CN105016355A - FeZSM-5 molecular sieve and synthetic method thereof - Google Patents

FeZSM-5 molecular sieve and synthetic method thereof Download PDF

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CN105016355A
CN105016355A CN201410165441.7A CN201410165441A CN105016355A CN 105016355 A CN105016355 A CN 105016355A CN 201410165441 A CN201410165441 A CN 201410165441A CN 105016355 A CN105016355 A CN 105016355A
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molecular sieve
fezsm
alumina ratio
mineral
synthetic method
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CN105016355B (en
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鲍晓军
岳源源
刘海燕
袁珮
石冈
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Beijing Cup Green Catalytic Technology Co Ltd
China University of Petroleum Beijing
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Beijing Cup Green Catalytic Technology Co Ltd
China University of Petroleum Beijing
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent

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  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention provides a FeZSM-5 molecular sieve and a synthetic method thereof. The method comprises the following steps: respectively activating low Si/Al ratio minerals and/or high Si/Al ratio minerals, wherein the low Si/Al ratio minerals are activated by mixing the low Si/Al ratio minerals with a sodium hydroxide solution uniformly and then drying the mixture, and the high Si/Al ratio minerals are activated through roasting treatment; mixing the activated low Si/Al ratio minerals and/or high Si/Al ratio minerals with sodium hydroxide, water and a template agent and crystallizing the mixture and controlling the feed quantity so that the molar ratio is 0.05-0.4Na2O to 1SiO2 to 0.02-0.5Al2O3 to 0.004-0.1Fe2O3 to 10-80H2O; cooling and filtering a product obtained through crystallization, washing a filter cake with water until the filter cake is neutral and drying the filter cake, thus obtaining the FeZSM-5 molecular sieve. The FeZSM-5 molecular sieve and the synthetic method have the advantages that not only can the production cost on molecular sieve synthesis be substantially reduced but also the greenness of the synthesis process and the atom utilization rate can be greatly increased; the obtained molecular sieve has excellent physiochemical properties.

Description

A kind of FeZSM-5 molecular sieve and synthetic method thereof
Technical field
The invention belongs to Zeolite synthesis field, relate to a kind of FeZSM-5 molecular sieve and synthetic method thereof, its with natural mineral for raw material provides whole silicon sources required for synthesis FeZSM-5 molecular sieve, aluminium source and source of iron.
Background technology
Si or Al in framework of molecular sieve can be obtained hetero-atom molecular-sieve by other elements as Fe, B, Ti, Ga etc. replace.Utilizing the backbone element in hybrid atom MCM-41 molecular sieve, is one of molecular sieve modified important method, and this method by the acidity of modulation molecular sieve, pore structure and then can change the activity of molecular sieve, stability and selectivity.In recent years, the focus of research has been become using the FeZSM-5 molecular sieve of transition-metal Fe modification as catalyzer.FeZSM-5 causes the broad interest of people, at N with the catalytic performance of its excellence 2o Direct Resolution, N 2o Selective catalytic reduction and N 2o is oxidized in the reactions such as Benzene to phenol and shows excellent catalytic performance.
Heteroatoms Fe is incorporated into method FeZSM-5 preparing by ZSM-5 molecular sieve a lot, is mainly divided into direct synthesis technique and post-modification method.In building-up process, add Fe species obtains FeZSM-5 molecular sieve to direct synthesis technique exactly, post-modification method is processed existing ZSM-5 molecular sieve by some special methods, mainly comprises: liquid ion exchange method, solid liposome nanoparticle method, isomorphous substitution method and chemical evapn phase method.
CN1256243 discloses a kind of preparation method of little crystal grain FeZSM-5 molecular sieve, with silicon-containing material, inorganic molysite, inorganic sodium, organic amine, mineral acid and deionized water for raw material, adopt hydrothermal synthesis method, low whipping speed is 400-500 rev/min, rises to 100 ~ 140 DEG C with the speed of 2 DEG C/min by room temperature, constant temperature 130h, completes crystallization.But the method must complete under agitation, higher to equipment requirements, experiment proves, can not obtain FeZSM-5 molecular sieve in a static condition by the method; And crystallization time is long, reach 130h.
