CN105883847A - Preparation method of iron-containing Y-shaped zeolite - Google Patents
Preparation method of iron-containing Y-shaped zeolite Download PDFInfo
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- CN105883847A CN105883847A CN201410776003.4A CN201410776003A CN105883847A CN 105883847 A CN105883847 A CN 105883847A CN 201410776003 A CN201410776003 A CN 201410776003A CN 105883847 A CN105883847 A CN 105883847A
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Abstract
The invention belongs to the preparation field of heteroatom modified micropore zeolites and particularly relates to a preparation method of a ferric oxide-loaded modified Y-shaped zeolite. The preparation method particularly comprises the following steps: firstly adequately mixing a silicon source, an aluminum source, sodium hydroxide and water, ageing, and preparing a guiding agent solution; uniformly mixing sodium metaaluminate, sodium hydroxide, water and the guiding agent solution to form initial gel, directly adding ferric nitrate into the initial gel, carrying out suction filtration on iron-containing hydrogel, carrying out crystallization at a hydrothermal condition, and washing, filtering, drying and roasting solids, so as to obtain the product. By virtue of the preparation method, Fe<3+> is directly introduced into the initial gel synthesized from the Y-shaped zeolite, so that the processing steps of dipping, ion exchange and the like can be omitted, and the operation is simple and convenient; and by virtue of a method of sequential pump-drying and crystallization, the water content in a water treatment process for synthesizing zeolite materials in a traditional technique can be substantially decreased, the yield of a single-kettle molecular sieve can be increased, the energy efficiency can be improved through the process, and the production cost can be lowered. The preparation method has industrial practical value.
Description
Technical field
The invention belongs to the preparation field of hetero atom modified micropore zeolite, be specifically related to a kind of iron oxide modified y-type zeolite of loading
Preparation method.
Background technology
Along with developing rapidly of the industry such as petrochemical industry, metallurgy, printing and dyeing, create a large amount of industrial wastewater containing persistent organic pollutants,
One of main source becoming water environment pollution.Removal to high-concentration hardly-degradable organic pollution, recognizes current water treatment field
A great problem.
Use homogeneous catalyst (such as Fenton reagent, ferrous salt etc.) catalysis H2O2Oxidation, can make organic pollutant degradation extremely
CO2And H2O, the advanced oxidation processes hence with hydroxyl radical free radical degraded and mineralising organic pollution receives significant attention.But
The homogeneous catalyst that this method uses is difficult to separate with reaction medium, brings active component to run off and secondary pollution problems.Use non-
Homogeneous solid catalyst replaces homogeneous iron salt, can overcome the deficiency of homogeneous method, become current study hotspot.
Zeolite molecular sieve is a very important inorganic porous material of class, have high heat and hydrothermal stability, bigger serface,
The character such as good ion-exchange performance and the pore passage structure with molecular dimension size (usually 0.3～2.0nm), quilt
It is widely used in many industrial circles, such as shape-selective catalyst, adsorbent, ion-exchanger etc..Iron oxides is carried on boiling
Make iron-containing zeolite heterogeneous catalysis among stone structure for catalytic degradation organic pollution (such as phenol, waste water from dyestuff), have
Well degradation effect.But traditional zeolite synthesis technique mostly is silicon source, aluminum source to be thoroughly mixed to form initial solidifying with alkali source solution
Glue, obtains solid by this Primogel through hydro-thermal reaction, crystallization.The method of doping iron has infusion process, ion exchange, coprecipitated
Shallow lake methods etc., are the method using iron salt solutions that zeolite materials is carried out post processing, relate to many operating procedures, be unfavorable for industry
Implement and reduce cost.At the beginning of zeolite synthesis, ferrum species are introduced in its Primogel, then carry out crystallization, then can simplify
Synthesis step.
