CN103570036B - A kind of synthetic method of Y zeolite - Google Patents
A kind of synthetic method of Y zeolite Download PDFInfo
- Publication number
- CN103570036B CN103570036B CN201210249568.8A CN201210249568A CN103570036B CN 103570036 B CN103570036 B CN 103570036B CN 201210249568 A CN201210249568 A CN 201210249568A CN 103570036 B CN103570036 B CN 103570036B
- Authority
- CN
- China
- Prior art keywords
- mineral
- zeolite
- alumina ratio
- activation
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to the technical field of Zeolite synthesis, relate to a kind of synthetic method of Y zeolite.The method is whole silicon source using natural mineral as Zeolite synthesis and aluminium source, wherein a kind of mineral are low silicon crystal form natural mineral, another kind of mineral are high amorphized silicon state natural mineral, described low silicon crystal form natural mineral forms active aluminosilicate after sub-molten salt activation, described high silicon natural mineral forms active high-silicon mineral through thermal activation, by the active aluminosilicate of acquisition and active high-silicon mineral Homogeneous phase mixing, through aging and crystallization under hydrothermal condition, obtain Y zeolite.The present invention is by regulating the silica alumina ratio of the proportion adjustment molecular sieve product of two kinds of mineral in synthesis material.The present invention extends raw material range prepared by molecular screen material, and significantly reduce the production cost of molecular sieve, production process is environmental friendliness more.
Description
Technical field
The invention belongs to Zeolite synthesis field, relate to a kind of synthetic method of Y zeolite, it is characterized in that, with natural mineral for raw material provide synthesis Y zeolite required for whole silicon source and aluminium source.
Background technology
At petrochemical industry, Y zeolite remains the large molecular screen material of consumption at present.According to the difference of synthesis material, the synthetic method of molecular sieve can be divided into two classes: utilize industrial chemicals synthesis of molecular sieve and utilize natural mineral synthesis of molecular sieve.The mature technology being Material synthesis molecular sieve with conventional inorganic Chemicals, technical qualification are easy to control, quality product is high, but these inorganic chemical products as Zeolite synthesis raw material are produce from natural mineral through complicated reaction and sepn process mostly, production process route length, energy consumption and material consumption are high, and most of process exists serious disposal of pollutants.Therefore, if directly to be rich in the natural mineral of silicon species and aluminium species for Material synthesis molecular sieve, not only abundant raw material source, and the synthetic route that can greatly shorten from raw material to molecular sieve product, significantly reduce the energy consumption of molecular sieve production, material consumption and disposal of pollutants, and significantly reduce production cost, thus open up a new way for the synthesis of molecular sieve.Therefore this technology has development prospect.
At present, in the open report adopting natural mineral synthesis of molecular sieve, mainly concentrate on the natural mineral such as kaolin or rectorite as part silicon source or aluminium source synthesis of molecular sieve.
USP 3574538 discloses the method for a kind of kaolin synthesis Y zeolite, and kaolin roasting is first unbodied metakaolin by the method, then adds a certain amount of water glass and sodium hydroxide, by after the water glass that adds regulate the SiO of synthetic system
2/ Al
2o
3mol ratio, makes the SiO that itself and product molecule sieve
2/ Al
2o
3mol ratio is close, then adds the directed agents that mass percentage is 0.1% to 10%, obtained highly purified Y zeolite after 60 DEG C to 110 DEG C crystallization, the SiO of product
2/ Al
2o
3mol ratio is 4.5 to 5.95.
EP 0209332 (A2) discloses a kind of method under agitation being prepared by kaolin starting material crystallization Y zeolite, kaolin roasting is first after metakaolin by this method, add the additional silicon source such as water glass, silicon sol again, the mol ratio of regulation system is (2 to 4.5) Na
2o: (3 to 8) SiO
2: Al
2o
3: (30 to 315) H
2o, and then add directed agents, under hydrothermal condition, synthesis obtains the powder that NaY purity reaches 97%.
The roasting at 940 to 1000 DEG C of part kaolin is become the height soil containing spinel by CN 1334142A, another part roasting at 700 to 900 DEG C becomes metakaolin, then two kinds of roasting soil are mixed in proportion, as aluminium source and the part silicon source of Zeolite synthesis, and adding portion water glass is additional silicon source, add directed agents, sodium hydroxide and water, at 90 to 95 DEG C, synthesize the molecular sieve that NaY mass percentage is 40 to 90%.
The aluminium source that CN 1533982 and USP 7067449 synthesizes for Y zeolite with the metakaolin after 500 to 690 DEG C of roastings and part silicon source, adding water glass is additional silicon source, add directed agents, sodium hydroxide solution and water, make mol ratio for (1 to 2.5) Na
2o: (4 to 9) SiO
2: Al
2o
3: (40 to 100) H
2the reaction raw materials of O, stirs crystallization at 88 to 98 DEG C, obtains the molecular sieve that NaY mass percentage is 30 to 85% after filtration.