CN103183359A discloses a kind of nano level FeZSM-5 molecular sieve and its preparation method and application, concrete preparation method is: be dissolved in deionized water by template and aluminium source, silicon source is dripped after stirring to clarify at 25 ~ 40 DEG C, add alkali source again, molysite is added after alkali source dissolves completely, stirring 3 ~ 6h is placed in hydrothermal reaction kettle, in 40 ~ 60 DEG C of aging 1 ~ 4h of static state constant-temperature after sealing; Static state constant-temperature crystallization 24 ~ 60h at 140 ~ 180 DEG C again after static state constant-temperature is aging; After crystallization terminates, synthetic system is cooled to room temperature, then reaction mixture is filtered or centrifugation, and particle diameter will be obtained after gained filter cake washing, drying, roasting be less than the particle nano level FeZSM-5 molecular sieve of 50nm.
Pieterse (Applied Catalysis B, 2004,51:215-228) etc. compare the activity of the FeZSM-5 obtained through ion-exchange for source of iron with ferrous sulfate, Mohr's salt, iron nitrate respectively, experimental result shows, the catalytic activity of the FeZSM-5 molecular sieve prepared as source of iron with Mohr's salt is best.
The preparation method of the FeZSM-5 molecular sieve that above patent or document are reported is all take inorganic chemical as silicon source, aluminium source and source of iron, these inorganic chemicals are obtain from natural mineral through numerous and diverse reaction and sepn process mostly, production process route is long, material consumption energy consumption is high, and most of process exists serious disposal of pollutants.Therefore, if can directly to be rich in the natural mineral of silicon, aluminium and iron for Material synthesis molecular sieve, not only raw material sources are extensive, and the synthetic route that can greatly shorten from raw material to molecular sieve product, significantly reduce the energy consumption of process of producing molecular sieve, material consumption and disposal of pollutants, and significantly reduce production cost, thus open up new approach for the synthesis of molecular sieve, there is vast potential for future development.
Kaolin belongs to 1:1 type dioctahedron lamellar aluminosilicate clay mineral, and its basic structure is that the cladding periodicity repeated arrangement on c-axis direction be made up of one deck alumina octahedral and one deck silicon-oxy tetrahedron is formed, and its typical chemical constitution is Al 2o 32SiO 22H 2o, thus can as the synthesis of the silicon source of molecular sieve and aluminium source; In natural kaolin mineral, association has iron contamination simultaneously, can provide source of iron for synthesis containing heteroatoms FeZSM-5 molecular sieve.
The basic structural unit of rectorite is silicon-oxy tetrahedron and alumina octahedral, and silicon-oxy tetrahedron is with the oxygen of three bottom it, and three tetrahedrons be adjacent respectively are connected in the mode of corner-sharing top oxygen, forms the unit layer of layer silicate mineral.In unit layer, the combination of tetrahedral sheet and octahedral sheet can be 1:1 type or 2:1 type, and the chemical formula of its unit cell is Al 4[Si 8o 20] (OH) 4, thus also can as the synthesis of the silicon source of molecular sieve and aluminium source; Meanwhile, in natural rectorite mineral, also association has iron contamination, can provide source of iron for synthesis containing heteroatoms FeZSM-5 molecular sieve.
Diatomite be diatom under the physical and chemical conditions such as certain light, temperature and nutritive substance by the soluble silica in bio-absorbable water, and with a kind of biogenic sediment rock that diatom form preserves.The general theoretical construct formula of diatomite is Mg 8[Si 12o 30] (OH) 4(OH 2) 48H 2o, the chain laminate structure in 2:1 type.Diatomaceous chemical composition mainly amorphous Si O 2, simultaneously also containing a small amount of Al 2o 3and Fe 2o 3, activated can be used as synthesis of molecular sieve silicon source, aluminium source and source of iron.Diatomite is industrially mainly used in flocculating aids, filler and support of the catalyst, and utilizes diatomite mainly to concentrate on LTA, SOD and MOR zeolite of low silica-alumina ratio as Material synthesis zeolite, there is not yet and uses it for the report of synthesis containing the molecular sieve of heteroatoms Fe.
In recent years, along with the rise of green chemistry and engineering tide, use nontoxic raw material, improve the focus that raw material availability, the energy consumption reducing production process and decreasing pollution discharge etc. have become Novel chemical process study exploitation concern.In Zeolite synthesis field, if the sial source of iron in natural mineral can be utilized completely, and regulate as additional silicon source the silica alumina ratio that feeds intake using the natural mineral being rich in amorphous silicon oxide, be expected the molecular sieve green syt new technology path of soil boy structure close friend.
