CN1927714A - Preparation method of ZSM-type molecular sieve without binding agent - Google Patents
Preparation method of ZSM-type molecular sieve without binding agent Download PDFInfo
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- CN1927714A CN1927714A CN 200510029462 CN200510029462A CN1927714A CN 1927714 A CN1927714 A CN 1927714A CN 200510029462 CN200510029462 CN 200510029462 CN 200510029462 A CN200510029462 A CN 200510029462A CN 1927714 A CN1927714 A CN 1927714A
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Abstract
The present invention relates to preparation process of adhesive-free ZSM type molecular sieve, and aims at solving the problem of adding adhesive causing decrease in effective surface area and limited diffusion. Technologically, the present invention is that adhesive silica in 5-50 wt% and ZSM type molecular sieve powder are made to form mixture, and the mixture is hydrothermally converted inside water solution or steam containing organic amine halide and alkyl diamine into integrated ZSM type molecular sieve. The process of the present invention may be used in the industrial preparation of ZSM type molecular sieve catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of ZSM-type molecular sieve without binding agent.
Background technology
Molecular sieve has uniform sequential micropore, big specific surface, high hydrothermal stability, is widely used in catalytic field.Small crystal grain molecular sieve is owing to have short intracrystalline diffusion orifice throat length and bigger outside surface, the touch opportunity that helps active sites in augmenting response thing and the micropore, thereby improve every performance of molecular sieve, in reaction, show special advantages, as had macromole selectivity, the advantages of high catalytic activity of uniqueness and the catalyst life of growing etc.But molecular sieve is undersized, and is not very convenient in actual applications, has weakness such as difficult recovery, easy inactivation and gathering, needs to add binding agent in the moulding process, and the result reduces effective surface area, and has introduced diffusional limitation, causes side reaction to increase.Adhesive-free Molecular Sieve is meant and does not contain inert binder in the sieve particle or only contain small amount of binder to have higher molecular sieve content, and therefore available effective surface area is bigger, may have better catalytic performance.
ZSM type molecular sieve comprises ZSM-5, ZSM-48, and ZSM-22 becomes very important catalytic material with its unique pore passage structure and good catalytic performance, is used widely in the organic catalysis conversion reaction.The binding agent conversion method is one of method for preparing by the Adhesive-free Molecular Sieve molecular sieve: an imperial outstanding person with ZSM-5 type hydrophobic silicon molecular sieve powder and silica containing binding agent mixing moulding drying after, in organic amine or organic quaternary ammonium hydroxide aqueous solution or steam, make a kind of adhesiveless ZSM-5 type hydrophobic silicon molecular sieve [an imperial outstanding person a kind of binder free hydrophobic silicon adsorbent of molecular sieve and the preparation patent No. thereof: ZL 94112035.X] through crystallization processing, roasting.Molecular sieve in the aforesaid method only limits to type ZSM 5 molecular sieve, and does not relate to the silica alumina ratio of molecular sieve, and has adopted single template.We arrive ZSM type molecular sieve to the range extension of molecular sieve, comprise ZSM-5, ZSM-48, ZSM-22, and adopted the mixed templates that contains halogenation organic amine and alkyl diamine, the mixture that contains ZSM type molecular sieve and binding agent silicon oxide is converted into incorporate ZSM type binder free molded molecular sieve.This method can be converted into ZSM type molecular sieve to binding agent easily simply.Prepared integrated binderless ZSM-5 molded molecular sieve has more macroporous structure simultaneously, can in actual catalyzed reaction, act synergistically with the performance of molecular sieve intracrystalline micropore, for example with micropore as reacting environment, macropore is as the transport passage of reactant molecule, thereby eliminated diffusional limitation to a certain extent, molecular sieve can be used more effectively.This inventive method might develop into a kind of economic means for preparing the molecular sieve catalytic material.
