CN103043680A - NaY molecular sieve/natural mineral composite material having multistage pore structure and preparation method thereof - Google Patents
NaY molecular sieve/natural mineral composite material having multistage pore structure and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of petrochemical industry, and relates to a NaY molecular sieve/natural mineral composite material having a multistage pore structure and a preparation method thereof. The composite material is a crystal product formed through in-situ crystallization by taking a natural kaolin mineral and a natural kieselguhr mineral as entire silicon sources and aluminum sources for molecular sieve synthesis and using the minerals as substrates for molecular sieve growth. In the composite material, the mass percent of the NaY molecular sieve is 25-50%, and the silicon-aluminum ratio of the NaY molecular sieve is 3-5.5. The invention widens the raw material sources in the preparation of the molecular sieve/natural mineral composite material through an in-situ synthesis method, and can simultaneously greatly lower the production cost of the molecular sieve/natural mineral composite material.
Description
Technical field
The invention belongs to petrochemical industry, relate to a kind of NaY molecular sieve with hierarchical porous structure/natural mineral matrix material and preparation method thereof, natural mineral wherein is kaolin mineral and diatomite mineral, it provides the synthetic needed whole silicon and aluminum sources of NaY molecular sieve, and as matrix or the solid support material of matrix material preparation.
Background technology
The in-situ crystallization technology is to have the SiO of chemical reactivity in the natural mineral
2And Al
2O
3As part silicon source and the aluminium source of synthesis of molecular sieve, make it under certain condition with the silicon source that adds, the aluminium source building-up process at outside surface and the inner duct surface growth molecular sieve of natural mineral.
Adopt the standby matrix material of in-situ crystallization legal system to have following important feature: (1) molecular sieve is connected with chemical bond with matrix, so crystallization product has good heat and hydrothermal stability; (2) high-temperature roasting is so that the part SiO in the kaolin
2And Al
2O
3Be activated, in the building-up process of molecular sieve, entered liquid phase by the basic solution extracting, thereby formed abundant macropore in stromal surface, this not only makes matrix itself have comparatively ideal pore size distribution, and for molecular sieve in the substrate, even growth on the outside surface provides the space, can greatly improve the utilization ratio of molecular sieve, make it in catalytic reaction process, have good active centre accessibility; (3) molecular sieve/groundmass composite material that forms has micropore, macropore multi-stage artery structure; The grain fineness number of the molecular sieve that (4) is synthesized is less, has improved the outer surface area of molecular sieve, more is conducive to the carrying out of surface-catalyzed reactions; (5) matrix has the advantage that thermal capacitance is large, rate of heat transfer is high, can prevent caving in of catalyst structure under the high temperature, is conducive to the work-ing life of extending catalyst.
Adopt at present the open report of in-situ crystallization technology synthesis of molecular sieve/natural mineral matrix material mainly to concentrate on take kaolin as raw material, by adding the in-situ crystallization preparation process of chemical silicon source (silicon sol, water glass etc.).USP3367886, USP 3367887, USP 34333587, USP 3503900, USP 3506594, USP 3647718, USP 36577154, USP 3663165, USP 3932268, USP 4493902, USP 4965233, USP5023220, USP 5395809, USP 5559067 and USP 6696378B2, CN 00122006, CN1436835, the basic preparation process of the descriptions such as CN101722024 is as follows: at first prepare kaolin microsphere by spray shaping, then through roasting microballoon is activated, and then adding adds silicon source (or aluminium source), the molecular sieve original position is grown in the surface and hole of kaolin microsphere, prepares molecular sieve/natural mineral mixture finally by aftertreatment.
At petrochemical industry, Y zeolite remains present most important molecular sieve.Y zeolite is that crystallization in strong alkali solution generates by polysilicate and aluminate.The synthetic used main raw material of Y zeolite industry is the Chemicals such as water glass, silicon sol, although the preparation technology of these Chemicals is quite ripe, but technical process length, energy consumption and material consumption are high, disposal of pollutants is serious, and the traditional Zeolite synthesis technology take it as raw material has been difficult to adapt to the development trend of green chemical industry.Therefore, many investigators attempt utilizing the mineral that are rich in sial of all kinds of cheapnesss to replace conventional industrial chemicals synthesizing for molecular sieve, with compare as the process of raw material synthesis of molecular sieve take the chemical product that routinizes, the process for preparing molecular sieve with natural mineral raw has more economy and environment friendly.In addition, during take natural mineral as the raw material synthesis of molecular sieve, the nucleation crystallization that depolymerizes to glue and molecular sieve of mineral is simultaneous, a large amount of gels be can not produce, owing to making appear in a large amount of gels difficulty, mass-and heat-transfer effect bad drawback stirred when preparing molecular sieve thereby overcome take the chemical product that routinizes as raw material.