In the hydrothermal reaction process of this external crystal growth, substantial amounts of water is as solvent, and in still, major part volume is by shared by aqueous solvent,
Make output per single reactor limited, consume energy bigger.If able to the water content in minimizing hydrothermal reaction process, then can improve in one-pot
Solid content, improves one-pot molecular sieve yield, reduces energy consumption, cost-effective.To commercial production, the reduction of production cost is i.e. meaned
The raising of economic benefit, meanwhile, low energy consumption is also the requirement of environmental protection.
Summary of the invention
It is desirable to provide the preparation method of a kind of iron content y-type zeolite, the method is directly by Fe3+Introduce y-type zeolite synthesis
Among Primogel, it is to avoid the post-processing steps such as dipping, ion exchange, and use iron content Primogel is drained, then enter
The method of row high temperature crystallization, reduces the water content in hydrothermal reaction process, improves the output per single reactor of iron content molecular sieve, this technical staff
Skill is simple, it is easy to operation, it is simple to industrializing implementation.The concrete technical scheme of the present invention is:
1) preparation of directed agents
By waterglass, sodium metaaluminate, sodium hydroxide and water, being sufficiently mixed, form a clear transparent solutions, room temperature stands aging
24～60 hours, obtain directing agent solution.In this directing agent solution, the addition molar ratio of each reaction raw materials is: Na2O/
Al2O3/SiO2/H2O=12～20/1/19/300～400.
2) preparation of Primogel
A certain amount of sodium metaaluminate, sodium hydroxide and water are mixed, is slowly added dropwise above-mentioned directed agents wherein, is sufficiently stirred for 15～60
Minute, forming Primogel, the addition of described each reaction raw materials should make the molar ratio of each composition in Primogel be: Na2O
/Al2O3/SiO2/H2O=3.2～4.5/1/3/120～180；
3) incorporation of ferrum
A certain amount of iron salt (Fe (NO it is slowly added in above-mentioned Primogel3)3·9H2O), Fe in Primogel is made2O3With SiO2
Molar ratio be 0.1～1.0: 3, continue stirring 30～60 minutes, obtain iron-bearing water gel；
4) crystallization synthesis iron content y-type zeolite is drained
Above-mentioned iron-bearing water gel being carried out sucking filtration, drips to no liquid, half dry solid obtained carries out hydro-thermal reaction at 80～100 DEG C,
Stand crystallization 18～24 hours；
5) filter, wash, be dried, roasting
After crystallization completes, by the product washing obtained, sucking filtration, and it is dried more than 20 hours at 80 DEG C.By product after being dried
It is placed in the Muffle kiln roasting 5 hours of 550 DEG C
Beneficial effect: the synthetic method of the iron content y-type zeolite that the present invention provides, due to directly by Fe3+Introducing y-type zeolite synthesizes
Primogel among, it is to avoid the post processing such as dipping, ion exchange introduces the step of ferrum, easy and simple to handle；Use at the beginning of iron content
Beginning gel is drained, then the method carrying out high temperature crystallization, it is possible to water content in conventional hydrothermal processing procedure is greatly decreased, makes
In one-pot, the solids content of iron content molecular sieve increases, and this process can improve efficiency, saves production cost, has huge industry
Practical value and application prospect.
Detailed description of the invention
The following is the specific embodiment of the present invention, be that the present invention is further described.But specific embodiment is not intended to present invention power
Profit requirement.
The raw material used in specific embodiment is as follows:
Waterglass: Jin Nan Ju Xing water glass plant, Tianjin produces, and wherein siliconoxide mass mark is 20.3%；
Sodium metaaluminate: Tianjin recovery fine chemistry industry institute produces；
Sodium hydroxide: sky, the north, Tianjin medical chemistry chemical reagent work produces.
Embodiment 1:
The preparation of directed agents: be dissolved in 10.0 milliliters of water by 0.7 gram of sodium metaaluminate, adds 3 grams of sodium hydroxide, stirs to clarify,
22.5 grams of waterglass of dropping, mechanical agitation about 30 minutes, obtain a clear transparent solutions wherein, and left at room temperature is aging 24 little
Time, obtain directed agents.