Summary of the invention
Technical problem to be solved by this invention is the binding agent that in the past exists in the molecular sieve catalyst, can reduce effective constituent in the unit mass catalyzer, hinder the diffusion in catalyzer of reactant, product, reduce the reactive behavior of catalyzer and produce the problem of more by product, a kind of preparation method of new ZSM-type molecular sieve without binding agent is provided.This preparation method has molecular sieve catalyst degree of crystallinity height, does not contain binding agent, the simple advantage of preparation flow.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of ZSM-type molecular sieve without binding agent, and at first with silica alumina ratio SiO
2/ Al
2O
3Be that 10～2000 ZSM type molecular sieve powder mixes with the amorphous silica binding agent, wherein the weight concentration of silica binder is 5～50%, behind the shaping and drying, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into ZSM-type molecular sieve without binding agent through hydrothermal treatment consists, wherein crystallization temperature is 100～240 ℃, and crystallization time is 10～240 hours.
In the technique scheme, ZSM type molecular screening is from ZSM-5, ZSM-48 or ZSM-22, the silica alumina ratio SiO of ZSM type molecular sieve
2/ Al
2O
3Preferable range is 20～600.Used silica binder is selected from silicon sol, water glass or its mixture, and the weight concentration preferable range of silicon-dioxide is 5～30%.Organic amine template halogenation organic amine preferred version is selected from 4-propyl bromide, and the alkyl diamine preferred version is selected from 1, the 6-hexanediamine.The temperature of reaction preferable range of hydrothermal treatment consists is 120～200 ℃, and the preferable range in the reaction times of hydrothermal treatment consists is 24～120 hours.The weight ratio preferable range of halogenation organic amine and alkyl diamine is 1: 0.1～10, and more preferably scope is 1: 0.5～7.5.
The present invention can prepare silica alumina ratio SiO by to hydrothermal treatment consists temperature, time and optimization of formulation
2/ Al
2O
3Scope is at 20～600 ZSM-5, ZSM-48 and ZSM-22.Owing to adopted the mixed templates of halogenation organic amine and alkyl diamine, given full play to the high characteristics of organic amine template template index, improved molecular sieve catalyst degree of crystallinity; Reduce expensive halogenation organic amine template agent simultaneously, reduced production cost, helped practical application, obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 3 products.
Fig. 2 is the XRD figure spectrum of embodiment 6 products.
Fig. 3 is the XRD figure spectrum of embodiment 10 products.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 20 ZSM-5 molecular sieve, add after 62.5 gram 40% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample A-1.
The tetrapropyl amine bromide, 10 grams 1 that add 5 grams in the reactor in advance, the mixture of 6-hexanediamine and 30 gram distilled water, place sealing back, the online side of reactor Porous Stainless Steel under 180 ℃, to carry out gas-solid 10 gram sample A-1 and handled mutually 24 hours, 72 hours, 120 hours.
Product takes out the back and use distilled water wash, dry back in air atmosphere in 600 ℃ of roastings.The product X RD collection of illustrative plates of handling 24 hours shows that at this moment degree of crystallinity increases to some extent, and showing has new ZSM-5 molecular sieve crystal to generate; The degree of crystallinity of handling the product after 72 hours is higher; Prolong treatment time to 120 hour, the degree of crystallinity of product no longer continues to increase.
[embodiment 4～5]
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 100 ZSM-5 molecular sieve, add after 13 gram 40% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample B-1.
The tetrapropyl amine bromide, 15 grams 1 that add 2 grams in the reactor in advance, the mixture of 6-hexanediamine and 30 gram distilled water places sealing back, the online side of reactor Porous Stainless Steel to carry out gas-solid under 120 ℃ 10 gram sample B-1 and handled 120 hours mutually 72 hours.
Product takes out the back and use distilled water wash, dry back in air atmosphere in 550 ℃ of roastings.The product X RD collection of illustrative plates of handling 72 hours shows that the degree of crystallinity of product is higher; Prolong treatment time to 120 hour, the degree of crystallinity of product no longer continues to increase.
[embodiment 6～8]
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 600 ZSM-48 molecular sieve, after the water glass that adds 68 gram silica contents and be 25.9% (weight) mixed, extrusion moulding through 120 ℃ of oven dry, obtained sample C-1.
The tetrapropyl amine bromide, 5 grams 1 that add 10 grams in the reactor in advance, the mixture of 6-hexanediamine and 30 gram distilled water, place sealing back, the online side of reactor Porous Stainless Steel under 200 ℃, to carry out gas-solid 10 gram sample C-1 and handled mutually 24 hours, 72 hours, 120 hours.
