CN110028080A - A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity - Google Patents
A kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity Download PDFInfo
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- CN110028080A CN110028080A CN201910462013.3A CN201910462013A CN110028080A CN 110028080 A CN110028080 A CN 110028080A CN 201910462013 A CN201910462013 A CN 201910462013A CN 110028080 A CN110028080 A CN 110028080A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of methods of rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity, belong to technical field of molecular sieve.Including precursor preparation, crystallization, filtering, drying and roasting, wherein there are two types of crystallization methods.Method one, is to prepare presoma using dry gel conversion method, carries out crystallization using ethyl alcohol self-generated pressure.Method two is to carry out heating to the presoma in sealing container using saturated vapor to carry out Crystallizing treatment.The temperature of the saturated vapor of Crystallizing treatment is 160~180 DEG C, and crystallization time is 1-6 hours.Presoma joined silicon source and template in crystallization process in mass ratio, and the molar ratio of silicon source and template is 1:(0.01~0.5), the mass ratio of initial presoma and silicon source is 2~15%.The method have the advantages that: the temperature of simple process, crystallization process is uniform, and product crystallinity is high, template dosage is few, and crystallization time is short, can be improved productivity, energy saving.
Description
Technical field
The invention belongs to technical field of molecular sieve, are related to a kind of rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity
Method.
Background technique
The oxygen-octahedron and aluminum-oxygen tetrahedron that zeolite is connected by oxygen bridge are constituted, it is defined as micropore silicon aluminate crystal.
The exclusive crystal structure of zeolite makes it have higher thermal stability and hydrothermal stability.Due to including less than 1nm's in zeolite
Duct and hole, therefore most reaction moleculars can enter in its inside；Simultaneously because its range of micropores inner duct is uniform, therefore
Zeolite has good shape selectivity to various sizes of molecule.Aluminium ion is+trivalent in zeolite skeleton, and silicon ion is -4 valences, because
Additional cation is needed to carry out balancing charge in this zeolite skeleton, this makes zeolite have ion-exchange capacity, can be used as water
Deionization processing and one of the ingredient as washing.Structure, the difference of composition silica alumina ratio and pretreatment condition according to zeolite,
The ratio of B acid and the L acid of zeolite is adjustable in very large range, therefore it can be used as catalyst applied to petroleum refining and petrochemical industry
In many catalysis reaction of industry.Zeolite has high specific surface area and micro pore volume, can be used as the load of catalytic active component
Body.Therefore, can by ion-exchange perhaps infusion process by it is metal-doped enter zeolite skeleton prepare double acidic sites or
Bifunctional catalyst.The acidity of zeolite and plus the/bi-functional of dehydrogenation so that it is widely used in the hydrotreating of oil and is reformed anti-
Ying Zhong.
Compared with micropore ZSM-5 molecular sieve, the higher external surface area of multi-stage porous ZSM-5 molecular sieve has preferably big point
The accessibility of sub- reactant makes it have higher catalytic activity.In addition to this, multi-stage porous ZSM-5 molecular sieve pore size
Short, diffusion is good, has adjustable pore structure, and surface utilisation is high, this makes it have the advantage of many uniquenesses, to big point
The cracking ability of sub- reactant is significantly enhanced.There are many problems for the common synthetic method of multi-stage porous ZSM-5 zeolite, such as operate
Complex steps, synthesis process control are difficult, with high costs, and pore performance is difficult to modulation etc..
There are many problems, such as complex for operation step, synthesis processes to control for the common synthetic method of multi-stage porous ZSM-5 zeolite
Difficult, with high costs, pore performance is difficult to modulation etc..
Summary of the invention
The object of the present invention is to provide a kind of mesoporous ZSM-5 molecular sieve of high-crystallinity of rapid crystallization synthesis, the molecular sieves
Crystallite dimension is 1~2 μm, and grain surface has the molecular sieve association crystal grain of 200~600nm, and molecular sieve concentrates mesopore size between 5
~20nm, specific surface area are not less than 400m2The total pore volume of/g, the molecular sieve are not less than 0.21cm3/ g, micro pore volume are not less than
0.1m2/g。
Further, the crystallinity of the molecular sieve is greater than 85%.
The present invention also provides a kind of methods of rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity, including following step
Suddenly.