At present, had with natural mineral is the report that type ZSM 5 molecular sieve prepared by raw material, but the part sial that only make use of in mineral, still needs and will add a certain amount of additional chemical silicon source or aluminium source to regulate silica alumina ratio, and the synthesis of existing FeZSM-5 needs additional chemical source of iron bar none.Without additional chemical silicon source, aluminium source and source of iron, be that raw material is prepared the technology of the FeZSM-5 molecular sieve that silica alumina ratio is adjustable, iron level is adjustable there is not been reported completely with natural mineral.FeZSM-5 type molecular sieve is widely used molecular screen material in denitration field, and research and development are the technology of Material synthesis FeZSM-5 type molecular sieve completely with natural mineral, have broad application prospects.
Summary of the invention
One object of the present invention is to provide a kind of FeZSM-5 molecular sieve; FeZSM-5 molecular sieve of the present invention provides whole silicon sources required for synthesis, aluminium source and source of iron by natural mineral, obtains FeZSM-5 type molecular sieve through hydrothermal crystallizing.
Another object of the present invention is to the synthetic method that described FeZSM-5 molecular sieve is provided.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of synthetic method of FeZSM-5 molecular sieve, described method comprises the steps:
(1) activation of mineral: get low silica-alumina ratio mineral and/or high silica alumina ratio mineral activate respectively; Wherein the activation of low silica-alumina ratio mineral is for mix with sodium hydroxide solution, then dries; Wherein the activation of high silica alumina ratio mineral is calcination process;
(2) crystallization: the low silica-alumina ratio mineral after step (1) being activated and/or high silica alumina ratio mineral mixs crystallization afterwards with sodium hydroxide, water, template, and control charging capacity and make mol ratio satisfied: 0.05 ~ 0.4Na 2o:1SiO 2: 0.02-0.5Al 2o 3: 0.004-0.1Fe 2o 3: 10 ~ 80H 2o;
(3) aftertreatment: product cooling step (2) crystallization obtained, filtration, filter cake is washed to neutrality, obtains FeZSM-5 molecular sieve after super-dry.
According to synthetic method of the present invention, the low silica-alumina ratio mineral wherein described in step (1) and high silica alumina ratio mineral are the usual term of those skilled in the art, and those skilled in the art are all clear knows its implication; And preferably the silica alumina ratio of wherein said low silica-alumina ratio mineral is below 10 in the present invention, the silica alumina ratio of described high silica alumina ratio mineral is more than 30;
According to synthetic method of the present invention, the described low silica-alumina ratio mineral of step (1) are kaolin and/or rectorite; Described high silica alumina ratio mineral are diatomite and/or white carbon black.
The present invention provides whole silicon sources required for synthesis of molecular sieve, aluminium source and source of iron by natural mineral raw, does not need to add other forms of chemical silicon source, aluminium source and source of iron, has widened the Application Areas of natural mineral and the raw material sources of synthesis of molecular sieve.
The additional proportion of low silica-alumina ratio mineral of the present invention and high silica alumina ratio mineral need meet mol ratio 1SiO 2: 0.02-0.5Al 2o 3; Meeting under above-mentioned mol ratio condition, the usage ratio of the two can be calculated according to the silica alumina ratio of selected low silica-alumina ratio mineral and high silica alumina ratio mineral, one of can be wherein the suitable mixing of low silica-alumina ratio mineral and high silica alumina ratio mineral, or even the two.
According to synthetic method of the present invention, step (2) preferably can also control charging capacity and mol ratio is met: 0.15 ~ 0.35Na 2o:1SiO 2: 0.02-0.06Al 2o 3: 0.005-0.1Fe 2o 3: 15 ~ 75H 2o.
According to synthetic method of the present invention, step (2) described template is the combination of one or two or more kinds in 4-propyl bromide, tetraethylammonium bromide, TPAOH and triethylamine;
Wherein preferred template is 4-propyl bromide.
According to synthetic method of the present invention, SiO in the consumption of the further preferred steps of the present invention (2) described template and synthetic system 2mol ratio be 0.01 ~ 0.3:1.
According to synthetic method of the present invention, step (2) described crystallization is crystallization at 140-220 DEG C;
Wherein crystallization time is preferably 30-80h;
Can also preferred described crystallization be wherein crystallization at 160-210 DEG C;
Preferably crystallization time is 36-72h further.
