CN1557707A - Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material - Google Patents
Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material Download PDFInfo
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- CN1557707A CN1557707A CNA2004100159758A CN200410015975A CN1557707A CN 1557707 A CN1557707 A CN 1557707A CN A2004100159758 A CNA2004100159758 A CN A2004100159758A CN 200410015975 A CN200410015975 A CN 200410015975A CN 1557707 A CN1557707 A CN 1557707A
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Abstract
The present invention is the preparation process of Fe-ZSM-5 zeolite microsphere with diatomite as material. Diatomite is used industrially as filtering assistant, stuffing and catalyst carrier, and available diatomite synthesized zeolite includes mainly LTA, SOD and MOR zeolite with low Si/Al ratio. The present invention obtains zeolite product with high Si/Al ratio with diatomite material, tetrapropyl ammonium bromide as template agent and sodium chloride as additive, and through ageing and subsequent hydrothermal crystallization without need high temperature alkali dissolution to activate diatomite. The said process can utilize fully the three kinds of components including Si, Al and Fe in the material, and the zeolite product has high crystallizing degree, may be used in catalyzing nitroxide reducing reaction in environment protection.
Description
Technical field
The present invention be a kind of be the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite.
Background technology
Diatomite be diatom under physical and chemical conditions such as certain light, temperature and nutritive substance by the soluble silica in the bio-absorbable water, and preserve a kind of biogenic sediment rock of getting off with diatom remains form.Clay mineral and detrital minerals such as quartz, feldspar such as normal association kaolin, montmorillonite, hydromica in diatomite.The oxide compound of diatomaceous main chemical compositions silicon, aluminium, iron, calcium, magnesium etc., wherein silicon oxide mainly exists with amorphous form.Diatomite is the natural resource that a kind of distributed pole is wide, reserves are bigger, place's diatomite ore China has found 70 in 14 provinces (autonomous region) surplus, and 3.2 hundred million tons of proven reserve, prospective reserves is more than 1,000,000,000 tons.At present, diatomite is in the industrial preparation that is mainly used in flocculating aids, lagging material and support of the catalyst, and added value of product is relatively low, utilizes diatomite resource how more profoundly, and to improve its utility value still be a problem demanding prompt solution.
In recent years, overseas utilization diatomite is the silicon source, has synthesized the LTA and the SOD zeolite of low silica-alumina ratio by the method for adding the aluminium source.Utilize organic amine to be template, synthesized the MOR zeolite.During but these products all concentrate on, the zeolite of low silica-alumina ratio, and high-quality diatomaceous silica content can reach more than the 90wt%, should be directly as the raw material of synthesizing high-silicon aluminum ratio zeolite.Simultaneously, the ferro element in the natural diatomaceous earth can be fully utilized to synthesize heteroatom zeolite, and it has very high activity in the environment protection catalytic reaction.
Summary of the invention
The purpose of this invention is to provide a kind of easy and simple to handle, with low cost, Fe-ZSM-5 microsphere of zeolite that effect is good.
The used diatomite material of the present invention can be the higher diatomite of various types of silica contents, the diatomite that the promptly different places of production, composition differ.
The method for preparing the Fe-ZSM-5 microsphere of zeolite involved in the present invention is as follows:
1. raw material is removed non-mineral impurity by the settling process screening;
2. take by weighing an amount of alkali, template and additive and be dissolved in a certain amount of water, stir an amount of garbled diatomite of adding down, stir aging for some time;
3. the mixture that will wear out is transferred in the stainless steel cauldron of band tetrafluoroethylene liner, at a certain temperature crystallization for some time;
4. get product after product filtration, washing, drying and the high-temperature roasting that crystallization is good.
Said raw material is the higher diatomite of various types of silica contents in 1, and said settling process screening is meant raw material and water thorough mixing are discarded settling velocity very fast and long-time non-settling impurity, suction filtration drying then.
Said alkali is meant the highly basic of solubilities such as NaOH, KOH, LiOH in 2, and template is meant that 4-propyl bromide (TPABr), hexanediamine etc. can be used for the structure directing agent of synthetic ZSM-5 zeolite, and additive is meant NaCl, Na
2SO
4Sodium salt etc. solubility.During practical application, SiO in the diatomite
2(use M with alkali
2O represents, M=Li, and Na, mol ratio K) is 5.0~20.0; SiO
2With the mol ratio of template be 5.0~15.0; SiO
2With the mol ratio of Na in the sodium salt be 0.1~0.5.The concentration range of all ingredients is respectively: alkali 0.03~0.17mol L
-1Template 0.025~0.075mol L
-1, approaching with the reagent concentration of existing synthetic ZSM-5 zeolite method.The concentration range of additive (concentration with Na in the sodium salt is represented) is 0.50~3.00mol L
-1Aging temperature is 5~60 ℃, and digestion time is 0.5~24 hour.
Said crystallization temperature can be 140~200 ℃ in 3, and crystallization time can be 3~10 days.
Said maturing temperature can be 450~600 ℃ in 4, and roasting time can be 3~10 hours.
Better condition of the present invention is: silicon oxide and alkali are (according to M in the raw material
2The O form is calculated, M=Li, and Na, K), the molar ratio range of template, additive is respectively 10.0~15.0,7.5~12.5,0.2~0.4.Aging temperature is 15~30 ℃, and digestion time is 3~5 hours.
Crystallization temperature is 170~190 ℃, and crystallization time is 5~7 days.
Maturing temperature is 500~550 ℃, and roasting time is 4~6 hours.
Above-mentioned condition had both improved preparation efficiency, had guaranteed quality product again.