(1) preparation of presoma: being SiO by molar ratio2∶R∶Na2O∶H2O: EtOH=1: (0.01~1.0): (0.001~
0.01): (5-400): the silicon source of (1~10), structure directing agent, alkali (NaOH or Na2CO3), water, ethyl alcohol be uniformly mixed obtain it is anti-
Mixture is answered, obtains dry glue in 20~60 DEG C of 2~12h of processing；After 5~40mL deionized water stirring, 2~12h is added in dry glue,
Reaction kettle is packed into 50~180 DEG C of 1~12h of crystallization, is cooled to room temperature, obtains initial presoma；R is represented in reaction mixture and is tied
Structure directed agents molal quantity；
(2) by silicon source, silicon source, alkali (NaOH or Na2CO3) and nitrogenous long-chain compound template be mixed to get mixture, should
SiO in mixture2∶Al2O3∶Na2O∶2H2O: N molar ratio is 1: (0.01~0.1): (0.01~1): (0.1~5): (0.01
~0.5), N represents the molal quantity of template in reaction mixture；Add initial presoma in (1), initial presoma and silicon source
Mass ratio be 2~15%, obtain reaction mixture；
(3) heating crystallization processing is carried out to the reaction mixture that (2) obtain using saturated vapor, the saturation of Crystallizing treatment is steamed
The temperature of vapour is 160~180 DEG C, and crystallization time is 1~6 hour, obtains crystallization product；
(4) crystallization product in recycling step (3).
In some specific embodiments, silicon source described in step (1) and step (2) is methyl orthosilicate, positive silicic acid
At least one of second vinegar, the third vinegar of positive silicic acid, positive silicic acid fourth vinegar, silica gel, white carbon black and silica solution.
In some specific embodiments, silicon source described in step (2) is sodium metaaluminate, aluminium isopropoxide, aluminum sulfate
It is at least one.
In some specific embodiments, the partial size of initial presoma described in step (1) is less than 100nm.
In some specific embodiments, structure directing agent described in step (1) is selected from tetramethylammonium hydroxide, tetrem
At least one of base ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
In some specific embodiments, crystallization temperature described in step (1) is 60~160 DEG C, time of crystallization is 2~
10h。
In some specific embodiments, nitrogenous long-chain compound template described in step (2) is selected from urea, 4 third
At least one of base ammonium bromide, tetrapropylammonium hydroxide.
In some specific embodiments, this method further includes step (5): the crystallization product of step (4) recycling is carried out
Calcination process.Further, the condition of calcination process described in step (5) is: maturing temperature is 400~600 DEG C, calcining time
It is 1~6 hour.
The method have the advantages that: the temperature of simple process, crystallization process is uniform, product crystallinity height, mould
Plate agent dosage is few, and crystallization time is short, can be improved productivity, energy saving.
Detailed description of the invention
Fig. 1 is the XRD spectra for the multi-stage porous ZSM-5 molecular sieve that embodiment 1 obtains.
Fig. 2 is the BJH pore size distribution curve for the multi-stage porous ZSM-5 molecular sieve that embodiment 1 obtains.
Fig. 3 is the SEM photograph for the multi-stage porous ZSM-5 molecular sieve that embodiment 1 obtains.
Specific embodiment
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
According to the present invention, the crystalline phase figure of X-ray diffraction (XRD) is measured with Philips Panalytical X'pert
It arrives, test condition are as follows: Cu target, Ka radiation, Ni filter plate, super detector, tube voltage 30KV, tube current 40mA.Multi-stage porous
The relative crystallinity of ZSM-5 molecular sieve can be calculated according to the size of the characteristic peak of molecular sieve in XRD spectrum.
Embodiment 1
Under agitation, it is 1:0.36:0.004:60 according to molar ratio by silicon source, structure directing agent, alkali, water, ethyl alcohol:
5 ratio is mixed evenly, and obtains dry glue in 20 DEG C of processing 12h；After 40mL deionized water stirring 12h is added in dry glue, it is packed into anti-
It answers kettle in 50 DEG C of crystallization 12h, is cooled to room temperature, obtain initial presoma.
Silicon source, silicon source, alkali and template TPABr are mixed to get mixture, SiO in the mixture2: Al2O3: Na2O:
H2The molar ratio of O:N is 1:0.012:0.15:0.6:0.3, adds initial presoma and obtains reaction mixture.Initial presoma
Mass ratio with silicon source is 3%；N represents the molal quantity of template TPABr in reaction mixture.
Heating crystallization processing is carried out to reaction mixture using saturated vapor, the temperature of the saturated vapor of Crystallizing treatment is
160 DEG C, crystallization time is 6 hours, obtains crystallization product.The multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, 110 DEG C dry
After dry 6h, then multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.The XRD characterization of multi-stage porous ZSM-5 molecular sieve
As a result as shown in Figure 1, pore size distribution figure is as shown in Fig. 2, SEM result is as shown in Figure 3.After isometric load 0.8%Pt, 200 DEG C also
Former 3h tests its guaiacol hydrogenation reaction, conversion ratio 99%, cyclohexanol selectivity 90%.
