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 PDF

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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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diatomite
zeolite
zsm
microsphere
sio
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CN1281495C (en
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巍 山
山巍
唐颐
张亚红
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Fudan University
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Fudan University
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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

With diatomite is the method for feedstock production Fe-ZSM-5 microsphere of zeolite
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.
CN 200410015975 2004-01-19 2004-01-19 Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material Expired - Fee Related CN1281495C (en)

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Cited By (15)

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CN101318132B (en) * 2007-06-08 2010-09-01 中山大学 Method for preparing supported nano-iron oxide/tripolite compound catalyst
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
CN102602954A (en) * 2011-12-23 2012-07-25 内蒙古师范大学 Method for preparing SBA-15 and P-type molecular sieves by hangjin2# clay
CN103687810A (en) * 2011-09-15 2014-03-26 雪佛龙美国公司 Method for preparing lta-type zeolites using a novel structure directing agent
CN103831127A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Catalyst for C4 hydrogenation aromatization and preparation method
CN103831128A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof
CN103831126A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 C4 liquefied gas hydrogenation aromatization catalyst and preparation method thereof
CN104150505A (en) * 2013-05-16 2014-11-19 中国石油化工股份有限公司 Method for preparing nano ZSM-5 zeolite by taking diatomite as raw material
CN104174355A (en) * 2014-08-19 2014-12-03 中国地质科学院水文地质环境地质研究所 Zeolite-loaded nano-iron material for removing heavy metals in water and preparation method of zeolite nano-iron material for removing heavy metals in water
WO2015161630A1 (en) * 2014-04-23 2015-10-29 中国石油大学(北京) Fezsm-5 molecular sieve and synthesis process therefor
CN105084390A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Method for preparation of spherical ZSM-5 zeolite from diatomite
CN105749961A (en) * 2016-03-22 2016-07-13 河南永大化工有限公司 Shape-selective catalyst for preparing p-xylene as well as preparation and application thereof
CN108698017A (en) * 2016-02-18 2018-10-23 水泽化学工业株式会社 Volatile organic compounds adsorbent and blending have the resin combination of volatile organic compounds adsorbent
CN110240177A (en) * 2019-07-02 2019-09-17 华东理工大学 A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318132B (en) * 2007-06-08 2010-09-01 中山大学 Method for preparing supported nano-iron oxide/tripolite compound catalyst
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
CN102295299B (en) * 2010-06-23 2013-01-02 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
CN103687810A (en) * 2011-09-15 2014-03-26 雪佛龙美国公司 Method for preparing lta-type zeolites using a novel structure directing agent
CN102602954A (en) * 2011-12-23 2012-07-25 内蒙古师范大学 Method for preparing SBA-15 and P-type molecular sieves by hangjin2# clay
CN103831127A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Catalyst for C4 hydrogenation aromatization and preparation method
CN103831128A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 Modified nano molecular sieve hydrogenation aromatization catalyst and preparation method thereof
CN103831126A (en) * 2012-11-27 2014-06-04 中国石油天然气股份有限公司 C4 liquefied gas hydrogenation aromatization catalyst and preparation method thereof
CN103831128B (en) * 2012-11-27 2016-12-21 中国石油天然气股份有限公司 A kind of modified nano molecular sieve hydroaromatization catalyst and preparation method
CN104150505A (en) * 2013-05-16 2014-11-19 中国石油化工股份有限公司 Method for preparing nano ZSM-5 zeolite by taking diatomite as raw material
WO2015161630A1 (en) * 2014-04-23 2015-10-29 中国石油大学(北京) Fezsm-5 molecular sieve and synthesis process therefor
CN105016355A (en) * 2014-04-23 2015-11-04 中国石油大学(北京) FeZSM-5 molecular sieve and synthetic method thereof
CN105084390A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Method for preparation of spherical ZSM-5 zeolite from diatomite
CN104174355A (en) * 2014-08-19 2014-12-03 中国地质科学院水文地质环境地质研究所 Zeolite-loaded nano-iron material for removing heavy metals in water and preparation method of zeolite nano-iron material for removing heavy metals in water
CN104174355B (en) * 2014-08-19 2016-08-24 中国地质科学院水文地质环境地质研究所 A kind of for zeolite-loaded nano-iron material removing Heavy Metals in Waters and preparation method thereof
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CN108698017B (en) * 2016-02-18 2021-07-27 水泽化学工业株式会社 Volatile organic compound adsorbent and resin composition blended with volatile organic compound adsorbent
CN105749961A (en) * 2016-03-22 2016-07-13 河南永大化工有限公司 Shape-selective catalyst for preparing p-xylene as well as preparation and application thereof
CN110240177A (en) * 2019-07-02 2019-09-17 华东理工大学 A kind of laminated structure MFI type zeolite molecular sieve and preparation method thereof

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