CN102274742A - Method for preparing mesoporous catalytic composite material - Google Patents
Method for preparing mesoporous catalytic composite material Download PDFInfo
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- CN102274742A CN102274742A CN2011101690091A CN201110169009A CN102274742A CN 102274742 A CN102274742 A CN 102274742A CN 2011101690091 A CN2011101690091 A CN 2011101690091A CN 201110169009 A CN201110169009 A CN 201110169009A CN 102274742 A CN102274742 A CN 102274742A
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Abstract
The invention discloses a method for preparing a mesoporous catalytic composite material. The method is characterized by taking diatomaceous earth and kaolin as raw materials and comprising the following steps of: A, adding water and a dispersing agent into the diatomaceous earth and kaolin, uniformly stirring to obtain a slurry, adjusting a slurry destination pH value to 4.0-12.0 by using acid or alkali, spraying and drying to form a microsphere, and calcining the microsphere to obtain a mixed clay calcined microsphere; B, adding water and an adhesive into the kaolin and a zeolite molecular sieve, uniformly stirring to form a slurry, spraying and drying to form a microsphere, and calcining the microsphere to obtain a calcined microsphere; and C, adding sodium silicate, alkali liquor and a zeolite guide agent into the mixed clay calcined microsphere obtained in the step A and/or the calcined microsphere obtained in the step B, then putting into a crystallized reaction kettle for hydrothermal crystallization, filtering to remove mother liquor, washing the filter material by using deionized water, filtering again to obtain the washed filter material, and drying the filter material to obtain the mesoporous catalytic composite material containing a NaY zeolite molecular sieve. The method disclosed by the invention is mainly used for preparing the mesoporous catalytic composite material containing the NaY zeolite molecular sieve.
Description
Technical field
The present invention relates to a kind of method for preparing mesoporous catalytic composite materials, specifically, be a kind of be raw material with diatomite and kaolin, contain the method for the mesoporous catalytic composite materials of NaY zeolite molecular sieve by hydro-thermal in-situ crystallization method preparation.
Background technology
Announced with kaolin to be since raw material synthesizes the NaY zeolite molecular sieve from U.S. Pat 3119659 in 1964, the natural minerals synthesis zeolite just becomes the research focus day by day with advantages such as its utilization rate height, with low cost, technological process in simple and practical, and is increasing to its report.
With diatomite and kaolin is primary raw material, utilizes the synthetic mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve of hydro-thermal in-situ crystallization technology not appear in the newspapers as yet.Diatomite is in industrial filter aid, filler and the catalyst carrier of being mainly used in, and the study on the synthesis that is used for zeolite molecular sieve is few, mainly concentrate on zeolites such as NaP1, SOD, MOR and ZSM-5, adopt diatomite synthesizing flokite (MOR zeolite) as people such as V.Sanhueza; People such as A.Chaisena adopt diatomite to synthesize NaP1 type zeolite molecular sieve, sodalite (ANA); Chinese patent CN 1915820 discloses small crystal grain without bonding agent ZSM-5 prepare zeolite method, with diatomite or white carbon is primary raw material, add the crystal seed directed agents,, handle mutually with organic amine and water vapour gas-solid then and be converted into integrated small-grain ZSM-5 as the binding agent moulding with Ludox or sodium metasilicate; Chinese patent CN 101348261 relates to binderless ZSM-5-11 prepare zeolite method, with at least a in diatomite, white carbon, Ludox or the waterglass is the silicon source, is the synthetic ZSM-11 zeolite in aluminium source with at least a in oxide, aluminium salt or the aluminate of aluminium; Chinese patent CN 1557707 has announced with diatomite to be the method for feedstock production Fe-ZSM-5 microsphere of zeolite, need not high temperature alkali dissolution activation diatomite material, with the 4-propyl bromide is that template agent, sodium chloride are additive, and the direct hydrothermal crystallizing in aging back obtains the zeolite molecular sieve product of high silica alumina ratio.
The present invention is a raw material with diatomite and kaolin, adopts the synthetic mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve of in-situ crystallization technology, and this material contains degree of crystallinity at 20～70% NaY zeolite molecular sieve, its SiO
2/ Al
2O
3In 4.6～5.8 (mol ratios), specific surface is at 260～700m
2/ g, pore volume are at 0.20～0.45ml/g, and mesoporous distribution concentrates on about 10nm.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with diatomite and kaolin, contains the method for the mesoporous catalytic composite materials of NaY zeolite molecular sieve by the preparation of hydro-thermal in-situ crystallization method.This method can be utilized diatomite resource profoundly, improves its value, can reduce production costs significantly.