According to synthetic method of the present invention, for improving the degree of crystallinity of molecular sieve further, the present invention further preferred step (1) is activated after mineral mix with sodium hydroxide, water, template after, first adjustment pH is crystallization again after 9-14.
According to synthetic method of the present invention, described in step (2), adjust ph is this area routine operation, adopt conventional inorganic acid alkali, such as the present invention can adopt sulphuric acid soln adjust ph.
According to synthetic method of the present invention, mineral after step (1) being activated wherein described in step (2) and sodium hydroxide, water, template are mixed into this area routine operation, such as directly feed intake and to be mixed by above-mentioned whole material;
Even also can fed batch, for example the present invention can also be, after high silica alumina ratio mineral, sodium hydroxide and suitable quantity of water are mixed, at 60-80 DEG C, stir 2-6h (stirring 4h at being preferably 70 DEG C), then add low silica-alumina ratio mineral, template and residue water.
Described appropriate water can judge to determine according to practical condition, with make material can blending dispersion even, such as the present invention is preferably by high silica alumina ratio mineral, sodium hydroxide and the water mixing accounting for total Water 1/4-1/2.
According to synthetic method of the present invention, in step (1), the mass ratio of low silica-alumina ratio mineral and sodium hydroxide solution is 1:1-10.
According to synthetic method of the present invention, the maturing temperature of step (1) is 600-1000 DEG C;
Wherein also preferred maturing temperature is 600-900 DEG C;
Wherein preferably roasting time is 2-8h.
According to synthetic method of the present invention, wherein preferred steps (1) sodium hydroxide solution is aqueous sodium hydroxide solution;
Wherein more preferably in described aqueous sodium hydroxide solution sodium hydroxide and quality than being 10-0.2:1;
According to synthetic method of the present invention, wherein also preferred steps (1) described oven dry is dry at 100-400 DEG C;
Wherein also preferably dry at 250-350 DEG C;
Synthetic method according to any one of the present invention, regulate pH to be after 9-14 in step (2), first burin-in process carries out crystallization again.
According to synthetic method of the present invention, described aging be aging 1-20h at 50-80 DEG C;
Wherein preferably aging is further aging 4-15h at 60-80 DEG C.
On the other hand, present invention also offers the FeZSM-5 molecular sieve that the synthetic method above described in any one prepares.
According to FeZSM-5 molecular sieve of the present invention, mole silica alumina ratio of described FeZSM-5 molecular sieve is 2.0-48.0, Fe 2o 3content is 0.7-3.5wt%; Wherein preferred described FeZSM-5 molecular sieve is 70 ~ 98% relative to the degree of crystallinity of the FeZSM-5 type molecular sieve being Material synthesis with pure chemistry reagent.
Wherein further preferred described silica alumina ratio is 15-38;
Wherein can also preferred described Fe 2o 3content is 0.7-1.5wt%;
In sum, the invention provides a kind of FeZSM-5 molecular sieve and synthetic method thereof.FeZSM-5 molecular sieve of the present invention has the following advantages:
Method of the present invention provides whole silicon sources required for synthesis, aluminium source and source of iron by natural mineral, obtains FeZSM-5 type molecular sieve through hydrothermal crystallizing.Adopt method provided by the invention to prepare to have the FeZSM-5 type molecular sieve of different crystallinity, Different Silicon aluminum ratio, different iron level, the relative crystallinity of the FeZSM-5 molecular sieve obtained is 70 ~ 98%, mole silica alumina ratio is 2.0 ~ 48.0, and wherein said natural mineral raw is the mixture of the natural mineral of low silica-alumina ratio and the natural mineral of high silica alumina ratio.
Synthesis route provided by the present invention not only significantly can reduce the production cost of Zeolite synthesis, and greatly can improve green and the atom utilization of building-up process, the molecular sieve obtained has more excellent physicochemical property, as higher degree of crystallinity, with chemical reagent (NaAlO 2, water glass and iron nitrate carry out alternative natural clay) be only 60% for the relative crystallinity of the FeZSM-5 of aluminium source, silicon source and source of iron synthesis, and its synthesis cost is lower.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of the embodiment of the present invention 1 gained FeZSM-5 molecular sieve.