Embodiment 2
Under agitation, it is 1:0.36:0.004:60 according to molar ratio by silicon source, structure directing agent, alkali, water, ethyl alcohol:
5 ratio is mixed evenly, and obtains dry glue in 30 DEG C of processing 10h；After 30mL deionized water stirring 10h is added in dry glue, it is packed into anti-
It answers kettle in 80 DEG C of crystallization 10h, is cooled to room temperature, obtain initial presoma.
Silicon source, silicon source, alkali and template TPABr are mixed to get mixture, SiO in the mixture2: Al2O3: Na2O:
H2The molar ratio of O:N is 1:0.012:0.15:0.6:0.3, adds initial presoma and obtains reaction mixture.Initial presoma
Mass ratio with silicon source is 5%；N represents the molal quantity of template TPABr in reaction mixture.
Heating crystallization processing is carried out to reaction mixture using saturated vapor, the temperature of the saturated vapor of Crystallizing treatment is
165 DEG C, crystallization time is 5 hours, obtains the multi-stage porous ZSM-5 molecular sieve that crystallization product recycling gained does not roast, 110 DEG C dry
After dry 6h, then multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt, 200 DEG C also
Former 3h tests its guaiacol hydrogenation reaction, conversion ratio 90%, cyclohexanol selectivity 93%.
Embodiment 3
It is under agitation 1:0.36:0.004:60:5 according to molar ratio by silicon source, structure directing agent, alkali, water, ethyl alcohol
Ratio be mixed evenly, obtain dry glue in 50 DEG C of processing 4h；After 20mL deionized water stirring 5h is added in dry glue, it is packed into reaction kettle
It in 120 DEG C of crystallization 3h, is cooled to room temperature, obtains initial presoma.
Silicon source, silicon source, alkali and template TPABr are mixed to get mixture, SiO in the mixture2: Al2O3: Na2O:M:
H2The molar ratio of O:N is 1:0.012:0.15:0.1:0.6:0.4, adds initial presoma and obtains reaction mixture.Before initial
The mass ratio for driving body and silicon source is 3%；M represents the molal quantity of mineralizer in reaction mixture；N represents template in reaction mixture
The molal quantity of agent TPABr；
Heating crystallization processing is carried out to reaction mixture using saturated vapor, the temperature of the saturated vapor of Crystallizing treatment is
1670 DEG C, crystallization time is 4 hours, obtains crystallization product.The multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast, 110 DEG C dry
After dry 6h, then multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt, 200 DEG C also
Former 3h tests its guaiacol hydrogenation reaction, conversion ratio 86%, cyclohexanol selectivity 95%.
Embodiment 4
It is under agitation 1:0.36:0.004:60:5 according to molar ratio by silicon source, structure directing agent, alkali, water, ethyl alcohol
Ratio be mixed evenly, obtain dry glue in 60 DEG C of processing 2h；After 10mL deionized water stirring 2h is added in dry glue, it is packed into reaction kettle
It in 180 DEG C of crystallization 1h, is cooled to room temperature, obtains initial presoma.
Silicon source, silicon source, alkali and template TPABr are mixed to get mixture, SiO in the mixture2: Al2O3: Na2O:
H2The molar ratio of O:N is 1:0.012:0.15:0.6:0.6, adds initial presoma and obtains reaction mixture.Initial presoma
Mass ratio with silicon source is 3%；N represents the molal quantity of template TPABr in reaction mixture.
Heating crystallization processing, the saturated vapor of Crystallizing treatment are carried out to the reaction mixture that (2) obtain using saturated vapor
Temperature be 180 DEG C, crystallization time be 1 hour, obtain crystallization product.The multi-stage porous ZSM-5 molecular sieve that recycling gained does not roast,
After 110 DEG C of dry 6h, then multi-stage porous ZSM-5 molecular sieve is obtained after 550 DEG C of calcination process 4h.After isometric load 0.8%Pt,
200 DEG C of reduction 3h test its guaiacol hydrogenation reaction, conversion ratio 89%, cyclohexanol selectivity 90%.
The crystallinity and pore structure data of 1 embodiment 1-4 molecular sieve of table
Claims (11)
1. a kind of mesoporous ZSM-5 molecular sieve of high-crystallinity of rapid crystallization synthesis, which is characterized in that the zeolite crystal having a size of
1~2 μm, grain surface has the molecular sieve association crystal grain of 200~600nm, and molecular sieve concentrates mesopore size between 5~20nm, than
Surface area is not less than 400m2The total pore volume of/g, the molecular sieve are not less than 0.21cm3/ g, micro pore volume are not less than 0.1m2/g。
2. the mesoporous ZSM-5 molecular sieve of high-crystallinity according to claim 1, which is characterized in that the crystallinity of the molecular sieve
Greater than 85%.