USP 3574538 discloses a kind of method with the synthetic Y zeolite of kaolin.The method is unbodied metakaolin with the kaolin roasting first, adds a certain amount of water glass and sodium hydroxide, the SiO of regulation system again
2/ Al
2O
3Mol ratio approaches the silica alumina ratio of itself and product molecular sieve, adds at last the quality percentage composition and be 0.1% to 10% directed agents, makes highly purified Y zeolite after 60 ℃ to 110 ℃ crystallization, the SiO of product
2/ Al
2O
3Mol ratio is 4.5 to 5.95.
EP 0209332 (A2) discloses a kind of method that kaolin raw material crystallization is prepared Y zeolite under agitation condition, after this method is metakaolin with the kaolin roasting first, add water glass, silicon sol etc. again and add the silicon source, 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
2Then O adds directed agents, syntheticly under reaction conditions obtains NaY purity and reaches 97% powder.
CN 1334142A becomes to contain the high soil of spinel 940 to 1000 ℃ of lower roastings with part kaolin, another part becomes metakaolin 700 to 900 ℃ of lower roastings, then two kinds of roasting soil are mixed in proportion aluminium source and part silicon source as Zeolite synthesis, and addition portion divided silicic acid sodium is for adding the silicon source, adding directed agents, sodium hydroxide and water, is 40% to 90% molecular sieve at 90 to 95 ℃ of lower synthetic NaY quality percentage compositions.
CN 1533982 and USP 7067449 take through the metakaolin of 500 to 690 ℃ of roastings as Y zeolite synthetic aluminium source and part silicon source, add water glass for adding the silicon source, add directed agents, sodium hydroxide solution and water, make mol ratio and be (1 to 2.5) Na
2O: (4 to 9) SiO
2: Al
2O
3: (40 to 100) H
2The reaction raw materials of O, crystallization under 88 to 98 ℃ of stirrings obtains NaY quality percentage composition and is 30 to 85% molecular sieve after the filtration.
The report for preparing Y zeolite take natural mineral such as kaolin, rectorite, polynite, wilkinites as raw material has been arranged at present, report take kaolin, rectorite as silicon and aluminum source and matrix composition Y zeolite/natural mineral matrix material is also arranged, but in these reports only part utilized the sial species in the mineral, still needing to add a certain amount ofly adds chemical silicon source or the aluminium source prepares Y zeolite/natural mineral matrix material.Need not to add chemical silicon and aluminum source, the technology for preparing hierarchical porous structure Y zeolite/natural mineral matrix material fully take natural mineral as raw material there is not yet report.Y zeolite is the most widely used carrier and catalyzer in the petrochemical industry, and research and development are synthetic hierarchical porous structure Y zeolite/natural mineral composite manufacture technology take natural mineral as raw material fully, and good application prospect is arranged.
The method of the synthetic Y zeolite of in the past reporting/natural mineral matrix material, need to add the silica alumina ratio that adds silicon source or aluminium source adjusting synthetic system, these industrial chemicals are to produce through numerous and diverse reaction and sepn process from natural mineral mostly, the production process technology route is long, energy and material consumption is high, and there is the severe contamination discharging in most of process.In addition, in the past less in the matrix material of report have micropore, mesoporous, a multi-stage artery structure that macropore is compound, can only form micropore and macropore or micropore and mesoporous matrix material, and the formation of mixture intermediary hole is that introducing or the aftertreatment of the template passed through forms, preparation process is complicated, and the material preparation cost is higher.
