CN105195212B - The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst - Google Patents
The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst Download PDFInfo
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- CN105195212B CN105195212B CN201510668927.7A CN201510668927A CN105195212B CN 105195212 B CN105195212 B CN 105195212B CN 201510668927 A CN201510668927 A CN 201510668927A CN 105195212 B CN105195212 B CN 105195212B
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Abstract
The invention discloses the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, the molecular sieves of ZSM 5 are mixed with chitosan, binding agent, hydrochloric acid regulation is added until the pH value of mixed liquor is 1~2, stir the mixture for, until mixture drips ball forming, then filter, drop ball is dried 2 hours in the environment of 35 DEG C；Ball hydrothermal crystallizing 5~48 hours in the environment of 100 DEG C~200 DEG C will be dripped, decontamination is filtered afterwards, and will be washed until pH value reaches 7, is dried at normal temperatures, is then calcined 6h at 550 DEG C, obtain the spherical full skeleton monolithic construction zeolite molecular sieve catalyst.The product of the present invention can be applied in Catalyst Production application, and the catalyst size that mainly solution industrial requirements are used is small, the problem of mechanical strength is not high.
Description
Technical field
The present invention relates to integral catalyzer field, and in particular to spherical full skeleton monolithic construction Zeolite molecular sieve catalysis
The preparation method of agent.
Background technology
Integral catalyzer is widely used in industrial catalyst field because of unique pore passage structure, and conventional shape has cylinder
It is shape, ring-type, spherical, sheet, powdered, cellular and membranaceous etc., and it is general using having good streamline in fixed bed reaction
The spheric catalyst of type, thus spherical integral catalyst receives much concern.In traditional synthetic method, aluminum oxide compares table due to it
The acid-base property that area is high, compressive resistance is good and suitable, is conventional binding agent.And forming method is typically by molecular sieve and oxygen
Change aluminium mixing, add nitric acid, then kneading, extrusion molding.The catalyst being molded with the method is to original property of molecular sieve, such as
Specific surface area, reactivity etc. have influenceed.
Amino, the hydroxyl enriched in chitosan molecule makes it have excellent chelating, absorption, bridging action.It is molten in alkalescence
The flocculation glomeration such as cationic flocculant, adsorbent of organic matter is used as in liquid.And chitosan is in itself as mesoporous material,
Therefore calcining can form mesopore orbit during the course of the reaction.Tetraethyl orthosilicate issues raw hydrolysis in acid or alkaline environment,
Then condensation-polymerized reaction is carried out, the polymer with 3-D solid structure by major key of silicon-oxygen is generated, so as to conduct
The binding agent of reaction.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of large scale, high mechanical properties it is spherical complete
The preparation method of skeleton monolithic construction zeolite molecular sieve catalyst.
Present invention solves the technical problem that can be realized using following technical scheme：Spherical full skeleton monolithic construction boiling
The preparation method of stone molecular sieve catalyst, the size of the spherical full skeleton monolithic construction zeolite molecular sieve catalyst is 14 mesh
~35 mesh, its mechanical strength is 10~20N/mm, is comprised the following steps：
(1), mix：ZSM-5 molecular sieve is mixed with chitosan, binding agent, hydrochloric acid regulation is added until the pH of mixed liquor
Be worth for 1~2, stir the mixture for, until mixture drips ball forming, then filter, will drop ball that 2 are dried in the environment of 35 DEG C is small
When；
(2) hydrothermal crystallizing：Ball hydrothermal crystallizing 5~48 hours in the environment of 100 DEG C~200 DEG C will be dripped, crosses filter off afterwards
Impurity, and wash until pH value reaches 7, dry at normal temperatures, then calcine 6h at 550 DEG C, obtain the spherical full skeleton whole
Body formula structural zeolite molecular sieve catalyst.
It is preferred that, ZSM-5 molecular sieve in the step (1) includes silica and alundum (Al2O3), silica and
Alundum (Al2O3) is with molar ratio computing, and ratio is 30~300.
It is preferred that, the chitosan in the step (1) is with ZSM-5 molecular sieve according to mass ratio meter, and ratio is 0.2~2.
It is preferred that, the binding agent is mixing one or more of in Ludox, aerosil and tetraethyl orthosilicate
Thing.
It is preferred that, the content of the binding agent in the step (1) is the 10%~30% of aluminum oxide.
It is preferred that, the drop ball in the step (1) immerses solution for sodium hydroxide, ammoniacal liquor and tetrapropyl hydrogen-oxygen after shaping
Change one or more of mixtures in ammonium.
It is preferred that, the concentration of the sodium hydroxide is 0.1~1mol/L.
It is preferred that, the mass fraction of the ammoniacal liquor is 7%~28%.
It is preferred that, the mass fraction of the TPAOH is 5%~25%.
