10/min and is placed in the stainless closed reactor that has the polytetrafluoroethyllining lining pad, 170 ℃ of following crystallization 24 hours, is cooled to 25 ℃; With product centrifuging, washing, drying, roasting; Obtain the silicon gallium than the nanometer GaZSM-5 molecular sieve that is 60, be designated as GaZSM-5 (60), its XRD spectra and SEM photo are seen Fig. 5 and Fig. 6 respectively;
Wherein, the middle mixed gel B of step 1 (b) is in molar ratio by 1 mole of Ga
2O
3, 60 moles of SiO
2, 21.4 moles of TPAOH and 650 moles of H
2O forms;
SiO in the step 3
2Mass content be 30%;
Mixed gel D is in molar ratio by 1 mole of Ga in the step 3
2O
3, 60 moles of SiO
2, 7.2 moles of Na
2O and 1500 moles of H
2O forms;
The silicon gallium is than the mol ratio that is meant silicon-dioxide and gallium oxide in the step 4;
The XRD spectra of the nanometer GaZSM-5 molecular sieve of this test three preparations is as shown in Figure 5, can know by Fig. 5, and be 22.92 ° at 2 θ, 23.78 ° and 24.24 ° of characteristic diffraction peaks of locating all to have the ZSM-5 molecular sieve do not have other stray crystal;
The SEM photo of the nanometer GaZSM-5 molecular sieve of this test three preparations is as shown in Figure 6, can be known by Fig. 6, and what this test made is to have crystal regular cubic structure, height accumulative nanoscale.
Claims (7)
1. the preparation method of a nanometer GaZSM-5 molecular sieve is characterized in that the preparation method of nanometer GaZSM-5 molecular sieve realizes according to the following steps:
One, takes by weighing 1 part aluminum isopropylate, 42 ~ 108 parts tetrapropyl oxyammonia, 2 ~ 4 parts of deionized waters, 31 ~ 78 parts tetraethoxy, 1 part of Gallium trioxide, 3.2 ~ 8 parts of NaOH, 99 ~ 247 parts deionized water and 64 ~ 159 parts SiO by weight
2Mass content be 30% silicon sol;
Two, in advance the preparation of crystallization crystal seed: a, aluminum isopropylate is joined in the mixing solutions of TPAOH and deionized water, low whipping speed is to stir 20 ~ 50min under the condition of 300 ~ 500r/min, makes A solution; B, low whipping speed are under the condition of 300 ~ 700r/min, tetraethoxy are dropwise joined in the A solution of step a, and after adding, low whipping speed is to stir 3 hours under the condition of 100 ~ 300r/min, processes mixed gel B; C, the mixed gel B that step b is prepared place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, after 3 ~ 24 hours, are cooled to 25 ℃ in crystallization under 130 ~ 160 ℃ the temperature condition, obtain preparatory crystallization crystal seed;
Three, in Gallium trioxide, add NaOH and deionized water, place the stainless closed reactor that has the polytetrafluoroethyllining lining pad, under 150 ~ 180 ℃ temperature condition, dissolve 1 ~ 3 hour postcooling to 25 ℃, promptly be mixed with solution C;
Four, low whipping speed is in the solution C that step 3 obtains, to add SiO under the condition of 300 ~ 700r/min
2Mass content be 30% silicon sol, add continued and stir 10min, process mixed gel D;
Five, the preparatory crystallization crystal seed that in the mixed gel D that step 4 obtains, adds the step 2 preparation; Low whipping speed is after stirring 10 ~ 20min under the condition of 300 ~ 800r/min; Place the stainless closed reactor that has the polytetrafluoroethyllining lining pad; 160 ~ 185 ℃ of following crystallization 2 ~ 24 hours, be cooled to 25 ℃, after centrifugal, filtration, washing, drying, obtain nanometer GaZSM-5 molecular sieve then;
Wherein, the preparatory crystallization crystal seed in the step 5 accounts for 1% ~ 5% of mixed gel D gross weight;
Centrifugal condition in the step 5 is the centrifugal 5 ~ 10min of 3000 ~ 5000r/min, and wash conditions is with the secondary deionized water washing, washs 3 ~ 5 times, and drying conditions is 100 ~ 120 ℃ of dry 12h.
2. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 is characterized in that crystallization temperature is 135 ~ 155 ℃ in the c step of step 2, and crystallization time is 5 ~ 24 hours.
3. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 and 2 is characterized in that crystallization temperature is 140 ℃ in the c step of step 2, and crystallization time is 24 hours.
4. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 and 2 is characterized in that solvent temperature is 155 ~ 175 ℃ in the step 3, and dissolution time is 1.5 ~ 2.5 hours.
5. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 and 2 is characterized in that solvent temperature is 168 ℃ in the step 3, and dissolution time is 2 hours.
6. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 and 2 is characterized in that crystallization temperature is 165 ~ 180 ℃ in the step 5, and crystallization time is 5 ~ 24 hours.
7. the preparation method of a kind of nanometer GaZSM-5 molecular sieve according to claim 1 and 2 is characterized in that crystallization temperature is 170 ℃ in the step 5, and crystallization time is 24 hours.
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| CN104826654A (en) * | 2015-04-15 | 2015-08-12 | 黑龙江大学 | Method for rapidly synthesizing Ga/Al-MFI zeolite molecular sieve through two-step microwave radiation heating crystal seed guiding method |
| CN109231235A (en) * | 2018-06-04 | 2019-01-18 | 吉林化工学院 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN109437233A (en) * | 2019-01-17 | 2019-03-08 | 黑龙江大学 | A kind of method of dry gel conversion method synthesis nanometer GaZSM-5 gallosilicate molecular sieve |
| CN109592695A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
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| CN104826654A (en) * | 2015-04-15 | 2015-08-12 | 黑龙江大学 | Method for rapidly synthesizing Ga/Al-MFI zeolite molecular sieve through two-step microwave radiation heating crystal seed guiding method |
| CN104826654B (en) * | 2015-04-15 | 2017-12-08 | 黑龙江大学 | A kind of method of the crystal seed guidance method Fast back-projection algorithm Ga/Al MFI zeolite molecular sieves of two steps microwave radiation heating |
| CN109592695A (en) * | 2017-09-30 | 2019-04-09 | 中国石油天然气股份有限公司 | ZSM-5 molecular sieve and synthetic method thereof |
| CN109231235A (en) * | 2018-06-04 | 2019-01-18 | 吉林化工学院 | A kind of preparation method of nano-ZSM-5 molecular sieve |
| CN109437233A (en) * | 2019-01-17 | 2019-03-08 | 黑龙江大学 | A kind of method of dry gel conversion method synthesis nanometer GaZSM-5 gallosilicate molecular sieve |
| CN109437233B (en) * | 2019-01-17 | 2021-11-09 | 黑龙江大学 | Method for synthesizing nano GaZSM-5 silicon gallate molecular sieve by dry glue conversion method |
| CN114804136A (en) * | 2021-01-28 | 2022-07-29 | 中国科学院大连化学物理研究所 | Preparation method and application of nano SSZ-13 molecular sieve |
| CN114804136B (en) * | 2021-01-28 | 2023-12-26 | 中国科学院大连化学物理研究所 | Preparation method and application of nano SSZ-13 molecular sieve |
| CN115999623A (en) * | 2022-12-15 | 2023-04-25 | 黄河三角洲京博化工研究院有限公司 | Preparation method of catalyst for increasing propylene concentration in liquefied gas of catalytic cracking product |
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