Summary of the invention
For addressing the above problem, the invention provides a kind of NaY molecular sieve with hierarchical porous structure/natural mineral composite manufacture method, wherein utilize natural diatomaceous earth mineral and natural kaolin mineral that whole aluminium source and the silicon source of synthetic NaY molecular sieve are provided, and as the matrix of molecular sieve growth, through in-situ crystallization, make have micropore, the NaY molecular sieve of three grades of pore structures of mesoporous and macropore/natural mineral matrix material.
Therefore, the present invention also provides a kind of NaY molecular sieve with hierarchical porous structure/natural mineral matrix material, this matrix material has three grades of pore structures of micropore, mesoporous and macropore, wherein said natural mineral is kaolin mineral and diatomite mineral, this natural mineral provides the synthetic needed whole silicon and aluminum sources of NaY molecular sieve, and as matrix or the solid support material of matrix material, in NaY molecular sieve/natural mineral matrix material, the quality percentage composition of described NaY molecular sieve is 25% to 50%, and the silica alumina ratio of NaY molecular sieve is 3 to 5.5.
The present invention does not need to add other chemical silicon sources or aluminium source with whole silicon source and the aluminium source of natural mineral as Zeolite synthesis, has not only significantly reduced the synthetic cost of molecular sieve, and has widened the Application Areas of natural mineral.
Beneficial effect of the invention process is mainly reflected in following several respects:
(1) expands the raw material range of NaY Zeolite synthesis, opened up the new way that natural mineral utilizes.
(2) synthesize required whole silicon source and the aluminium source of NaY molecular sieve take natural diatomaceous earth and natural kaolin as raw material provides, do not need to add silicon source or aluminium source, reduced the preparation cost of NaY molecular sieve.
(3) content of molecular sieve is regulated and control the ratio of macropore in the matrix material, mesoporous and micropore in ratio that can be by natural mineral in the modulation raw material and the product, need not to add the preparation that expensive template can realize multilevel hole material under conventional hydrothermal synthesizing condition.
(4) in building-up process, the nucleation crystallization that depolymerizes to glue and molecular sieve of mineral is progressively to occur simultaneously, can not produce a large amount of gels, thereby avoid conventional chemical reagent synthesis method owing to the appearance of a large amount of gels makes mass transfer, the bad drawback of heat-transfer effect.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) spectrogram of the synthetic NaY molecular sieve with hierarchical porous structure of the embodiment of the invention 1/natural mineral matrix material.
Fig. 2 is that the synthetic NaY molecular sieve with hierarchical porous structure of the embodiment of the invention 1/natural mineral matrix material amplifies 1000 times scanning electron microscope (SEM) photo.
Fig. 3 is that the synthetic NaY molecular sieve with hierarchical porous structure of the embodiment of the invention 1/natural mineral matrix material amplifies 5000 times SEM photo.
Fig. 4 is the graph of pore diameter distribution of the synthetic NaY molecular sieve with hierarchical porous structure of the embodiment of the invention 1/natural mineral matrix material.
Embodiment
NaY molecular sieve with hierarchical porous structure of the present invention/natural mineral composite manufacture method may further comprise the steps:
(1) diatomite mineral and kaolin mineral are mixed to 3 according to mass ratio 1: 0.8;
(2) mixture that step (1) is obtained is at the effect compacted under of water, and with products formed 650 ℃ to 850 ℃ roastings, crush and screen subsequently, obtain the mineral grain raw material;
(3) the mineral grain raw material that step (2) is obtained mixes with directed agents, sodium hydroxide and water, wears out at 40 ℃ to 65 ℃, subsequently at 90 ℃ to 110 ℃ hydrothermal crystallizings;
(4) the crystallization product cooling that step (3) is obtained, remove by filter mother liquor, it is below 10 that filter cake is washed till pH with deionized water, and drying obtains having the NaY molecular sieve of hierarchical porous structure/natural mineral matrix material.
More particularly, take natural diatomaceous earth mineral and kaolin mineral as whole silicon and aluminum sources, above two kinds of mineral are mixed in proportion afterwards spraying drying or kneading and compacting under the effect of water, through roasting, be broken into particle, then add directed agents and sodium hydroxide solution, aging 4 to 12 hours, 90 to 110 ℃ hydrothermal crystallizings are 10 to 30 hours under 40 to 65 ℃; Crystallization product through cooling, remove by filter mother liquor, it is below 10 that filter cake is washed till pH with deionized water, drying obtains the NaY molecular sieve of hierarchical porous structure/natural mineral matrix material.