The invention discloses a kind of method for preparing mesoporous catalytic composite materials, is raw material with diatomite and kaolin, it is characterized in that following steps:
A, diatomite and kaolin are added water and dispersant stir and make slurries, with acid or alkali the slurries endpoint pH is transferred to 4.0～12.0, be spray dried to microballoon, microballoon is 700～1000 ℃ of following roastings 0.5～10 hour, mixed clay roasting microballoon;
B, kaolin and zeolite molecular sieve are added water and binding agent stir and make slurries, be spray dried to microballoon, microballoon is 600～900 ℃ of following roastings 0.5～10 hour, the roasting microballoon;
The roasting microballoon that C, the mixed clay roasting microballoon that steps A is obtained and/or step B obtain drops in the crystallization still after adding sodium metasilicate, alkali lye, guiding agent for zeolite, 90～120 ℃ of following hydrothermal crystallizings 8～32 hours, after removing by filter mother liquor, filtrate is washed with deionized water, filter, must wash the back filtrate, make the mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve behind dry this filtrate.
In the described steps A, diatomaceous addition is 10～90% of a steps A total weight of solids.
Among the described step B, the addition of zeolite molecular sieve be step B total weight of solids 5～70%, kaolin is 0～90% of step B total weight of solids.
Among the described step B, the addition of binding agent is 5～30% of a step B total weight of solids.
Compared with the prior art the present invention also has the following advantages: in the prior art, many is that raw material carries out the synthetic of NaY zeolite molecular sieve with kaolin, and with diatomite and the kaolin mesoporous catalytic composite materials that to be raw material contain the NaY zeolite molecular sieve by the preparation of hydro-thermal in-situ crystallization method report not also, the present invention utilizes diatomite silica content height and the big advantage of pore volume, can effectively replenish the silica of synthetic system, the mesoporous distribution of control synthetic material.The mesoporous catalytic composite materials of this method preparation contains degree of crystallinity at 20～70% NaY zeolite molecular sieve, its SiO
2/ Al
2O
3In 4.6～5.8 (mol ratios), specific surface is at 260～700m
2/ g, pore volume are at 0.20～0.45ml/g, and mesoporous distribution concentrates on about 10nm.This method preparation flow is simple, saves raw material significantly, reduces production costs.Gained composite mesolite molecular sieve content height, structural stability is good, specific surface and pore volume are big, has abundant meso-hole structure, can be used as catalytic cracking catalyst, catalyst for cracking, fine chemistry industry catalyst, adsorbent or the like, be specially adapted to the processing of heavy raw oil in the catalytic cracking process.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, but does not therefore limit the present invention.
The invention is characterized in following steps:
A, diatomite and kaolin are added water and dispersant stir and make slurries, with acid or alkali the slurries endpoint pH is transferred to 4.0～12.0, be spray dried to microballoon, microballoon is 700～1000 ℃ of following roastings 0.5～10 hour, mixed clay roasting microballoon;
B, kaolin and zeolite molecular sieve are added water and binding agent stir and make slurries, be spray dried to microballoon, microballoon is 600～900 ℃ of following roastings 0.5～10 hour, the roasting microballoon;
The roasting microballoon that C, the mixed clay roasting microballoon that steps A is obtained and/or step B obtain drops in the crystallization still after adding sodium metasilicate, alkali lye, guiding agent for zeolite, 90～120 ℃ of following hydrothermal crystallizings 8～32 hours, after removing by filter mother liquor, filtrate is washed with deionized water, filter, must wash the back filtrate, make the mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve behind dry this filtrate.
In the described steps A, diatomaceous addition is 10～90% of a steps A total weight of solids.
Among the described step B, the addition of zeolite molecular sieve be step B total weight of solids 5～70%, kaolin is 0～90% of step B total weight of solids.
Among the described step B, the addition of binding agent is 5～30% of a step B total weight of solids.