Beneficial effect is：Tetraethyl orthosilicate is used in the present invention as binding agent, and successful conversion during the course of the reaction
For zeolite molecular sieve, the crystallinity of product is improved；Using chitosan as cationic flocculant, the adsorbent of organic matter,
Make product flocculation glomeration.And chitosan is in itself as mesoporous material, therefore calcining can form mesoporous hole during the course of the reaction
Road.Therefore it is safer using the method, it is smaller on environmental protection influence, and the product of shaping has larger size and higher machinery
Intensity.The shaped article prepared using the present invention is compared with conventional method, and product is that the higher spherical full skeleton of crystallinity is overall
Formula structural zeolite molecular sieve, the product size with shaping is big, high mechanical strength, small to molecular sieve structure and performance impact, and
More safe and environment-friendly advantage, achieves preferable technique effect.The sample of this method synthesis is the higher spherical full bone of crystallinity
Frame monolithic construction zeolite molecular sieve, the product size with shaping is big, high mechanical strength, to molecular sieve structure and performance impact
Small and more safe and environment-friendly advantage.
Brief description of the drawings
Fig. 1 is the XRD spectra of the embodiment 1 of the spherical full skeleton monolithic construction zeolite molecular sieve catalyst of the present invention；
Fig. 2 is the SEM image of the embodiment 1 of the spherical full skeleton monolithic construction zeolite molecular sieve catalyst of the present invention；
Fig. 3 for the embodiment 1 of the spherical full skeleton monolithic construction zeolite molecular sieve catalyst of the present invention nitrogen adsorption-de-
Accompanying drawing picture.
Embodiment
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
Embodiment 1
The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, by 0.3gZSM-5 molecular sieves and 10g
Chitosan solution stirs, and wherein the mol ratio of the silica of ZSM-5 molecular sieve and alundum (Al2O3) is 60, and chitosan is molten
The mass fraction of liquid is 3%, adds 244 μ L tetraethyl orthosilicates and appropriate hydrochloric acid, and regulation is 1~2 until the pH value of mixed liquor,
The sodium hydroxide solution drips ball forming that molar concentration is 1mol/L is instilled, is then filtered, drop ball is dried 2 in the environment of 35 DEG C
Hour, will drop ball in 170 DEG C of hydrothermal crystallizings 5 hours, decontamination is filtered afterwards, and wash until pH value reaches 7, done at normal temperatures
It is dry, 6h then is calcined at 550 DEG C, the spherical full skeleton monolithic construction zeolite molecular sieve catalyst is obtained.
With reference to accompanying drawing, Fig. 1 is used for characterizing molecular sieve crystalline structure, and Fig. 2 is used for characterizing zeolite crystal pattern, and Fig. 3 is used for
Characterize molecular sieve pore passage structure.
Embodiment 2
The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, by 0.3gZSM-5 molecular sieves and 10g
Chitosan solution stirs, and wherein the mol ratio of the silica of ZSM-5 molecular sieve and alundum (Al2O3) is 60, and chitosan is molten
The mass fraction of liquid is 3%, adds 244 μ L tetraethyl orthosilicates and appropriate hydrochloric acid, and regulation is 1~2 until the pH value of mixed liquor,
The ammonia spirit drips ball forming that mass fraction is 28% is instilled, is then filtered, drop ball is dried 2 hours in the environment of 35 DEG C,
Will drop ball in 170 DEG C of hydrothermal crystallizings 5 hours, decontamination is filtered afterwards, and wash until pH value reaches 7, dried at normal temperatures, so
6h is calcined at 550 DEG C afterwards, the spherical full skeleton monolithic construction zeolite molecular sieve catalyst is obtained.
Embodiment 3
The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, by 0.3gZSM-5 molecular sieves and 10g
Chitosan solution stirs, and wherein the mol ratio of the silica of ZSM-5 molecular sieve and alundum (Al2O3) is 60, and chitosan is molten
The mass fraction of liquid is 3%, adds 244 μ L tetraethyl orthosilicates and appropriate hydrochloric acid, and regulation is 1~2 until the pH value of mixed liquor,
The ammonia spirit drips ball forming that mass fraction is 28% is instilled, is then filtered, drop ball is dried 2 hours in the environment of 35 DEG C,
Will drop ball in 170 DEG C of hydrothermal crystallizings 5 hours, decontamination is filtered afterwards, and wash until pH value reaches 7, dried at normal temperatures, so
6h is calcined at 550 DEG C afterwards, the spherical full skeleton monolithic construction zeolite molecular sieve catalyst is obtained.
Embodiment 4
Remaining is same as Example 1, and difference is the silica of ZSM-5 molecular sieve and mole of alundum (Al2O3)
Than for 200.
Embodiment 5
Remaining is same as Example 1, and difference is that the quality of ZSM-5 molecular sieve is 0.15g.
Embodiment 6
Remaining is same as Example 1, and difference is that the molar concentration of sodium hydroxide solution is 0.8mol/L.
Embodiment 7
Remaining is same as Example 1, and difference is that the molar concentration of sodium hydroxide solution is 0.6mol/L.