In the NaY molecular sieve with hierarchical porous structure provided by the present invention/natural mineral composite manufacture method, all silicon source and whole aluminium source are provided by the natural kaolin mineral of low silica-alumina ratio and the natural diatomaceous earth mineral of high silica alumina ratio, in preparation process, by the ratio of two kinds of mineral of suitable modulation, can obtain the NaY molecular sieve of Different Silicon aluminum ratio/natural mineral matrix material.
Micropore in NaY molecular sieve described in the present invention/natural mineral matrix material, mesoporous and macropore refer to respectively the aperture less than 2nm, the aperture be 2 to 50nm and the aperture greater than the hole of 60nm.Micropore, material mesoporous, multi-stage artery structure that macropore is compound have important effect in petroleum and petrochemical industry, field of fine chemical.Catalytic cracking in the petroleum refining process is as example, at first cracking in the surface of granules of catalyst and macropore of macromole in the cracking process, and the form with intermediate product continues cracking in mesoporous and micro-pore zeolite then.Therefore, an important channel of improving oil product cracking process efficient is exactly introducing macropore and meso-hole structure in cracking catalyst, construct have micropore, the novel catalyst system of mesoporous, multi-stage artery structure that macropore is compound.
In the NaY molecular sieve with hierarchical porous structure provided by the present invention/natural mineral composite manufacture method, the micropore of matrix material derives from crystallization product NaY molecular sieve, the mesoporous naturally occurring a large amount of meso-hole structures of diatomite particle that derive from, macropore derives from naturally occurring macroporous structure in accumulation hole between kaolin particle and the diatomite particle, and the content of molecular sieve is realized in the ratio that the pore passage structure of mixture can be by natural mineral in the modulation raw material and the product.
According to method provided by the present invention, natural mineral can carry out acid treatment before calcination process, and with the content of some chemical ingredients (such as calcium, iron, nickel etc.) in the reduction mineral, but this is not necessary.The NaY molecular sieve with hierarchical porous structure that the present invention is prepared/natural mineral matrix material can be applied to many occasions, its result of use of not remarkably influenced of impurity that a small amount of impure mineral brings is so the present invention can be larger to the range of choice of kaolin and diatomite purity.Being the present invention is not strict with the purity of raw mineral materials, but kaolin and diatomaceous quality percentage composition are more than 75% in the preferred mineral.
In method provided by the present invention, described kaolin mineral is the natural mineral of low silica-alumina ratio, and it can also select the natural mineral such as polynite, wilkinite, Attapulgite except from the kaolin.Described diatomite mineral are high silicon mine, and it is except from the diatomite, also optional white carbon black in order to the natural mineral preparation.
The present invention has added homemade seeding director in the molecular sieve process, contain a large amount of Y zeolite primary structure and secondary structure unit in the prepared seeding director, in the Crystallization of Zeolite process, these primary and secondary structural units become the nucleus of Y zeolite growth, although add-on is few, but played the effect of accelerating the product conversion rate, shortening crystallization time, be conducive to production application.Directed agents can be synthesized according to a conventional method, and as synthetic according to the preparation method of USP 3574538, USP 4166099 and EP 0435625, the composition of described directed agents is take molar ratio computing as 16 to 18 Na
2O: 0.8 to 1.2 Al
2O
3: 16 to 18 SiO
2: 310 to 340 H
2O.The optimum condition of directed agents preparation is: synthetic and aging at 10 ℃ to 25 ℃ at 10 ℃ to 40 ℃.In preparation process of the present invention, the weight ratio of described directed agents solution and described mineral grain raw material is 0.6 to 1.5.
In above-mentioned preparation method, the mixture that also step (1) can be obtained is at the effect compacted under of water and binding agent, described binding agent can be silicon sol, aluminium colloidal sol or water glass, and the mass ratio of the natural mineral mixture of described binding agent and diatomite mineral and kaolin mineral is 0.02 to 0.2.