Below provide embodiments of the invention:
Embodiment 1
(1) 198g kaolin and 1792g diatomite are added water and stir that to make solid content be 47% slurries, add dispersant 120ml sodium metasilicate, regulating the slurries endpoint pH with 8% hydrochloric acid is 4.0, pulp 1 hour, spray drying forming is the microballoon of meso-position radius 71.37 μ m, microballoon is put into Muffle furnace,, get mixed clay roasting microballoon 700 ℃ of following roastings 10 hours;
(2) 490g ZSM-5 zeolite molecular sieve being added water, to make solid content be 45% slurries, add binding agent 210g aluminium colloidal sol, spray drying forming is the microballoon of meso-position radius 69.26 μ m, and microballoon is put into Muffle furnace, 820 ℃ of following roastings 3.5 hours, get the roasting microballoon;
(3) under stirring successively with sodium metasilicate 870ml, alkali lye (NaOH) 360ml, guiding agent for zeolite 130ml, mixed clay roasting microballoon 500g, roasting microballoon 300g drops in the stainless steel crystallization still, is warmed up to 98 ℃, thermostatic crystallization 20 hours.After crystallization finishes, remove by filter mother liquor, washing, filtration, dry cake obtain containing the mesoporous catalytic composite materials of NaY zeolite molecular sieve.Measure through X-ray diffraction, composite contains 63.7% NaY zeolite molecular sieve, and its silica alumina ratio (mol ratio) is 5.1; Abrasion index is 2.9; The BET specific surface is 612.6m
2/ g, micropore specific surface 492.9m
2/ g, pore volume are 0.37ml/g, micropore pore volume 0.24ml/g.
Guiding agent for zeolite is that those skilled in the art are according to Na
2O: SiO
2: Al
2O
3: H
2O=16: 15: 1: 320 (mol ratio) prepared voluntarily.
Embodiment 2
(1) kaolin 4104g, diatomite 456g add water slurrying, and solid content 35% adds the blue or green powder in dispersant 130g field, 15% NaOH is regulated pH value 12.0, pulp 4 hours, spray-drying, microballoon meso-position radius 73.51m, 1000 ℃ of following roastings 0.5 hour, mixed clay roasting microballoon;
(2) kaolin 600g, ZSM-5 zeolite molecular sieve 60g add water slurrying, solid content 37%, adding additives 53g aluminium colloidal sol, spray-drying, microballoon meso-position radius 75.14 μ m, 600 ℃ of following roastings 10 hours, the roasting microballoon;
(3) sodium metasilicate 2920ml, alkali lye 350ml, guiding agent for zeolite 130ml, mixed clay roasting microballoon 200g, roasting microballoon 120g drop in the stainless steel crystallization still, are warmed up to 120 ℃, thermostatic crystallization 8 hours.Composite contains 43.8% NaY zeolite molecular sieve, its silica alumina ratio 5.5, abrasion index 2.1, BET specific surface 432.7m
2/ g, micropore specific surface 301.1m
2/ g, pore volume 0.36ml/g, micropore pore volume 0.23ml/g.All the other are with embodiment 1.
Embodiment 3
(1) kaolin 713g, diatomite 100g add water slurrying, and solid content is 35%, add dispersant 25g Sodium Polyacrylate, 10% NaOH is regulated pH value 9.5, pulp 3 hours, spray-drying, microballoon meso-position radius 73.39 μ m, 930 ℃ of following roastings 2.5 hours, mixed clay roasting microballoon;
(2) kaolin 137g, NaX zeolite molecular sieve 320g add water slurrying, and solid content is 40%, adding additives 70g Ludox, spray-drying, microballoon meso-position radius 68.63 μ m, 900 ℃ of following roastings 0.5 hour, the roasting microballoon;
(3) sodium metasilicate 287ml, alkali lye 240ml, guiding agent for zeolite 80ml, mixed clay roasting microballoon 200g, roasting microballoon 30g drop in the stainless steel crystallization still, are warmed up to 90 ℃, thermostatic crystallization 32 hours.Composite contains 55.1% NaY zeolite molecular sieve, its silica alumina ratio 5.2, abrasion index 1.7, BET specific surface 552.6m
2/ g, micropore specific surface 483.6m
2/ g, pore volume 0.38ml/g, micropore pore volume 0.22ml/g.All the other are with embodiment 1.
Embodiment 4
(1) kaolin 529g, diatomite 540 add water slurrying, and solid content is 38%, add dispersant 305ml calgon, 21ml sodium carbonate, 15% phosphorus acid for adjusting pH value 7.1, pulp 2 hours, spray-drying, microballoon meso-position radius 72.81 μ m, 900 ℃ of following roastings 2.5 hours, mixed clay roasting microballoon;
(2) kaolin 478g, NaY molecular sieve 22g add water slurrying, and solid content is 33%, adding additives 25g Ludox, spray-drying, microballoon meso-position radius 73.18 μ m, 650 ℃ of following roastings 10.0 hours, the roasting microballoon;
(3) sodium metasilicate 333ml, alkali lye 200ml, guiding agent for zeolite 90ml, mixed clay roasting microballoon 217g, roasting microballoon 35g drop in the stainless steel crystallization still, are warmed up to 99 ℃, thermostatic crystallization 16 hours.Composite contains 68.3% NaY zeolite molecular sieve, its silica alumina ratio 5.8, abrasion index 2.0, BET specific surface 653.4m
2/ g, micropore specific surface 582.5m
2/ g, pore volume 0.39ml/g, micropore pore volume 0.25ml/g.All the other are with embodiment 1.