Fig. 2 is scanning electron microscope (SEM) photo that the embodiment of the present invention 1 gained FeZSM-5 type molecular sieve amplifies 40000 times.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
In embodiment, said relative crystallinity is according to ASTM D3906-03 standard, with 2 θ angles in the XRD spectra of products therefrom and molecular sieve standard specimen 22.5 ~ 25.0 obetween the ratio of characteristic peak area sum, be expressed as a percentage, the NaZSM-5 molecular sieve (Catalyst Factory, Nankai Univ is produced, and its silica alumina ratio is 38) that standard specimen is is Material synthesis with conventional chemical reagent, is defined as 100% by its degree of crystallinity.
Product silica alumina ratio is characterized by x-ray fluorescence (XRF) method, and adopt Rigaku ZSX-100e4580 type Xray fluorescence spectrometer, the silica alumina ratio of the molecular sieve described in the present invention refers to SiO 2with Al 2o 3mol ratio.
Embodiment 1
The preparation of reagent:
The selection of mineral: diatomite used, kaolin and rectorite are commercially available prod, diatomaceous main component is: SiO 2content be 93.2wt.%, Al 2o 3content be 3.3wt.%, Fe 2o 3content be 1.5wt.%; The main component of rectorite is: SiO 2content be 43.2wt.%, Al 2o 3content be 37.2wt.%, Fe 2o 3content be 0.5wt.%; Kaolinic main component is: SiO 2content be 50.5wt.%, Al 2o 3content be 44.6wt.%, Fe 2o 3content be 0.5wt.%.
The activation of mineral: commercially available diatomite and rectorite are dried respectively, are ground into powder.Take 50.00g diatomite powder at 800 DEG C of roasting 4h, for subsequent use.Take 12.00g rectorite powder, mix with 24.00g sodium hydrate solid, add 60.00g deionized water, dry at 250 DEG C, for subsequent use.
Acid solution prepare: take 50.00g massfraction be 98% concentrated sulfuric acid solution join in 50.00g deionized water, be cooled to room temperature, for subsequent use.
Molecular sieve: take the diatomite powder 5.20g after above-mentioned roasting, adds 0.97g sodium hydroxide, 2.15g 4-propyl bromide, 58.30g deionized water, mol ratio is met: 0.15Na 2o:1SiO 2: 0.02Al 2o 3: 0.006Fe 2o 3: 40H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.1:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 13, mix and blend 4h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 170 DEG C of static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 90%, and product silica alumina ratio is 48, and in product, Fe content is 1.4wt.%, and its XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo.
Embodiment 2
The pretreatment process of diatomite and rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.67g sodium hydroxide, the rectorite powder of the above-mentioned process of 0.45g, 4.30g 4-propyl bromide, 46.58g deionized water, mol ratio is met: 0.15Na 2o:1SiO 2: 0.03Al 2o 3: 0.006Fe 2o 3: 32H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.2:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 12, mix and blend 8h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 180 DEG C, static crystallization 36h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 92%, and product silica alumina ratio is 30, and in product, Fe content is 0.9wt.%.
Embodiment 3
The pretreatment process of rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take 50.00g diatomite powder at 600 DEG C of roasting 8h, for subsequent use.
Take the diatomite powder 5.20g after above-mentioned roasting, add 1.0g sodium hydroxide, 20.00g deionized water, mix and blend 4h at 70 DEG C.Then add the rectorite powder of the above-mentioned process of 0.90g, 3.23g 4-propyl bromide, 43.32g deionized water, mol ratio is met: 0.24Na 2o:1SiO 2: 0.033Al 2o 3: 0.006Fe 2o 3: 42.4H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.15:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 14, mix and blend 12h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 160 DEG C of static crystallization 72h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 85%, and product silica alumina ratio is 25, and in product, Fe content is 1.0wt.%.
Embodiment 4
Diatomaceous pretreatment process and sulphuric acid soln compound method are all with embodiment 1.
Take the kaolin powder that 20.00g is commercially available, mix with 32.00g sodium hydrate solid, add 24.00g deionized water, dry at 250 DEG C, for subsequent use.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.67g sodium hydroxide, the kaolin powder of the above-mentioned process of 0.50g, 4.30g 4-propyl bromide, 105.58g deionized water, mol ratio is met: 0.15Na 2o:1SiO 2: 0.027Al 2o 3: 0.006Fe 2o 3: 71H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.2:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 13, mix and blend 6h at 80 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 200 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 96%, and product silica alumina ratio is 35, and in product, Fe content is 0.8wt.%.