In above-mentioned preparation method.Being shaped in step (2), water or under water and binding agent effect extruded moulding, drying is broken into the mineral grain raw material again; Perhaps spray-dried one-tenth mineral microballoon, the mineral grain raw material that step (2) obtains or the particle diameter of mineral microballoon are 50 μ m to 130 μ m.
Preparation method of the present invention have preparation flow simple, use that raw material is easy to get, the advantage such as product silica alumina ratio and pore size distribution are controlled.The NaY molecular sieve with hierarchical porous structure that employing the inventive method is synthesized/natural mineral matrix material, its X-ray diffraction (XRD) spectrogram has the characteristic feature of NaY molecular sieve.This NaY molecular sieve is carried out ion modification and hydrothermal treatment consists with rare earth chloride, ammonium sulfate, ammonium phosphate etc., can make the dissimilar Modified Zeolite Y such as REY, REHY, USY, REUSY, P-REUSY/natural mineral matrix material, have identical or more excellent physico-chemical property with the congeneric elements sieve that synthesizes with chemical silicon source and aluminium source.
The invention will be further elaborated below in conjunction with embodiment, and these embodiment are intended to illustrate in detail embodiment of the present invention and characteristics, can not be interpreted as any restriction of the present invention.
The molecular sieve quality percentage composition of mentioned matrix material adopts marker method to calculate among the embodiment, method of calculation are as follows: at first metakaolin is mixed by different ratios with the NaY molecular sieve, calculate the area of NaY molecular sieve characteristic peak (2 θ angles are at 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 °) in the different ratios mixture, draw the feature work curve.Then calculate the characteristic peak peak area of Y zeolite in the matrix material of the following example preparation, and with itself and above-mentioned feature work curve comparison, obtain the quality percentage composition of NaY molecular sieve in the matrix material.
The product silica alumina ratio is by solid-state
29The Si magic-angle-spinning nuclear magnetic resonance (
29Si MAS NMR) method characterizes, and instrument is the German Brucker product DSX of company 500 type nuclear magnetic resonance analyser.The silica alumina ratio of the NaY molecular sieve of describing among the present invention refers to SiO
2With Al
2O
3Mol ratio.
The pore structure parameter of product is measured by the AutoPore IV 9500 type mercury injection apparatuses that U.S. Micromeritics company produces, and experimental pressure is 0-30000psia.In pore distribution, mercury penetration method mainly provides mesoporous and pore structure parameter macropore, and the micropore pore structure parameter is mainly determined by two portions in the matrix material: the type of first molecular sieve is Y zeolite among the present invention, so its aperture is fixing 0.74nm; It two is quality percentage compositions of molecular sieve in the matrix material, and the quality percentage composition height of the molecular sieve then micropore pore volume of matrix material is large.
Get 27.2 gram (g) sodium hydrate solids (Beijing Chemical Plant produces, and purity is 99%) and be dissolved in the 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 for preparing is dissolved in makes high alkali deflection aluminium acid sodium solution in the sodium hydroxide solution.With 96.63g water glass (molecular formula: Na
2SiO
39H
2O, Beijing modern chemistry reagent company, purity is 99%) be dissolved in the 115g water, add 82g silicon sol (Qingdao Marine Chemical Co., Ltd., SiO
2Content is 30.0%, Na
2O content is 0.06%), rapid stirring 2 hours.Then under agitation condition, add high alkali deflection aluminium acid sodium solution, stir ageings 4 hours down at 30 ℃ after mixing, under the room temperature still aging 2 days, make directed agents liquid.
Be that 1: 1.7 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that globule size is 65 μ m to 120 μ m after the bar shaped agent oven dry, 780 ℃ of lower roastings 4 hours, for subsequent use.
(Beijing Chemical Plant produces with the 5.8g sodium hydrate solid, purity is 99%) be dissolved in the 35g distilled water, add directed agents liquid 6g, mix with natural mineral particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, left standstill aging 12 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 105 ℃ and left standstill crystallization 24 hours.After crystallization finished, through cooling off, remove by filter mother liquor, solid product obtained crystallization product after washing, drying.Through XRD determining, its phase belongs to Y zeolite, the quality percentage composition of NaY molecular sieve is 42% in the product, the synthetic NaY silica alumina ratio of original position is 4.6, its XRD spectra is seen Fig. 1, the SEM photo of NaY molecular sieve/natural mineral matrix material is seen Fig. 2, and the SEM photo of NaY molecular sieve/natural mineral composite material surface Y zeolite is seen Fig. 3.The pore size distribution of NaY molecular sieve/natural mineral matrix material is seen Fig. 4, can obviously find out matrix material 11.2,20.7, there is concentrated mesoporous existence at the 33.4nm place, 82.1,147.6, the 413.9nm place has concentrated macropore to exist.