Embodiment 5
(1) kaolin 592g, diatomite 256g add water slurrying, solid content is 36%, add dispersant 130ml sodium pyrophosphate, 15ml carbonic hydroammonium, 8% salt acid for adjusting pH value 10.0, pulp 2.5 hours, spray-drying, microballoon meso-position radius 74.11 μ m, 978 ℃ of following roastings 1.5 hours, mixed clay roasting microballoon;
(2) sodium metasilicate 135ml, alkali lye (NaOH) 220ml, guiding agent for zeolite 30ml, mixed clay roasting microballoon 280g drop in the stainless steel crystallization still, are warmed up to 95 ℃, thermostatic crystallization 26 hours.Remove by filter mother liquor, washing, filtration, dry cake get product.Measure through X-ray diffraction, composite contains 23.5% NaY zeolite molecular sieve, its silica alumina ratio 4.8; Abrasion index 1.3; BET specific surface 267m
2/ g, micropore specific surface 182.5m
2/ g, pore volume 0.26ml/g, micropore pore volume 0.17ml/g.
From above 5 embodiment results, with diatomite and kaolin as raw material, prepare the NaY zeolite molecular sieve that the mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve contains degree of crystallinity 20～70%, its silica alumina ratio (mol ratio) 4.6～5.8, specific surface 260～700m by hydro-thermal in-situ crystallization method
2/ g, pore volume 0.20～0.45ml/g, mesoporous distribution concentrates on about 10nm.This method preparation flow is simple, with low cost, gained composite mesolite content height, and specific surface and pore volume are big, have abundant meso-hole structure.
Claims (4)
1. a method for preparing mesoporous catalytic composite materials is a raw material with diatomite and kaolin, it is characterized in that following steps:
A, diatomite and kaolin are added water and dispersant stir and make slurries, with acid or alkali the slurries endpoint pH is transferred to 4.0～12.0, be spray dried to microballoon, microballoon is 700～1000 ℃ of following roastings 0.5～10 hour, mixed clay roasting microballoon;
B, kaolin and zeolite molecular sieve are added water and binding agent stir and make slurries, be spray dried to microballoon, microballoon is 600～900 ℃ of following roastings 0.5～10 hour, the roasting microballoon;
The roasting microballoon that C, the mixed clay roasting microballoon that steps A is obtained and/or step B obtain drops in the crystallization still after adding sodium metasilicate, alkali lye, guiding agent for zeolite, 90～120 ℃ of following hydrothermal crystallizings 8～32 hours, after removing by filter mother liquor, filtrate is washed with deionized water, filter, must wash the back filtrate, make the mesoporous catalytic composite materials that contains the NaY zeolite molecular sieve behind dry this filtrate.
2. by the described method of claim 1, it is characterized in that in the described steps A that diatomaceous addition is 10～90% of a steps A total weight of solids.
3. by the described method of claim 1, it is characterized in that among the described step B that the addition of zeolite molecular sieve is 5～70% of a step B total weight of solids, kaolin is 0～90% of step B total weight of solids.
4. by the described method of claim 1, it is characterized in that among the described step B that the addition of binding agent is 5～30% of a step B total weight of solids.
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| CN104211086A (en) * | 2014-09-22 | 2014-12-17 | 湖南理工学院 | ZSM-5 zeolite molecular sieve and preparation method thereof |
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| CN104248993A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
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| CN104248993A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
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| CN104275206B (en) * | 2013-07-12 | 2016-08-10 | 中国石油天然气股份有限公司 | Preparation method of catalyst for improving yield of catalytically cracked gasoline |
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| CN104211086A (en) * | 2014-09-22 | 2014-12-17 | 湖南理工学院 | ZSM-5 zeolite molecular sieve and preparation method thereof |
| CN104649640B (en) * | 2015-01-06 | 2016-02-17 | 长白朝鲜族自治县北疆硅藻土新材料科技有限公司 | Multi-stage porous regulation type diatom ooze |
| CN104649640A (en) * | 2015-01-06 | 2015-05-27 | 长白朝鲜族自治县北疆硅藻土新材料科技有限公司 | Multilevel hole control type diatom ooze |
| CN104888840A (en) * | 2015-01-14 | 2015-09-09 | 任丘市华北石油科林环保有限公司 | Preparation method for high-framework silica-alumina-ratio in-situ crystallization FCC heavy oil transforming auxiliary agent |
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