Embodiment 8
Remaining is same as Example 2, and difference is the silica of ZSM-5 molecular sieve and mole of alundum (Al2O3)
Than for 200.
Embodiment 9
Remaining is same as Example 2, and difference is that the quality of ZSM-5 molecular sieve is 0.15g.
Embodiment 10
Remaining is same as Example 2, and difference is that ammonia spirit mass fraction is 14%.
Embodiment 11
Remaining is same as Example 2, and difference is that ammonia spirit mass fraction is 7%.
Embodiment 12
Remaining is same as Example 3, and difference is the silica of ZSM-5 molecular sieve and mole of alundum (Al2O3)
Than for 200.
Embodiment 13
Remaining is same as Example 3, and difference is that the quality of ZSM-5 molecular sieve is 0.15g.
Embodiment 14
Remaining is same as Example 3, and difference is that TPAOH liquid quality fraction is 12.5%.
Embodiment 15
Remaining is same as Example 3, and difference is that TPAOH liquid quality fraction is 6.25%.
The spherical full skeleton monolithic construction zeolite molecular sieve catalyst that the present invention is made, its related performance indicators is as follows
Table：
It can be seen from upper table, the size of the catalyst product obtained by embodiment 1~15 is in the mesh of 14 mesh~35, its machinery
Intensity is also all 10~20N/mm, all meets that size of the present invention is big, the technical specification of high mechanical strength.
Tetraethyl orthosilicate is used in the present invention as binding agent, and successful conversion is zeolite molecules during the course of the reaction
Sieve, improves the crystallinity of product；Using chitosan as cationic flocculant, the adsorbent of organic matter, product is flocculated
Glomeration.And chitosan is in itself as mesoporous material, therefore calcining can form mesopore orbit during the course of the reaction.Therefore use
The method is safer, smaller on environmental protection influence, and the product of shaping has larger size and higher mechanical strength.Use this
Shaped article prepared by invention is compared with conventional method, and product is crystallinity higher spherical full skeleton monolithic construction zeolite point
Son sieve, the product size with shaping is big, high mechanical strength, small to molecular sieve structure and performance impact and more safe and environment-friendly
Advantage, achieves preferable technique effect.The sample of this method synthesis is the higher spherical full skeleton monolithic construction of crystallinity
Zeolite molecular sieve, the product size with shaping is big, high mechanical strength, small to molecular sieve structure and performance impact and safer,
The advantage of environmental protection.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (9)
1. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, it is characterised in that：The spherical full bone
The size of frame monolithic construction zeolite molecular sieve catalyst is the mesh of 14 mesh~35, and its mechanical strength is 10~20N/mm, including with
Lower step：
(1), mix：ZSM-5 molecular sieve is mixed with chitosan, binding agent, hydrochloric acid regulation is added until the pH value of mixed liquor is 1
~2, stir the mixture for, until mixture drips ball forming, then filter, drop ball is dried 2 hours in the environment of 35 DEG C；
(2) hydrothermal crystallizing：Ball hydrothermal crystallizing 5~48 hours in the environment of 100 DEG C~200 DEG C will be dripped, decontamination is filtered afterwards,
And wash until pH value reaches 7, dry at normal temperatures, then calcine 6h at 550 DEG C, obtain the spherical full skeleton monoblock type knot
Structure zeolite molecular sieve catalyst.
2. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 1
It is：ZSM-5 molecular sieve in the step (1) includes silica and alundum (Al2O3), silica and alundum (Al2O3)
With molar ratio computing, ratio is 30~300.
3. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 1
It is：Chitosan in the step (1) is with ZSM-5 molecular sieve according to mass ratio meter, and ratio is 0.2~2.
4. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 1
It is：The binding agent is mixture one or more of in Ludox, aerosil and tetraethyl orthosilicate.
5. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 2
It is：The content of binding agent in the step (1) is the 10%~30% of aluminum oxide.
6. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 1
It is：It is one in sodium hydroxide, ammoniacal liquor and TPAOH that drop ball in the step (1) immerses solution after shaping
Plant or several mixtures.
7. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 6
It is：The concentration of the sodium hydroxide is 0.1~1mol/L.
8. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 6
It is：The mass fraction of the ammoniacal liquor is 7%~28%.
9. the preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst, its feature according to claim 7
It is：The mass fraction of the TPAOH is 5%~25%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191776A (en) * | 2013-03-22 | 2013-07-10 | 华东理工大学 | Preparation method of ZSM-5 molecular sieve catalyst |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN104163436A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Method for synthesizing monolithic 4A molecular sieve by dry glue process |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191776A (en) * | 2013-03-22 | 2013-07-10 | 华东理工大学 | Preparation method of ZSM-5 molecular sieve catalyst |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN104163436A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Method for synthesizing monolithic 4A molecular sieve by dry glue process |
Non-Patent Citations (1)
| Title |
|---|
| 大晶粒ZSM-5的合成;刘世奇等;《材料导报》;20141130;第28卷;111-113 * |
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