Embodiment 2
The preparation of directed agents liquid is with embodiment 1.
Be that 1: 2 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that granularity is 50 to 100 μ m after the bar shaped agent oven dry, 820 ℃ of lower roastings 4 hours, for subsequent use.
6.2g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) is dissolved in the 40g distilled water, adds directed agents liquid 7.8g, mixes with particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, leave standstill and wore out 15 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 95 ℃, left standstill crystallization 20 hours.After crystallization finished, through cooling off, remove by filter mother liquor, solid product obtained crystallization product after washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 45% in the product, and the synthetic NaY silica alumina ratio of original position is 4.2.NaY molecular sieve/natural mineral matrix material 16.7,26.4, there is concentrated mesoporous existence at the 40.3nm place, has concentrated macropore to exist at the 218.9nm place.
Embodiment 3
The preparation of directed agents liquid is with embodiment 1.
Be that 1: 1.5 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add water and silicon sol (mass ratio of silicon sol quality and diatomite and kaolinic natural mineral mixture is 0.05) extruded moulding, to be broken into the particle that granularity is 75 to 110 μ m after the bar shaped agent oven dry, 800 ℃ of lower roastings 3 hours, for subsequent use.
6.5g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) is dissolved in the 40g distilled water, adds directed agents liquid 5g, mixes with particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, leave standstill and wore out 10 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 95 ℃ and left standstill crystallization 16 hours.After crystallization finished, through cooling off, remove by filter mother liquor, solid product obtained crystallization product after washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 38% in the product, and the synthetic NaY silica alumina ratio of original position is 5.0.NaY molecular sieve/natural mineral matrix material 7.2,11.1, there is concentrated mesoporous existence at the 15.7nm place, has concentrated macropore to exist at the 160.9nm place.
Embodiment 4
Get 27.2g sodium hydrate solid (Beijing Chemical Plant produces, and purity is 99%) and be dissolved in the 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 for preparing is dissolved in makes high alkali deflection aluminium acid sodium solution in the sodium hydroxide solution.With 85.26g water glass (molecular formula: Na
2SiO
39H
2O, Beijing modern chemistry reagent company, purity is 99%) be dissolved in the 100g water, add 72g silicon sol (Qingdao Marine Chemical Co., Ltd., SiO
2Content is 30.0%, Na
2O content is 0.06%), rapid stirring 2 hours.Then under agitation condition, add high alkali deflection aluminium acid sodium solution, stir ageings 4 hours down at 30 ℃ after mixing, under the room temperature still aging 2 days, make the guiding fluid agent.
Be that 1: 3 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that granularity is 50 to 90 μ m after the bar shaped agent oven dry, 680 ℃ of lower roastings 5 hours, for subsequent use.
(Beijing Chemical Plant produces with the 7.2g sodium hydrate solid, purity is 99%) be dissolved in the 38g distilled water, add directed agents liquid 6.5g, mix with natural mineral particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, left standstill aging 12 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 110 ℃ and left standstill crystallization 12 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 25% in the product, and the synthetic NaY silica alumina ratio of original position is 3.6.NaY molecular sieve/natural mineral matrix material 11.1,21.4, there is concentrated mesoporous existence at the 33.3nm place, 80.5, the 428.7nm place has concentrated macropore to exist.
The directed agents preparation is with embodiment 4.
Be that 1: 1.4 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add water and silicon sol (mass ratio of silicon sol quality and diatomite and kaolinic natural mineral mixture is 0.15) extruded moulding, to be broken into the particle that granularity is 75 to 120 μ m after the bar shaped agent oven dry, 760 ℃ of lower roastings 2 hours, for subsequent use.