Liu Xinmei etc. (J.Natural Gas Chem., 2003,12:63-70) utilize Coaseries kaolin, in the alkaline system of additional water glass, synthesized the NaY molecular sieve that degree of crystallinity is 65 to 88% by hydrothermal method.
Above patent or document are that raw material all needs when preparing Y zeolite Extra Section chemistry silicon source (as water glass, silicon sol, water glass etc.) to carry out the silica alumina ratio of regulation system with kaolin mineral.This is because, in the above-mentioned methods, raw materials pretreatment adopts high-temperature activation mostly, and in kaolin mineral, alumina octahedral is totally disrupted, and silicon species still exists with the tetrahedron laminate structure of inertia.Therefore, the aluminium source in product and few a part of silicon source can only be utilized in reaction process, need to add a large amount of chemical silicon sources.Meanwhile, when adopting the method for above patent or bibliographical information to prepare NaY molecular sieve, owing to also remaining a large amount of unreacted kaolin in product, inevitable purity and the degree of crystallinity that also can affect molecular sieve.In addition, the activation of above-mentioned natural mineral all at high temperature (about 600 to 1000 DEG C) is carried out, and reactivation process energy consumption is high, and environmental pollution is serious.
In recent years, along with the rise of Green Chemical Engineering Process tide, using nontoxic raw material in chemical process, make full use of starting material, adopting less energy-consumption, oligosaprobic chemical reaction process to carry out production object product has been trend of the times.Therefore, the silicon and aluminum source in abundant active natural mineral, and the silica alumina ratio that feeds intake using the natural mineral being rich in amorphous silicon oxide as additional silicon source modulation, have cheap, eco-friendly advantage compared with conventional chemical silicon sources such as water glass, silicon sol, water glass.
Diatom is a kind of unicellular algae be distributed widely in various water body, and in certain circumstances, they can grow with surprising rapidity, breed, and its remains deposit to the bottom and buried, and after being stacked into certain thickness, will form diatomite ore.Diatomite mineral rich reserves, wide material sources, and its chemical composition mainly amorphous silicon oxide, through purifying, activating the silicon source that can be used as Zeolite synthesis.Owing to being rich in a large amount of amorphous silicon oxides in diatomite, be that the research of silicon source or part aluminium source synthesis of molecular sieve mainly concentrates on high silica ZSM-5 molecular sieve (as CN 1504410A and CN 1915820A) with diatomite.
At present, had with natural mineral such as kaolin, rectorite, polynite, wilkinites for the report of Y zeolite prepared by raw material, but only part make use of the part sial in mineral, still need and add a certain amount of additional chemical silicon source or aluminium source.Without additional chemical silicon and aluminum source, be that raw material is prepared the technology of molecular sieve there is not been reported completely with natural mineral.Y zeolite is the carrier and catalyzer that are most widely used in petrochemical industry, and research and development are the technology of Material synthesis Y zeolite completely with natural mineral, have good application prospect.
Reported in the past with natural kaolin mineral for the technology of Y zeolite prepared by raw material, also need to add the additional silicon source or aluminium source that provide with inorganic chemical product form, and the energy consumption of reactivation process is higher, makes the production cost of molecular sieve still higher.And, these inorganic chemical products as Zeolite synthesis raw material are produce from natural mineral through complicated reaction and sepn process mostly, production process technology route is long, energy and material consumption is high, and most of process exists severe contamination discharge, does not meet the theory of Modern Green chemical industry.
Summary of the invention
For solving the problem, the invention provides a kind of synthetic method of Y zeolite, the method is whole silicon source using natural mineral as Zeolite synthesis and aluminium source, described natural mineral is the mixture of low silica-alumina ratio mineral and high silicon mine, wherein mineral are a low silicon crystal form natural mineral, and another kind of mineral are high amorphized silicon state natural mineral.Wherein, low silicon crystal form natural mineral forms active aluminosilicate after sub-molten salt activation, and high silicon natural mineral forms active high-silicon mineral through thermal activation, by two kinds of natural mineral Homogeneous phase mixing, under hydrothermal condition, obtains product Y zeolite through aging and crystallization.Mole silica alumina ratio of this Y zeolite is 3.0 to 5.8, and the relative crystallinity of Y zeolite is 70% to 95%.
In the synthetic method of Y zeolite of the present invention, the step of Material synthesis comprises:
(1) the sub-molten salt activation of low silica-alumina ratio mineral: the ratio being 1: 1 to 2 in low silica-alumina ratio mineral and sodium hydrate solid mass ratio takes low silica-alumina ratio mineral, low silica-alumina ratio mineral are added in reactor together with aqueous sodium hydroxide solution, in 150 DEG C to 300 DEG C reactions, obtain the silico-aluminate of sub-molten salt activation;
(2) thermal activation of high silicon mine: by high silicon mine thermal activation, obtains the high silicon mine activated;
(3) silico-aluminate that the high silicon mine of described activation and sub-molten salt activate is mixed, obtain the raw material of synthesis Y zeolite.