The preparation of iron content y-type zeolite: be dissolved in 38.5 milliliters of water by 3.5 grams of sodium metaaluminates, adds 41.5 grams of waterglass, stirring
Uniformly, it is slowly added dropwise 33.5 grams of directing agent solution, mechanical agitation about 30 minutes wherein, after mix homogeneously, obtains Primogel,
It is added thereto to 1.2 grams of Fe(NO3)39H2Os, continues to stir 60 minutes, the gel sucking filtration that will obtain, to no longer there being liquid to drip,
This half dry solid being loaded in reactor, 100 DEG C of standing and reacting 24 hours, the product obtained was scrubbed, sucking filtration, and in 80
DEG C it is dried 20 hours, after being dried, product is placed in the Muffle kiln roasting 5 hours of 550 DEG C, obtains end product.
Embodiment 2:
The preparation of directed agents: be dissolved in 10.0 milliliters of water by 0.7 gram of sodium metaaluminate, adds 3 grams of sodium hydroxide, stirs to clarify,
22.5 grams of waterglass of dropping, mechanical agitation about 30 minutes, obtain a clear transparent solutions wherein, and left at room temperature is aging 40 little
Time, obtain directed agents.
The preparation of iron content y-type zeolite: be dissolved in 26 milliliters of water by 2.4 grams of sodium metaaluminates, adds 30 grams of waterglass, and mixing is all
Even, it is slowly added dropwise 16 grams of directing agent solution, mechanical agitation about 30 minutes wherein, after mix homogeneously, obtains Primogel, to
Wherein add 2.5 grams of Fe(NO3)39H2Os, continue to stir 60 minutes, the gel sucking filtration that will obtain, to no longer there being liquid to drip,
This half dry solid being loaded in reactor, 100 DEG C of standing and reacting 24 hours, the product obtained was scrubbed, sucking filtration, and in 80
DEG C it is dried 20 hours, after being dried, product is placed in the Muffle kiln roasting 5 hours of 550 DEG C, obtains end product.
Embodiment 3:
The preparation of directed agents: be dissolved in 10.0 milliliters of water by 0.7 gram of sodium metaaluminate, adds 3 grams of sodium hydroxide, stirs to clarify,
22.5 grams of waterglass of dropping, mechanical agitation about 30 minutes, obtain a clear transparent solutions wherein, and left at room temperature is aging 24 little
Time, obtain directed agents.
The preparation of iron content y-type zeolite: be dissolved in 37 milliliters of water by 3.2 grams of sodium metaaluminates, adds 1.6 grams of sodium hydroxide, and 47.2
Gram waterglass, mix homogeneously, it is slowly added dropwise 4 grams of directing agent solution wherein, mechanical agitation about 30 minutes, after mix homogeneously
To Primogel, being added thereto to 3.6 grams of Fe(NO3)39H2Os, continue stirring 60 minutes, the gel sucking filtration that will obtain, to not
There is liquid to drip again, this half dry solid is loaded in reactor, 100 DEG C of standing and reacting 24 hours, the product obtained is scrubbed,
Sucking filtration, and be dried 20 hours in 80 DEG C, after being dried, product is placed in the Muffle kiln roasting 5 hours of 550 DEG C, obtains
End-product.
The above, be only several case study on implementation of the present invention, and the present invention not does any pro forma restriction, any familiar
Professional and technical personnel, in the range of without departing from technical solution of the present invention, when structure and the technology contents of available the disclosure above
Make a little change or be modified to the equivalent case study on implementation of equivalent variations.But every content without departing from technical solution of the present invention,
Any simple modification above case study on implementation done according to the technical spirit of the present invention, equivalent variations and modification, the most still belong to this
In the range of bright technical scheme.