The present invention is not adding under other silicon, aluminium, the ferrous components condition according to raw material sources, can make the Fe-ZSM-5 microsphere of zeolite of high-crystallinity.The preparation method is simple, with low cost, and product application is respond well in the environment protection catalytic adsorbing domain.In addition, product has abundant macropore and microvoid structure, can improve the velocity of diffusion of reactant and product in catalyzed reaction.Following table be the different synthesis conditions relative crystallinity that obtains product with thing mutually:
Numbering | Relative crystallinity (%) | The thing phase |
??A 1 | ????93 | The Fe-ZSM-5 microsphere of zeolite |
??A 2 | ????12 | Diatomite and tabular Fe-ZSM-5 zeolite |
??A 3 | ????93 | The Fe-ZSM-5 microsphere of zeolite |
??A 4 | ????73 | Fe-ZSM-5 microsphere of zeolite and quartz |
??A 5 | ????100 | Tabular Fe-ZSM-5 zeolite |
??A 6 | ????95 | Tabular Fe-ZSM-5 zeolite and Fe-ZSM-5 microsphere of zeolite |
??A 7 | ????90 | The Fe-ZSM-5 microsphere of zeolite |
??A 8 | ????83 | Fe-ZSM-5 microsphere of zeolite and quartz |
Description of drawings
Fig. 1 is a product A
1SEM figure.
Fig. 2 is a product A
1High multiple SEM figure.
Fig. 3 is a product A
1Nitrogen adsorption curve figure.
Specific implementation method
Following example is to further specifying that Fe-ZSM-5 method for preparing microsphere of zeolite provided by the present invention is done.
Example 1
Take by weighing 0.06g sodium hydroxide, 0.20g 4-propyl bromide and 1.0g sodium-chlor, be dissolved in 15ml water.Add the 100# diatomite (main component: SiO that the garbled Changbai of 0.5g diatomite ore is produced under the vigorous stirring
286.7%, Al
2O
34.5%, Fe
2O
31.23%, and K
2O+Na
2O 0.9~1.1%), continue to stir 3 hours.Mixture is transferred to the stainless steel cauldron of band tetrafluoroethylene liner, 180 ℃ of hydrothermal crystallizings 6 days.Product is through washing, suction filtration, drying, and template is removed in roasting under 550 ℃ of air atmospheres at last.Product is designated as A
1
Example 2~4
Press the described method of example 1 and handle diatomite, but the add-on of sodium hydroxide changes into 0.02,0.04 and 0.08g, the proportioning and the reaction conditions of other reactant all do not change.The product that makes is designated as A
2, A
3And A
4
Example 5~8
Press the described method of example 1 and handle diatomite, but the add-on of sodium-chlor changes into 0,0.5,1.5 and 2.0g, the proportioning and the reaction conditions of other reactant all do not change.The product that makes is designated as A
5, A
6, A
7And A
8
Above-mentioned product adopts xrd method (carrying out on Rigaku D/max-II x-ray powder diffraction instrument) to measure relative crystallinity (with A
5Be benchmark), SEM figure is in Philips XL30 scanning electronic microscope photographs, and acceleration voltage is 20kV.Nitrogen adsorption curve figure measures on ASAP-2000 type physical adsorption appearance.
Claims (7)
1. one kind is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that diatomite is direct and alkali, template and additive mixing are aging, hydrothermal crystallizing obtains product then, and the sodium salt additive is to the control of product pattern, and actual conditions is:
(1) raw material of preparation microsphere of zeolite is a diatomite;
(2) used alkali is inorganic solubility highly basic, SiO in the diatomite
2With alkali M
2The mol ratio of O is 5.0~20.0;
(3) used template is the structure directing agent that is used for synthetic ZSM-5 zeolite, SiO in the diatomite
2With the mol ratio of template be 5.0~15.0;
(4) used additive is meant the sodium salt of solubility, SiO in the diatomite
2With the mol ratio of Na in the sodium salt be 0.1~0.5;
(5) aging temperature is 5~60 ℃, and the aged time is 0.5~24 hour;
(6) the hydrothermal crystallizing temperature is 140~200 ℃, and the time of crystallization is 3~10 days.
2. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that water soluble alkali is LiOH, or NaOH, or KOH, and the alkali consumption is SiO
2/ M
2O (M=Li, Na, K)=10.0~15.0.
3. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that template is a 4-propyl bromide, or 4-propyl ammonium chloride, or hexanediamine, or hexylene glycol, SiO in the diatomite
2With the mol ratio of template be 7.5~12.5.
4. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that additive is meant NaCl, or NaNO
3, or Na
2SO
4, SiO in the diatomite
2With the mol ratio of Na in the sodium salt be 0.2~0.4.
5. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that aging temperature is 15~30 ℃, and digestion time is 3~5 hours.
6. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, and the time that it is characterized in that hydrothermal crystallizing is 5~7 days, and crystallization temperature is 170~190 ℃.
7. according to claim 1 is the method for feedstock production Fe-ZSM-5 microsphere of zeolite with diatomite, it is characterized in that the microsphere of zeolite of this method preparation is used for catalyzer, sorbent material or exhaust gas treating agent.
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CN101450322B (en) * | 2007-12-05 | 2011-05-18 | 中国科学院大连化学物理研究所 | Preparation method Fe/ZSM-5 catalyst for directly decomposing N2O |
CN102295299A (en) * | 2010-06-23 | 2011-12-28 | 中国科学院大连化学物理研究所 | Fractional crystallization synthesis method for high-content skeleton iron ZSM-35 molecular sieve |
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CN101450322B (en) * | 2007-12-05 | 2011-05-18 | 中国科学院大连化学物理研究所 | Preparation method Fe/ZSM-5 catalyst for directly decomposing N2O |
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