The synthetic method of Y zeolite of the present invention comprises the following steps:
Step 1: the synthesis of raw material
(1) the sub-molten salt activation of low silica-alumina ratio mineral: compound concentration is 250g/L to 500g/L aqueous sodium hydroxide solution, the ratio being 1: 1 to 2 in low silica-alumina ratio mineral and sodium hydrate solid mass ratio takes low silica-alumina ratio mineral, is added in reactor by low silica-alumina ratio mineral together with aqueous sodium hydroxide solution; Reactor is warming up to 150 DEG C to 300 DEG C, and reaction 1 is little of 6 hours under normal pressure opens wide system, obtains the silico-aluminate of sub-molten salt activation;
(2) thermal activation of high silicon mine: by high silicon mine 600 DEG C to 700 DEG C thermal activations, obtains the high silicon mine activated;
(3) silico-aluminate that the high silicon mine of described activation and sub-molten salt activate is mixed with the ratio that mass ratio is 1.5 to 2.2: 1, obtain synthesis material;
The preparation of step 2:Y type molecular sieve
In the synthesis material that step 1 obtains, add directed agents and deionized water, the mol ratio of adjustment material is, the Na of 2.0 to 14.4
2the Al of O: 0.8 to 1.2
2o
3: the SiO of 5 to 12
2: the H of 180 to 250
2o, through aging and crystallization, obtains crystallization product; The crystallization product obtained is filtered, washes and drying, obtain Y zeolite.
In above-mentioned synthetic method, described low silica-alumina ratio mineral are selected from kaolin, feldspar, nepheline, white garnet, beryl, white mica, pyrophyllite, rectorite leng, jadeite, triphane, diaspore, perlite, trichroite, phlogopite, vermiculite, montmorillonite, talcum, serpentine, polygorskite, sepiolite, attapulgite, enstatite, diopside, amphibole, peridotites etc.; The white carbon black that high silicon mine is selected from diatomite and/or prepares with natural mineral.
The inventive method is by regulating the silica alumina ratio of the proportion adjustment molecular sieve product of two kinds of mineral in synthesis material.The inventive method extends raw material range prepared by molecular screen material, significantly reduces the production cost of molecular sieve, and significantly reduce material consumption and energy consumption, production process is environmental friendliness more.
In addition, according to synthetic method provided by the present invention, in building-up process, the depolymerization plastic of mineral and the nucleation crystallization of molecular sieve are simultaneously and progressively occur, a large amount of gel can not be produced, thus avoid and make due to the generation of a large amount of gel the drawback that mass transfer, heat-transfer effect worsen for during Material synthesis molecular sieve with conventional chemical reagent.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) spectrogram of the embodiment of the present invention 1 gained molecular sieve.
Fig. 2 is scanning electron microscope (SEM) photo that the embodiment of the present invention 1 gained molecular sieve amplifies 3000 times.
Embodiment
The invention provides a kind of synthetic method of Y zeolite, natural mineral is wherein utilized to provide silicon source needed for Zeolite synthesis and aluminium source, Y zeolite is obtained through hydrothermal crystallizing, mole silica alumina ratio of this Y zeolite is 3.0 to 5.8, the relative crystallinity of Y zeolite is 70% to 95%, wherein said natural mineral is the mixture of low silica-alumina ratio mineral and high silicon mine, and described low silica-alumina ratio mineral activate through sub-molten salt, and described high silicon mine is through thermal activation.
In the present invention, described low silica-alumina ratio mineral are selected from the mixture of kaolin, feldspar, nepheline, white garnet, beryl, white mica, pyrophyllite, rectorite leng, jadeite, triphane, diaspore, perlite, trichroite, phlogopite, vermiculite, montmorillonite, talcum, serpentine, polygorskite, sepiolite, attapulgite, enstatite, diopside, amphibole, peridotites or these materials; The white carbon black that described high silicon mine is selected from diatomite, prepare with natural mineral or this two mixture.
Specifically, the synthetic method of Y zeolite of the present invention comprises the following steps:
Step 1:
(1) the sub-molten salt activation of low silica-alumina ratio mineral: compound concentration is 250g/L to 500g/L aqueous sodium hydroxide solution, the ratio being 1: 1 to 2 in low silica-alumina ratio mineral and sodium hydrate solid mass ratio takes low silica-alumina ratio mineral, is added in reactor by low silica-alumina ratio mineral together with aqueous sodium hydroxide solution; Reactor is warming up to 150 DEG C to 300 DEG C, and reaction 1 is little of 6 hours under normal pressure opens wide system, obtains the silico-aluminate of sub-molten salt activation;
(2) thermal activation of high silicon mine: by high silicon mine 600 DEG C to 700 DEG C thermal activations, obtains the high silicon mine activated;
(3) silico-aluminate that the high silicon mine of described activation and sub-molten salt activate is mixed with the ratio that mass ratio is 1.5 to 2.2: 1, obtain synthesis material;
Step 2: add directed agents and deionized water in the synthesis material that step 1 obtains, the mol ratio of adjustment material is, the Na of 2.0 to 14.4
2the Al of O: 0.8 to 1.2
2o
3: the SiO of 5 to 12
2: the H of 180 to 250
2o, under agitation aging to 65 DEG C in 50 DEG C, crystallization at 95 DEG C to 105 DEG C, obtains crystallization product; Cooled by the crystallization product of acquisition, excessively filter mother liquor, it is less than 10 that filter cake deionized water is washed till pH, and drying obtains Y zeolite.