Claims (7)
1. the preparation method of an iron content y-type zeolite, it is characterised in that specifically include the following step:
1) preparation of directed agents
First by silicon source, aluminum source, alkali source and water, being sufficiently mixed according to a certain percentage, left at room temperature aging 24～60 is little
Time, i.e. obtain required directed agents；
2) preparation of Primogel
A certain amount of silicon source, aluminum source, alkali source and water are mixed, is slowly added dropwise above-mentioned directed agents wherein, is sufficiently stirred for 15～60 points
Clock, obtains Primogel；
3) incorporation of ferrum
In above-mentioned Primogel, it is slowly added to a certain amount of iron salt, continues stirring 30～60 minutes, obtain iron-bearing water gel；
4) crystallization method synthesis iron content y-type zeolite is drained
Above-mentioned iron-bearing water gel being carried out sucking filtration, drips to no liquid, half dry solid obtained by sucking filtration carries out water at 80～100 DEG C
Thermal response, standing crystallization 18～24 hours；
5) filter, wash, be dried, roasting
After crystallization completes, by the product washing obtained, sucking filtration, and it is dried more than 20 hours at 80 DEG C, by product after being dried
It is placed in the Muffle kiln roasting 5 hours of 550 DEG C.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the silicon source used in synthesis is water
Glass.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the aluminum source used in synthesis is inclined
Sodium aluminate.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the alkali source used in synthesis is hydrogen
Sodium oxide.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the water used in synthesis for go from
Sub-water.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the addition of described each reaction raw materials
The molar ratio of each composition in directed agents should be made: at Na to be2O/Al2O3/SiO2/H2O=12～20/1/19/300～400.
The preparation method of iron content y-type zeolite the most according to claim 1, it is characterised in that the addition of described each reaction raw materials
The molar ratio of each composition in Primogel should be made: Fe to be2O3/Na2O/Al2O3/SiO2/H2O=0.1～1.0/3.2～4.5/1/3
/ 120～180.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732747A (en) * | 2016-11-28 | 2017-05-31 | 天津工业大学 | A kind of molecular sieve fenton catalyst and high-efficiency synthesis method for eliminating organic dyestuff pollution |
| CN107265475A (en) * | 2017-06-19 | 2017-10-20 | 太原理工大学 | A kind of iron series element micro porous molecular sieve and preparation method and application |
| CN112939013A (en) * | 2021-03-10 | 2021-06-11 | 中国石油大学(北京) | High-silicon small-grain Y-type molecular sieve and preparation method and application of template-free molecular sieve |
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| US4309313A (en) * | 1980-05-23 | 1982-01-05 | W. R. Grace & Co. | Synthesis of cesium-containing zeolite, CSZ-1 |
| US4333859A (en) * | 1980-10-27 | 1982-06-08 | W. R. Grace & Co. | High silica faujasite polymorph - CSZ-3 and method of synthesizing |
| CN101134576A (en) * | 2006-09-01 | 2008-03-05 | 中国石油大学(北京) | Method for improving Y-shaped molecular sieve water heat stability by employing cage heteroatom |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732747A (en) * | 2016-11-28 | 2017-05-31 | 天津工业大学 | A kind of molecular sieve fenton catalyst and high-efficiency synthesis method for eliminating organic dyestuff pollution |
| CN107265475A (en) * | 2017-06-19 | 2017-10-20 | 太原理工大学 | A kind of iron series element micro porous molecular sieve and preparation method and application |
| CN107265475B (en) * | 2017-06-19 | 2019-04-26 | 太原理工大学 | A kind of iron series element micro porous molecular sieve and preparation method and application |
| CN112939013A (en) * | 2021-03-10 | 2021-06-11 | 中国石油大学(北京) | High-silicon small-grain Y-type molecular sieve and preparation method and application of template-free molecular sieve |
| CN112939013B (en) * | 2021-03-10 | 2022-11-01 | 中国石油大学(北京) | High-silicon small-grain Y-type molecular sieve and preparation method and application of template-free molecular sieve |
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Application publication date: 20160824 |