(Beijing Chemical Plant produces with the 6.4g sodium hydrate solid, purity is 99%) be dissolved in the 38g distilled water, add directed agents liquid 6.5g, mix with natural mineral particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, left standstill aging 10 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 100 ℃ and left standstill crystallization 24 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 32% in the product, and the synthetic NaY silica alumina ratio of original position is 5.2.NaY molecular sieve/natural mineral matrix material 7.1, there is concentrated mesoporous existence at the 20.9nm place, has concentrated macropore to exist at the 143.4nm place.
Embodiment 6
The directed agents preparation is with embodiment 4
Be that 1: 1 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that granularity is 50 to 110 μ m after the bar shaped agent oven dry, 800 ℃ of lower roastings 4 hours, for subsequent use.
5.8g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) is dissolved in the 38g distilled water, adds directed agents liquid 8g, mixes with particle 6g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, leave standstill and wore out 12 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 105 ℃ and left standstill crystallization 24 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 37% in the product, and the synthetic NaY silica alumina ratio of original position is 5.3.NaY molecular sieve/natural mineral matrix material 7.3,12.7,20.9, there is concentrated mesoporous existence at the 41.1nm place, has concentrated macropore to exist at the 179nm place.
Embodiment 7
The directed agents preparation is with embodiment 1.
Be that 1: 2 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that granularity is 60 to 110 μ m after the bar shaped agent oven dry, 820 ℃ of lower roastings 5 hours, for subsequent use.
4.5g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) is dissolved in the 35g distilled water, adds directed agents liquid 7g, mixes with particle 5g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, leave standstill and wore out 16 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 95 ℃ and left standstill crystallization 24 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 43% in the product, and the synthetic NaY silica alumina ratio of original position is 4.2.NaY molecular sieve/natural mineral matrix material 5.9, there is concentrated mesoporous existence at the 12.5nm place, has concentrated macropore to exist at the 160.9nm place.
Embodiment 8
The directed agents preparation is with embodiment 4.
Be that 1: 2.5 ratio is mixed in mass ratio with commercially available diatomite and kaolin, add the water extruded moulding, with being broken into the particle that granularity is 60 to 120 μ m after the bar shaped agent oven dry, 810 ℃ of lower roastings 3 hours, for subsequent use.
6.0g sodium hydrate solid (Beijing Chemical Plant produce, purity is 99%) is dissolved in the 45g distilled water, adds directed agents liquid 8g, mixes with particle 8g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, leave standstill and wore out 12 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 105 ℃ and left standstill crystallization 16 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 40% in the product, and the synthetic NaY silica alumina ratio of original position is 4.6.NaY molecular sieve/natural mineral matrix material 11.3, there is concentrated mesoporous existence at the 17.3nm place, 52.7, the 250.2nm place has concentrated macropore to exist.
Comparative Examples: prepare NaY/ kaolin mixture as the silicon source to add chemical reagent (silicon sol)
The preparation of directed agents liquid is with embodiment 1.
Commercially available kaolin is added the water extruded moulding, be 60 to 120 μ m natural mineral particles with being broken into granularity after the bar shaped agent oven dry, 800 ℃ of lower roastings 4 hours, for subsequent use.
5.8g sodium hydrate solid (Beijing Chemical Plant produces, and purity is 99%) is dissolved in the 34g distilled water, adds silicon sol 11.2g, directed agents liquid 8.6g, mix with the particle 8g after the above-mentioned calcination process, stirred about 1 hour, and under 60 ℃, left standstill aging 12 hours.
Said mixture is poured in the band teflon-lined stainless steel crystallizing kettle, be warming up to 105 ℃ and left standstill crystallization 24 hours.After crystallization finished, through cooling off, remove by filter mother liquor, the gained solid product obtained crystallization product through washing, drying.Through XRD determining, its phase belongs to Y zeolite, and the quality percentage composition of NaY molecular sieve is 40% in the product, and the synthetic NaY silica alumina ratio of original position is 4.5.Through Estimation of Pore Size, only have the macropore about micropore and 100nm in the matrix material, do not contain meso-hole structure.