Mole consisting of of directed agents described in above-mentioned steps 2: the Na of 16 to 18
2the Al of O: 0.8 to 1.2
2o
3: the SiO of 16 to 18
2: the H of 310 to 340
2o, directing agent solution consumption is 9% to 16% of synthetic system gross weight.
In an embodiment, the synthetic method of Y zeolite of the present invention comprises the following steps:
(1) mineral activation: first compound concentration is the aqueous sodium hydroxide solution of 250g/L to 500g/L, the ratio being 1: 1 to 2 in low silica-alumina ratio crystalline state mineral and sodium hydrate solid mass ratio takes mineral, and adds in reactor together with sodium hydroxide solution.Then 150 to 300 DEG C are warming up to, the temperature of reaction kettle of the sub-molten salt activation of preferred low silica-alumina ratio mineral is 180 DEG C to 250 DEG C, more preferably 180 DEG C to 220 DEG C, react 1 to 6 hour under normal pressure opens wide system, after reaction terminates, obtain the low silica-alumina ratio silico-aluminate solid of sub-molten salt activation.High amorphized silicon state mineral then mix, as synthesis material with the low silica-alumina ratio silico-aluminate that sub-molten salt activates after 600 to 700 DEG C of high-temperature hot activation.After mixing, be 1: 1.5 to 2.2 through the silico-aluminate solid of sub-molten salt activation with the mass ratio of the non-crystalline state mineral activated through high-temperature hot in mixture;
(2) add directed agents and deionized water in the synthesis material obtained to step (1), regulate the mol ratio of material to be, the Na of 2.0 to 14.4
2the Al of O: 0.8 to 1.2
2o
3: the SiO of 5 to 12
2: the H of 180 to 250
2o, under agitation aging 6 to 20 hours in 50 to 65 DEG C, in 95 DEG C to 105 DEG C crystallization 8 to 36 hours, obtain crystallization product; By above-mentioned crystallization product cooling, excessively filter mother liquor, it is less than 10 that filter cake deionized water is washed till pH, and drying obtains Y zeolite.
In the embodiment of the preparation method of Y zeolite provided by the present invention, whole silicon source and whole aluminium source provide by the natural kaolin of low silica-alumina ratio and the natural diatomaceous earth mineral of high silica alumina ratio, by the ratio of suitable modulation two kinds of mineral in preparation process, the Y zeolite of Different Silicon aluminum ratio can be obtained.
The present invention provides whole silicon source and the aluminium source of Zeolite synthesis with natural mineral, does not need to add other chemical silicon source or aluminium sources, widened the raw material sources of Zeolite synthesis and the Application Areas of natural mineral except directed agents.
According to method provided by the present invention, natural mineral can carry out acid treatment before calcination process, and to reduce the content of some chemical composition (as calcium, iron, nickel etc.) in mineral, but this is not necessary.Molecular sieve prepared by the present invention can be applied to many occasions, its result of use of a small amount of impurity not remarkably influenced in mineral beyond silica removal aluminium species, so the range of choice of the present invention to kaolin and diatomite purity is larger, namely the purity of method provided by the present invention to raw mineral materials is not strict with, but in preferred mineral, kaolin and diatomaceous mass percentage are more than 75%.
In the method for the invention, the natural mineral of low silica-alumina ratio, except kaolin, can also select feldspar, nepheline, white garnet, beryl, white mica, pyrophyllite, rectorite leng, jadeite, triphane, diaspore, perlite, trichroite, phlogopite, vermiculite, montmorillonite, talcum, serpentine, polygorskite, sepiolite, attapulgite, enstatite, diopside, amphibole, peridotites etc.; High silicon mine except diatomite, the also optional white carbon black prepared in order to natural mineral.
The present invention with the addition of homemade seeding director in molecular sieve process, containing a large amount of Y zeolite primary and secondary structural units in prepared seeding director, in Crystallization of Zeolite process, these primary structures and secondary structure unit become the nucleus of Y zeolite growth, although add-on is few, but serve and accelerate product synthesis speed, shortening crystallization time, be conducive to the effect of production application.
The directed agents used in the present invention can be synthesized according to a conventional method, and as synthesized according to the preparation method described by USP 3574538, USP4166099, EU 0435625, the constitutive molar ratio of directed agents is: (16 to 18) Na
2o: (0.8 to 1.2) Al
2o
3: (16 to 18) SiO
2: (310 to 340) H
2o, preferred directed agents preparation condition is: synthesize at 10 to 40 DEG C, aging at 10 to 25 DEG C, the transparent clear liquid state of directed agents of acquisition.
The method of the hydrothermal crystallizing synthesis Y zeolite used in the present invention can be the ordinary method used in aforesaid prior art, such as, under directed agents exists, carries out aging and crystallization.