Embodiment 5
Sulphuric acid soln and diatomaceous pretreatment process are all with embodiment 1.
Take 12.00g kaolin powder, mix with 16.00g sodium hydrate solid, add 64.00g deionized water, dry at 200 DEG C, for subsequent use.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.7g sodium hydroxide, the kaolin powder of the above-mentioned process of 1.56g, 1.08g 4-propyl bromide, 43.32g deionized water, mol ratio is met: 0.24Na 2o:1SiO 2: 0.05Al 2o 3: 0.0059Fe 2o 3: 28H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.047:1; The pH regulating mixture with above-mentioned sulphuric acid soln is about 12, mix and blend 4h at 70 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 210 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 94%, and product silica alumina ratio is 19, and in product, Fe content is 0.9wt.%.
Embodiment 6
The pretreatment process of rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take 50.00g diatomite powder at 900 DEG C of roasting 2h, for subsequent use.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.97g sodium hydroxide, 2.15g 4-propyl bromide, the rectorite powder of the above-mentioned process of 1.5g, 28.30g deionized water, mol ratio is met: 0.3Na 2o:1SiO 2: 0.04Al 2o 3: 0.006Fe 2o 3: 18.6H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.1:1; Mix and blend 4h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 170 DEG C of static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 75%, and product silica alumina ratio is 20, and in product, Fe content is 0.7wt.%.
Embodiment 7
The pretreatment process of diatomite and rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take the diatomite powder 8.41g after above-mentioned roasting, add 1.32g sodium hydroxide, the rectorite powder of the above-mentioned process of 3.9g, 11.17g 4-propyl bromide, 51.34g deionized water, mol ratio is met: 0.35Na 2o:1SiO 2: 0.053Al 2o 3: 0.0059Fe 2o 3: 20H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.3:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 12.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 170 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 72%, and product silica alumina ratio is 18, and in product, Fe content is 1.3wt.%.
Embodiment 8
Diatomaceous pretreatment process and sulphuric acid soln compound method are all with embodiment 1.
Take the rectorite powder that 20.00g is commercially available, mix with 30.00g sodium hydrate solid, add 3.00g deionized water, dry at 350 DEG C, for subsequent use.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.67g sodium hydroxide, the rectorite powder of the above-mentioned process of 1.0g, 4.30g 4-propyl bromide, 60.00g deionized water, mol ratio is met: 0.19Na 2o:1SiO 2: 0.046Al 2o 3: 0.006Fe 2o 3: 40H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.19:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 13, mix and blend 4h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 170 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 88%, and product silica alumina ratio is 20, and in product, Fe content is 1.1wt.%.
Embodiment 9
In order to regulate reaction system to feed intake the content of Fe, we adopt commercially available grade diatomaceously to synthesize for raw material.Wherein diatomaceous main component is: SiO 2content be 90.0wt.%, Al 2o 3content be 2.7wt.%, Fe 2o 3content be 2.5 wt.%;
The pretreatment process of diatomite and rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take the diatomite powder 5.40g after above-mentioned roasting, add 0.67g sodium hydroxide, the rectorite powder of the above-mentioned process of 0.45g, 4.30g 4-propyl bromide, 46.58g deionized water, mol ratio is met: 0.15Na 2o:1SiO 2: 0.024Al 2o 3: 0.10Fe 2o 3: 32H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.2:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 12, mix and blend 8h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 180 DEG C, static crystallization 36h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 88%, and product silica alumina ratio is 30, and in product, Fe content is 1.4wt.%.
Comparative example 1
Take 0.356g sodium metaaluminate, 0.574g iron nitrate, 16.56g water glass (containing 26wt.%SiO 2), 1.73g 4-propyl bromide, 41.76g deionized water, make mol ratio meet: 0.15Na 2o:1SiO 2: 0.03Al 2o 3: 0.006Fe 2o 3: 32H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.2:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 12, mix and blend 8h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 180 DEG C, static crystallization 36h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is 60%, and product silica alumina ratio is 25, and in product, Fe content is 0.4wt.%.
Comparative example 2
The pretreatment process of diatomite and rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take the diatomite powder 8.41g after above-mentioned roasting, add 2.44g sodium hydroxide, the rectorite powder of the above-mentioned process of 3.9g, 11.17g 4-propyl bromide, 51.34g deionized water, mol ratio is met: 0.45Na 2o:1SiO 2: 0.053Al 2o 3: 0.0059Fe 2o 3: 20H 2o, wherein SiO in template and synthetic system 2mol ratio is 0.3:1; The pH regulating mixture with above-mentioned sulphuric acid soln is 12.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 170 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product is quartz.