This presentation of results, provide whole silicon and aluminum sources as matrix material is synthetic take diatomite and kaolin, the NaY molecular sieve of employing in-situ crystallization technology preparation/natural mineral matrix material, have and the characteristic that the NaY molecular sieve/the natural mineral matrix material is close that adds the preparation of silicon source, and has more excellent pore passage structure, but its preparation cost is cheaper, and preparation process is environmental friendliness more.
Claims (9)
1. the NaY molecular sieve with hierarchical porous structure/natural mineral matrix material, this matrix material has three grades of pore structures of micropore, mesoporous and macropore, wherein said natural mineral is kaolin mineral and diatomite mineral, this natural mineral provides the synthetic needed whole silicon and aluminum sources of NaY molecular sieve, and as matrix or the solid support material of matrix material, in NaY molecular sieve/natural mineral matrix material, the quality percentage composition of described NaY molecular sieve is 25% to 50%, and the silica alumina ratio of NaY molecular sieve is 3 to 5.5.
2. the NaY molecular sieve with hierarchical porous structure as claimed in claim 1/natural mineral matrix material, wherein this micropore with the NaY molecular sieve of hierarchical porous structure/natural mineral matrix material derives from crystallization product NaY molecular sieve, the mesoporous naturally occurring meso-hole structure of diatomite particle that derives from, macropore derives from naturally occurring macroporous structure in kaolin mineral intergranular accumulation hole and the diatomite ore composition granule.
3. the NaY molecular sieve with hierarchical porous structure claimed in claim 1/natural mineral composite manufacture method, it is characterized in that, utilize natural diatomaceous earth mineral and natural kaolin mineral that whole aluminium source and the silicon source of synthetic NaY molecular sieve are provided, and as the matrix of molecular sieve growth, through in-situ crystallization, make have micropore, the NaY molecular sieve of three grades of pore structures of mesoporous and macropore/natural mineral matrix material.
4. the NaY molecular sieve with hierarchical porous structure as claimed in claim 3/natural mineral composite manufacture method, the method may further comprise the steps:
(1) diatomite mineral and kaolin mineral are mixed to 3 according to mass ratio 1: 0.8;
(2) mixture that step (1) is obtained is at the effect compacted under of water, and with products formed 650 ℃ to 850 ℃ roastings, crush and screen subsequently, obtain the mineral grain raw material;
(3) the mineral grain raw material that step (2) is obtained mixes with directed agents, sodium hydroxide and water, wears out at 40 ℃ to 65 ℃, subsequently at 90 ℃ to 110 ℃ hydrothermal crystallizings;
(4) the crystallization product cooling that step (3) is obtained, remove by filter mother liquor, it is below 10 that filter cake is washed till pH with deionized water, and drying obtains having the NaY molecular sieve of hierarchical porous structure/natural mineral matrix material.
5. the NaY molecular sieve with hierarchical porous structure as claimed in claim 4/natural mineral composite manufacture method, wherein in step (2), the mixture that step (1) is obtained is at the effect compacted under of water and binding agent.
6. such as claim 4 or 5 described NaY molecular sieve with hierarchical porous structure/natural mineral composite manufacture methods, wherein, the composition of described directed agents is take molar ratio computing as 16 to 18 Na
2O: 0.8 to 1.2 Al
2O
3: 16 to 18 SiO
2: 310 to 340 H
2O; The weight ratio of described directed agents solution and described mineral grain raw material is 0.6 to 1.5.
7. the NaY molecular sieve with hierarchical porous structure as claimed in claim 4/natural mineral composite manufacture method, wherein, in step (2) be shaped to water or under water and binding agent effect extruded moulding, drying is broken into the mineral grain raw material again; Perhaps spray-dried one-tenth mineral microballoon.
8. such as claim 5 or 7 described NaY molecular sieve with hierarchical porous structure/natural mineral composite manufacture methods, wherein, described binding agent is silicon sol, aluminium colloidal sol or water glass, and the mass ratio of the mineral intermixture of described binding agent and diatomite mineral and kaolin mineral is 0.02 to 0.2.
9. such as claim 4,5 or 7 described NaY molecular sieve with hierarchical porous structure/natural mineral composite manufacture methods, wherein, the particle diameter of described mineral grain raw material or mineral microballoon is 50 μ m to 130 μ m.
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