Preparation method of the present invention have preparation flow simple, use the advantages such as raw material is easy to get, product silica alumina ratio is controlled.Adopt the molecular sieve synthesized by the inventive method, there is X-ray diffraction (XRD) the feature spectrogram of NaY molecular sieve.These NaY molecular sieve rare earth chloride, ammonium sulfate, ammonium phosphate etc. are carried out ion modification and hydrothermal treatment consists, the Modified Zeolite Y that REY, REHY, USY, REUSY, P-REUSY etc. are dissimilar can be obtained, have identical physico-chemical property with the congeneric elements sifter device adopting chemical silicon source and aluminium source to synthesize.
Below in conjunction with example, the invention will be further elaborated, and it is intended to illustrate embodiment of the present invention and feature in detail, can not be interpreted as any restriction of the present invention.
In embodiment, said relative crystallinity is according to ASTM D 390-603 standard,, be expressed as a percentage at the ratio of eight characteristic peak area sums of 15.7 ° ± 0.2 °, 18.7 ° ± 0.2 °, 20.4 ° ± 0.3 °, 23.7 ° ± 0.4 °, 27.1 ° ± 0.5 °, 30.8 ° ± 0.5 °, 31.5 ° ± 0.5 °, 34.2 ° ± 0.6 ° with 2 θ angles in the XRD spectra of products therefrom and NaY molecular sieve standard specimen.The business NaY molecular sieve (silica alumina ratio is 5.0 for Tianjin Nan Hua catalyzer company limited, Catalyst Factory, Nankai Univ NaY type molecular sieve) 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 by solid-state
29si magic-angle-spinning nuclear magnetic resonance (
29si MAS NMR) method characterizes, and instrument is that German Brucker company produces DSX 500 type nuclear magnetic resonance analyser.The silica alumina ratio of the molecular sieve described in the present invention refers to SiO
2with Al
2o
3mol ratio.
Embodiment 1
(1) directed agents preparation: get 27.2 grams of (g) sodium hydrate solids (Beijing Chemical Plant produces, and purity is 99%) and be dissolved in 38g water, be cooled to room temperature, for subsequent use.Get 26.66g Tai-Ace S 150 (molecular formula: Al
2(SO
4)
318H
2o, Beijing Yili Fine Chemicals Co., Ltd., purity is 99%) and be dissolved in 38g water, the alum liquor of preparation is added in sodium hydroxide solution and makes high alkali deflection aluminium acid sodium solution.By 85.26g water glass (molecular formula: Na
2siO
39H
2o, Beijing modern chemistry Reagent Company, purity is 99%) be dissolved in 100g water, add 72g silicon sol (Red Star water glass plant, Beijing, SiO
2content is 24.96%, Na
2o content is 0.05%), rapid stirring 2 hours.Then under agitation condition, add high alkali deflection aluminium acid sodium solution, after mixing, at 30 DEG C, stir ageing 4 hours, left at room temperature ageing 2 days, obtained directing agent solution.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.Take 50g sodium hydrate solid to be dissolved in 150mL deionized water, add 35g kaolin powder and Homogeneous phase mixing, open wide system stirring reaction 6 hours, pulverized by reacted solid under 180 DEG C of normal atmosphere, the kaolin obtaining activating is for subsequent use.Take 105g diatomite powder, 600 DEG C of roastings 4 hours, for subsequent use.
(3) Zeolite synthesis: take the kaolin powder 4.6g after above-mentioned activation, diatomite powder 8.0g, with 1.2g sodium hydrate solid Homogeneous phase mixing, adds 35g deionized water, 7g directed agents, mix and blend 12 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 100 DEG C of static crystallization 12 hours.After crystallization terminates, cool, excessively filter mother liquor, filter cake washing is less than 10 to pH value, dry at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to NaY molecular sieve mutually, and in product, the relative crystallinity of Y zeolite is 92%, and silica alumina ratio (mol ratio) is 5.2, and its XRD spectra is shown in Fig. 1, and Fig. 2 is shown in by SEM photo.
Embodiment 2
(1) directed agents preparation: preparation method is with embodiment 1.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.Take 60g sodium hydrate solid to be dissolved in 140mL deionized water, add 35g kaolin powder and Homogeneous phase mixing, open wide system stirring reaction 4 hours, pulverized by reacted solid under 220 DEG C of normal atmosphere, the kaolin obtaining activating is for subsequent use.Take 105g diatomite powder, 700 DEG C of roastings 2 hours, for subsequent use.
(3) Zeolite synthesis: take the kaolin powder 4.6g after above-mentioned activation, diatomite powder 10.0g Homogeneous phase mixing, add 40g deionized water, 7.8g directed agents, mix and blend 14 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 105 DEG C of static crystallization 16 hours.After crystallization terminates, cool, excessively filter mother liquor, filter cake washing is less than 10 to pH value, dry at 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to NaY molecular sieve mutually, and in product, the relative crystallinity of Y zeolite is 90%, and silica alumina ratio (mol ratio) is 5.0.