Comparative example 3
The pretreatment process of diatomite and rectorite and the compound method of sulphuric acid soln are all with embodiment 1.
Take the diatomite powder 5.20g after above-mentioned roasting, add 0.67g sodium hydroxide, the rectorite powder of the above-mentioned process of 0.45g, 46.58g deionized water, mol ratio is met: 0.15Na 2o:1SiO 2: 0.03Al 2o 3: 0.006Fe 2o 3: 32H 2o; The pH regulating mixture with above-mentioned sulphuric acid soln is 12, mix and blend 4h at 60 DEG C.This mixture is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 180 DEG C, static crystallization 48h.After crystallization terminates, cooling, cross and filter mother liquor, washing is to neutral, dry at 120 DEG C, obtains crystallization product.Through XRD determining, product thing belongs to MFI-type molecular sieve mutually, and in product, the relative crystallinity of FeZSM-5 type molecular sieve is only 20%.

Claims (10)

1. a synthetic method for FeZSM-5 molecular sieve, is characterized in that, described method comprises the steps:
(1) activation of mineral: get low silica-alumina ratio mineral and/or high silica alumina ratio mineral activate respectively; Wherein the activation of low silica-alumina ratio mineral is for mix with sodium hydroxide solution, then dries; Wherein the activation of high silica alumina ratio mineral is calcination process; Wherein the silica alumina ratio of preferred described low silica-alumina ratio mineral is below 10, and the silica alumina ratio of described high silica alumina ratio mineral is more than 30; Wherein also preferred sodium hydroxide solution is aqueous sodium hydroxide solution; More preferably in described aqueous sodium hydroxide solution, sodium hydroxide and quality ratio are 10-0.2:1; Wherein also preferred described oven dry is dry at 100-400 DEG C;
(2) crystallization: the low silica-alumina ratio mineral after step (1) being activated and/or high silica alumina ratio mineral mixs crystallization afterwards with sodium hydroxide, water, template, and control charging capacity and make mol ratio satisfied: 0.05 ~ 0.4Na 2o:1SiO 2: 0.02-0.5Al 2o 3: 0.004-0.1Fe 2o 3: 10 ~ 80H 2o; Wherein also preferred step (1) is activated after mineral mix with sodium hydroxide, water, template, first adjustment pH is crystallization again after 9-14;
(3) aftertreatment: product cooling step (2) crystallization obtained, filtration, filter cake is washed to neutrality, obtains FeZSM-5 molecular sieve after super-dry.
2. synthetic method according to claim 1, is characterized in that, the described low silica-alumina ratio mineral of step (1) are kaolin and/or rectorite; Described high silica alumina ratio mineral are diatomite and/or white carbon black.
3. synthetic method according to claim 1, is characterized in that, step (2) described template is the combination of one or two or more kinds in 4-propyl bromide, tetraethylammonium bromide, TPAOH and triethylamine.
4. synthetic method according to claim 1, is characterized in that, step (2) described crystallization is crystallization 6-96h at 140-220 DEG C.
5. synthetic method according to claim 1, is characterized in that, in step (1), the mass ratio of low silica-alumina ratio mineral and sodium hydroxide solution is 1:1-10.
6. synthetic method according to claim 1, is characterized in that, the maturing temperature of step (1) is 600-1000 DEG C, and roasting time is 1-10h.
7. the synthetic method according to claim 1-6 any one, is characterized in that, regulate pH to be after 9-14 in step (2), first burin-in process carries out crystallization again.
8. synthetic method according to claim 7, is characterized in that, described aging be aging 1-20h at 50-80 DEG C.
9. the FeZSM-5 molecular sieve that the synthetic method described in claim 1 ~ 8 any one prepares.
10. FeZSM-5 molecular sieve according to claim 9, is characterized in that, mole silica alumina ratio of described FeZSM-5 molecular sieve is 2.0-48.0, Fe 2o 3content is 0.7-3.5wt%; Wherein preferred described FeZSM-5 molecular sieve is 70 ~ 98% relative to the degree of crystallinity of the NaZSM-5 type molecular sieve being Material synthesis with pure chemistry reagent.
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