Product takes out the back and use distilled water wash, dry back in air atmosphere in 600 ℃ of roastings.The product X RD collection of illustrative plates of handling 24 hours shows that at this moment degree of crystallinity is higher; Prolong treatment time to 72 hour and 120 hours, the degree of crystallinity of product no longer continues growth.
[embodiment 9～11]
Take by weighing 82 gram silica alumina ratio SiO
2/ Al
2O
3Be 300 ZSM-22 molecular sieve, add after water glass, 44 gram 40% (weight) silicon sol that 68 gram silica contents are 25.9% (weight) mix that extrusion moulding through 120 ℃ of oven dry, obtains sample D-1.
The tetrapropyl amine bromide, 12 grams 1 that add 4 grams in the reactor in advance, the mixture of 6-hexanediamine and 30 gram distilled water, place sealing back, the online side of reactor Porous Stainless Steel under 150 ℃, to carry out gas-solid 10 gram sample D-1 and handled mutually 24 hours, 72 hours, 120 hours.
Product takes out the back and use distilled water wash, dry back in air atmosphere in 600 ℃ of roastings.The product X RD collection of illustrative plates of handling 24 hours shows that at this moment degree of crystallinity increases to some extent, and showing has new ZSM-5 molecular sieve crystal to generate; The degree of crystallinity of handling the product after 72 hours is higher; Prolong treatment time to 120 hour, the degree of crystallinity of product no longer continues to increase.
[embodiment 12～14]
Take by weighing 100 gram silica alumina ratio SiO
2/ Al
2O
3Be 200 ZSM-5 molecular sieve, add after 44 gram 40% (weight) silicon sol mix that extrusion moulding through 120 ℃ of oven dry, obtains sample E-1.
The tetrapropyl amine bromide, 15 grams 1 that add 2 grams in the reactor in advance, the mixture of 6-hexanediamine and 30 gram distilled water adds 10 gram sample E-1 again, and handled under 120 ℃ 24 hours the sealing back, and 72 hours, 120 hours.
Product takes out the back and use distilled water wash, dry back in air atmosphere in 550 ℃ of roastings.The product X RD collection of illustrative plates of handling 72 hours shows that the degree of crystallinity of product is higher; Prolong treatment time to 120 hour, the degree of crystallinity of product no longer continues to increase.
Claims (10)
1, a kind of preparation method of ZSM-type molecular sieve without binding agent is characterized in that at first with silica alumina ratio SiO
2/ Al
2O
3Be that 10～2000 ZSM type molecular sieve powder mixes with the amorphous silica binding agent, wherein the weight concentration of silica binder is 5～50%, behind the shaping and drying, in the aqueous solution that contains halogenation organic amine and alkyl diamine or steam, be converted into ZSM-type molecular sieve without binding agent through hydrothermal treatment consists, wherein crystallization temperature is 100～240 ℃, and crystallization time is 10～240 hours.
2,, it is characterized in that ZSM type molecular screening is from ZSM-5, ZSM-48 or ZSM-22 according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1.
3,, it is characterized in that the silica alumina ratio SiO of ZSM type molecular sieve according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1
2/ Al
2O
3Be 20～600.
4,, it is characterized in that used silica binder is selected from silicon sol, water glass or its mixture according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1.
5, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1, the weight concentration that it is characterized in that binding agent silicon-dioxide is 5～30%.
6, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1, the temperature of reaction that it is characterized in that hydrothermal treatment consists is 120～200 ℃.
7, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1, the reaction times that it is characterized in that hydrothermal treatment consists is 24～120 hours.
8, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1, it is characterized in that organic amine is selected from 4-propyl bromide, alkyl diamine is selected from 1, the 6-hexanediamine.
9, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 1, the weight ratio that it is characterized in that halogenation organic amine and alkyl diamine is 1: 0.1～10.
10, according to the preparation method of the described ZSM-type molecular sieve without binding agent of claim 9, the weight ratio that it is characterized in that halogenation organic amine and alkyl diamine is 1: 0.5～7.5.
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