Embodiment 3
(1) directed agents preparation: get 27.2g sodium hydrate solid (Beijing Chemical Plant produces, and purity is 99%) and be dissolved in 38g water, be cooled to room temperature, for subsequent use.Get 26.66g Tai-Ace S 150 (molecular formula: Al
2(SO
4)
318H
2o, Beijing Yili Fine Chemicals Co., Ltd., purity is 99%) and be dissolved in 38g water, the alum liquor of preparation is dissolved in sodium hydroxide solution and makes high alkali deflection aluminium acid sodium solution.By 96.63g water glass (molecular formula: Na
2siO
39H
2o, Beijing modern chemistry Reagent Company, purity is 99%) be dissolved in 115g water, add 82g silicon sol (Red Star water glass plant, Beijing, SiO
2content is 24.96%, Na
2o content is 0.05%), rapid stirring 2 hours.Then under agitation condition, add high alkali deflection aluminium acid sodium solution, after mixing, at 30 DEG C, stir ageing 4 hours, standing at room temperature ageing 2 days, obtained directing agent solution.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.Take 50g sodium hydrate solid to be dissolved in 130mL deionized water, add 30g kaolin powder and Homogeneous phase mixing, open wide system stirring reaction 3 hours, pulverized by reacted solid under 200 DEG C of normal atmosphere, the kaolin obtaining activating is for subsequent use.Take 105g diatomite powder, 600 DEG C of roastings 4 hours, for subsequent use.
(3) Zeolite synthesis: take the kaolin powder 5g after above-mentioned activation, adds above-mentioned Diatomite mineral powder 8.7g, mixes.Then 55g deionized water is added, 7.6g directed agents, mix and blend 10 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 105 DEG C of static crystallization 36 hours.After crystallization terminates, cool, excessively filter mother liquor, filter cake washing is less than 10 to pH value, dry at being placed in 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to NaY molecular sieve mutually, and in product, the relative crystallinity of Y zeolite is 87%, and silica alumina ratio (mol ratio) is 5.1.
Embodiment 4
(1) directed agents preparation: with embodiment 3.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.
Take 25g sodium hydrate solid to be dissolved in 50mL deionized water, add 22g kaolin powder and Homogeneous phase mixing, under 200 DEG C of normal atmosphere, open wide system stirring reaction 5 hours, reacted solid is pulverized, for subsequent use.Take 25g diatomite powder 650 DEG C of roastings 4 hours, for subsequent use.
(3) Zeolite synthesis: take the kaolin 5g after above-mentioned activation, the diatomite 9.3g after activation, mixes with 2.3g sodium hydrate solid.Then 50g deionized water is added, 5.7g directed agents, mix and blend 16 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 100 DEG C of static crystallization 15 hours.After crystallization terminates, cool, excessively filter mother liquor, wash and be less than 10 to pH value, dry at being placed in 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to NaY molecular sieve mutually, and in product, the relative crystallinity of Y zeolite is 77%, and silica alumina ratio (mol ratio) is 4.2.
Embodiment 5
(1) directed agents preparation: with embodiment 3.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.Take 50g sodium hydrate solid to be dissolved in 50mL deionized water, add 37.5g kaolin powder and Homogeneous phase mixing, under 200 DEG C of normal atmosphere, open wide system stirring reaction 3.5 hours, reacted solid is pulverized, for subsequent use.Take 25g diatomite powder 650 DEG C of roastings 4 hours, the kaolin obtaining activating is for subsequent use.Commercially available diatomite in powder is broken into powder, roasting 2 hours at 400 DEG C, the sulfuric acid being 40% with mass percentage reacts 4 hours under 90 DEG C of water-baths, filters, washs to medium-sized, dry obtained pickling diatomite.
(3) Zeolite synthesis: take the kaolin 4.8g after above-mentioned activation, the diatomite 7.2g after activation, mixes with 1.3g sodium hydrate solid.Then 45g deionized water is added, 7.8g directed agents, mix and blend 20 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 110 DEG C of static crystallization 24 hours.After crystallization terminates, cool, excessively filter mother liquor, wash and be less than 10 to pH value, dry at being placed in 120 DEG C, obtain crystallization product.Through XRD determining, its thing belongs to NaY molecular sieve mutually, and in product, the relative crystallinity of Y zeolite is 87%, and silica alumina ratio (mol ratio) is 4.9.
Comparative example 1
(1) directed agents preparation: with embodiment 1.
(2) mineral activation: commercially available kaolin and diatomite are dried respectively, are ground into powder.Respectively by the roasting 6 hours at 800 DEG C of kaolin and diatomite powder, for subsequent use after activation.
(3) Zeolite synthesis: take the kaolin powder 1.9g after above-mentioned activation, diatomite powder 8.0g, with 3.9g sodium hydrate solid Homogeneous phase mixing, adds 35g deionized water, 7g directed agents, mix and blend 12 hours at 60 DEG C.This mixing solutions is poured in band teflon-lined stainless steel crystallizing kettle, be warming up to 100 DEG C of static crystallization 12 hours.After crystallization terminates, cool, excessively filter mother liquor, wash and be less than 10 to pH value, at 120 DEG C, drying, obtains crystallization product.Through XRD determining, its thing is the mixture of NaY molecular sieve and euthalite mutually, can not obtain pure Y zeolite.