3. a kind of method of the rapid crystallization synthesis mesoporous ZSM-5 molecular sieve of high-crystallinity, which comprises the following steps:
(1) preparation of presoma: being SiO by molar ratio2∶R∶Na2O∶H2O: EtOH=1: (0.01~1.0): (0.001~
0.01): (5-400): the silicon source of (1~10), structure directing agent, alkali, water, ethyl alcohol, which are uniformly mixed, obtains reaction mixture, in 20
~60 DEG C of 2~12h of processing obtain dry glue；After 5~40mL deionized water stirring, 2~12h is added in dry glue, reaction kettle is packed into 50
~180 DEG C of 1~12h of crystallization, are cooled to room temperature, and obtain initial presoma；R represents structure directing agent mole in reaction mixture
Number；
(2) silicon source, silicon source, alkali and nitrogenous long-chain compound template are mixed to get mixture, SiO in the mixture2∶Al2O3
∶Na2O∶2H2O: N molar ratio is 1: (0.01~0.1): (0.01~1): (0.1~5): (0.01~0.5), it is mixed that N represents reaction
Close the molal quantity of template in object；Adding initial presoma in (1), the mass ratio of initial presoma and silicon source is 2~15%,
Obtain reaction mixture；
(3) heating crystallization processing is carried out to the reaction mixture that (2) obtain using saturated vapor, the saturated vapor of Crystallizing treatment
Temperature is 160~180 DEG C, and crystallization time is 1~6 hour, obtains crystallization product；
(4) crystallization product in recycling step (3).
4. according to the method described in claim 3, the silicic acid it is characterized in that, silicon source described in step (1) and step (2) is positive
At least one of methyl esters, positive silicic acid second vinegar, the third vinegar of positive silicic acid, positive silicic acid fourth vinegar, silica gel, white carbon black and silica solution.
5. according to the method described in claim 3, it is characterized in that, silicon source described in step (2) is sodium metaaluminate, isopropanol
At least one of aluminium, aluminum sulfate.
6. according to the method described in claim 3, the partial size of initial presoma described in step (1) is less than 100nm.
7. according to the method described in claim 3, it is characterized in that, structure directing agent described in step (1) is selected from tetramethyl
At least one of ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
8. brilliant according to the method described in claim 3, it is characterized in that, crystallization temperature described in step (1) is 60~160 DEG C
The time of change is 2~10h.
9. synthetic method according to claim 3, which is characterized in that nitrogenous long-chain compound mould described in step (2)
Plate agent is selected from least one of urea, 4-propyl bromide, tetrapropylammonium hydroxide.
10. synthetic method according to claim 3, which is characterized in that this method further includes step (5): step (4) are returned
The crystallization product of receipts carries out calcination process.
11. synthetic method according to claim 10, which is characterized in that the condition of calcination process described in step (5) is:
Maturing temperature is 400~600 DEG C, and calcining time is 1~6 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484035A (en) * | 2020-04-03 | 2020-08-04 | 中国神华煤制油化工有限公司 | Preparation method and application of ZSM-5 molecular sieve precursor |
| CN112875721A (en) * | 2021-01-11 | 2021-06-01 | 中国石油天然气股份有限公司 | Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body |
| CN114229865A (en) * | 2021-12-10 | 2022-03-25 | 成都理工大学 | Seed crystal-free rapid aging crystallization synthesis method of ZSM-5 micro mesoporous molecular sieve |
-
2019
- 2019-05-30 CN CN201910462013.3A patent/CN110028080A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484035A (en) * | 2020-04-03 | 2020-08-04 | 中国神华煤制油化工有限公司 | Preparation method and application of ZSM-5 molecular sieve precursor |
| CN111484035B (en) * | 2020-04-03 | 2023-08-15 | 中国神华煤制油化工有限公司 | Preparation method and application of ZSM-5 molecular sieve precursor |
| CN112875721A (en) * | 2021-01-11 | 2021-06-01 | 中国石油天然气股份有限公司 | Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body |
| CN112875721B (en) * | 2021-01-11 | 2023-05-26 | 中国石油天然气股份有限公司 | Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body |
| CN114229865A (en) * | 2021-12-10 | 2022-03-25 | 成都理工大学 | Seed crystal-free rapid aging crystallization synthesis method of ZSM-5 micro mesoporous molecular sieve |
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Application publication date: 20190719 |