Comparative example 2
The preparation of directed agents is with embodiment 3.
Getting 14.3g sodium hydrate solid (Beijing Chemical Plant produces, and purity is 99%) is dissolved in 30g water, for subsequent use.Get 27.8g Tai-Ace S 150 (molecular formula: Al
2(SO
4)
318H
2o, Beijing Yili Fine Chemicals Co., Ltd., purity is 99%) and be dissolved in 30g water, the alum liquor of preparation is dissolved in sodium hydroxide solution and makes high alkali deflection aluminium acid sodium solution.Then 100g silicon sol (Red Star water glass plant, Beijing, SiO is added
2content is 24.96%, Na
2o content is 0.05%), 11g directed agents.At 60 DEG C, stir ageing 12 hours after mixing, load in stainless steel cauldron, static ageing 24 hours at 100 DEG C, then filter, wash to pH and be less than 9, dry obtained NaY molecular sieve product at 120 DEG C.It is 5.3 that XRD records its silica alumina ratio, and relative crystallinity is 86%.
The result of comparative example illustrates, provides the NaY molecular sieve prepared by whole silicon and aluminum sources of Zeolite synthesis to have the physicochemical property similar with the NaY molecular sieve adopting chemical reagent to synthesize with the kaolin mineral of thermal activation natural diatomaceous earth and sub-molten salt activation.And the kaolin mineral of the thermal activation of routine is under the condition without additional silicon and aluminum source, reacts with diatomite and cannot prepare pure Y zeolite.This illustrates that described in this patent, method fully can not only activate mineral at low temperatures, and has higher chemical reactivity, thus realizes low cost synthesis Y zeolite.
Claims (7)
1. the synthetic method of a Y zeolite, the method utilizes natural mineral to provide silicon source needed for Zeolite synthesis and aluminium source, Y zeolite is obtained through hydrothermal crystallizing, mole silica alumina ratio of this Y zeolite is 3.0 to 5.8, the relative crystallinity of Y zeolite is 70% to 95%, wherein said natural mineral is the mixture of low silica-alumina ratio mineral and high silicon mine, and the synthesis step of the raw material of the method comprises:
(1) the sub-molten salt activation of low silica-alumina ratio mineral: the ratio being 1:1 to 1:2 in low silica-alumina ratio mineral and sodium hydrate solid mass ratio takes low silica-alumina ratio mineral, low silica-alumina ratio mineral are added in reactor together with aqueous sodium hydroxide solution, in 150 DEG C to 300 DEG C reactions, obtain the silico-aluminate of sub-molten salt activation;
(2) thermal activation of high silicon mine: by high silicon mine thermal activation, obtains the high silicon mine activated;
(3) silico-aluminate that the high silicon mine of described activation and sub-molten salt activate is mixed, obtain the raw material of synthesis Y zeolite.
2. the synthetic method of Y zeolite as claimed in claim 1, wherein said low silica-alumina ratio mineral are selected from the mixture of kaolin, feldspar, nepheline, white garnet, beryl, white mica, pyrophyllite, rectorite leng, jadeite, triphane, diaspore, perlite, trichroite, phlogopite, vermiculite, montmorillonite, talcum, serpentine, polygorskite, sepiolite, attapulgite, enstatite, diopside, amphibole, peridotites or these materials; The white carbon black that described high silicon mine is selected from diatomite, prepare with natural mineral or this two mixture.
3. the synthetic method of Y zeolite as claimed in claim 2, the method comprises the following steps:
Step 1: the synthesis of raw material
(1) the sub-molten salt activation of low silica-alumina ratio mineral: compound concentration is 250g/L to 500g/L aqueous sodium hydroxide solution, the ratio being 1:1 to 1:2 in low silica-alumina ratio mineral and sodium hydrate solid mass ratio takes low silica-alumina ratio mineral, is added in reactor by low silica-alumina ratio mineral together with aqueous sodium hydroxide solution; Reactor is warming up to 150 DEG C to 300 DEG C, and reaction 1 is little of 6 hours under normal pressure opens wide system, obtains the silico-aluminate of sub-molten salt activation;
(2) thermal activation of high silicon mine: by high silicon mine 600 DEG C to 700 DEG C thermal activations, obtains the high silicon mine activated;
(3) silico-aluminate that the high silicon mine of described activation and sub-molten salt activate is mixed with the ratio that mass ratio is 1.5 to 2.2:1, obtain synthesis material;
The preparation of step 2:Y type molecular sieve
In the synthesis material that step 1 obtains, add directed agents and deionized water, the mol ratio of adjustment material is, the Na of 2.0 to 14.4
2the Al of O:0.8 to 1.2
2o
3: the SiO of 5 to 12
2: the H of 180 to 250
2o, through aging and crystallization, obtains crystallization product; The crystallization product obtained is filtered, washes and drying, obtain Y zeolite.
4. the synthetic method of Y zeolite as claimed in claim 3, wherein in step 2, under agitation aging to 65 DEG C in 50 DEG C, crystallization at 95 DEG C to 105 DEG C, obtains crystallization product.
5. the synthetic method of Y zeolite as claimed in claim 4, wherein in step 1, the temperature of reaction kettle of the sub-molten salt activation of low silica-alumina ratio mineral is 180 DEG C to 250 DEG C.
6. the synthetic method of Y zeolite as claimed in claim 5, wherein in step 1, the temperature of reaction kettle of the sub-molten salt activation of low silica-alumina ratio mineral is 180 DEG C to 220 DEG C.
7. the synthetic method of the Y zeolite as described in claim 3 to 6 any one, mole consisting of of wherein said directed agents: the Na of 16 to 18
2the Al of O:0.8 to 1.2
2o
3: the SiO of 16 to 18
2: the H of 310 to 340
2o, directing agent solution consumption is 9% to 16% of synthetic system gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210249568.8A CN103570036B (en) | 2012-07-18 | 2012-07-18 | A kind of synthetic method of Y zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210249568.8A CN103570036B (en) | 2012-07-18 | 2012-07-18 | A kind of synthetic method of Y zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103570036A CN103570036A (en) | 2014-02-12 |
| CN103570036B true CN103570036B (en) | 2015-10-28 |
Family
ID=50042844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210249568.8A Active CN103570036B (en) | 2012-07-18 | 2012-07-18 | A kind of synthetic method of Y zeolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103570036B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176744B (en) * | 2014-08-26 | 2016-05-18 | 河北工业大学 | The sub-fused salt activation of a kind of KOH potassic feldspar is produced the method for full potassium W type molecular sieve |
| WO2016078016A1 (en) * | 2014-11-19 | 2016-05-26 | 中国石油大学(北京) | Preparation method for beta zeolite |
| WO2016078035A1 (en) * | 2014-11-19 | 2016-05-26 | 中国石油大学(北京) | Active aluminosilicate material and preparation method therefor |
| CN105126899B (en) * | 2015-07-16 | 2017-12-29 | 福州大学 | A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application |
| CN106215614A (en) * | 2016-07-19 | 2016-12-14 | 浙江绿冠环保科技有限公司 | A kind of anionic molecule sieve is dual except formaldehyde purifying agent and preparation method thereof |
| CN111715196B (en) * | 2020-06-17 | 2022-12-16 | 青岛科技大学 | Method for preparing magnetic activated carbon NaX molecular sieve composite material by taking coal gasification fine slag as raw material |
| CN114044522B (en) * | 2021-11-24 | 2023-04-14 | 福州大学 | Functional active aluminosilicate and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107882A (en) * | 2009-12-23 | 2011-06-29 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
-
2012
- 2012-07-18 CN CN201210249568.8A patent/CN103570036B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107882A (en) * | 2009-12-23 | 2011-06-29 | 深圳市海川实业股份有限公司 | Method for preparing NaY zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103570036A (en) | 2014-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103570036B (en) | A kind of synthetic method of Y zeolite | |
| CN106185977B (en) | A kind of method of green syt ZSM-5 molecular sieve | |
| CN103848439B (en) | Synthetic method of ZSM-5 type molecular sieve | |
| CN104276586B (en) | A kind of preparation method of modenite | |
| CN105016355B (en) | A kind of molecular sieves of FeZSM 5 and its synthetic method | |
| KR102096040B1 (en) | Method for preparing zeolite ssz-52 | |
| GB1580928A (en) | Manufacture of low silica faujasites | |
| CN105776246A (en) | Method for low-cost synthesis of ZSM-5 molecular sieve | |
| EP0108486B1 (en) | Preparation of zeolites | |
| CN103572362A (en) | Method for hydrothermally synthesizing analcime monocrystal | |
| CN103043679B (en) | Synthesis method of Y type molecular sieve | |
| CN1281495C (en) | Method for preparing Fe-ZSM-5 zeolite microsphere using kieselguhr as raw material | |
| CN102107880B (en) | Method for preparing zeolite 4A | |
| CN112174164B (en) | ZSM-5 molecular sieve and preparation method thereof | |
| US5165906A (en) | Zeolite from the class of mazzite, process for its synthesis, an its use as a catalyst | |
| CN102701232B (en) | Preparation method of NaY molecular sieve | |
| CN101863492A (en) | Synthesis method of 4A-type zeolite | |
| KR920003219B1 (en) | Process for the production of zeolite | |
| Meftah et al. | Synthesis of zeolites A and P from 1: 1 and HS from 2: 1 clays | |
| US20060286029A1 (en) | Microporous crystalline zeolite material, zeolite ITQ-28, production method thereof and use of same | |
| CN101817539A (en) | Method for synthesizing A type molecular sieve by adopting attapulgite clay | |
| CN103204505A (en) | Preparation method of aluminum-containing layered kenyaite | |
| US5219813A (en) | Process for the preparation of novel molecular sieves | |
| KR100274118B1 (en) | Method for manufacturing A-type zeolite from coal fly ash | |
| EP0688738B1 (en) | A gallium silicate having 12-ring pores (ECR-34) and a method for its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |