CN104649296A - H[beta] molecular sieve preparing method capable of increasing silicon-aluminum ratio - Google Patents
H[beta] molecular sieve preparing method capable of increasing silicon-aluminum ratio Download PDFInfo
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Abstract
The invention relates to an H[beta] molecular sieve preparing method capable of increasing the silicon-aluminum ratio. The preparing method comprises following steps: (1) mixing a silicon dioxide source, an aluminum oxide source, a sodium oxide source and water, wherein molar ratios of the raw materials are described as follows: SiO2/Al2O3=5-25, Na2O/SiO2=0.18-0.5 and H2O/SiO2=1-6, stirring the raw materials to generate initial gel and continuously stirring the gel until the gel is turned into dry gel, adding a [beta]-molecular sieve seed crystal, performing hydrothermal crystallization at 100-180 DEG C for 12-130 h, and filtering and washing a reaction product to obtain Na[beta] zeolite; and (2) adding water to the Na[beta] zeolite sample with pulping, adding an ammonium salt and an acid, performing a reaction at 20-110 DEG C for 0.5-24 h, filtering and washing a reaction product, and drying and roasting the reaction product to obtain an H[beta] molecular sieve. Because that the preparation process is free of organic template agents, a high-temperature roasting for removing the organic template agent is not required, so that the preparing method is reduced in cost effectively and is reduced in pollutant discharge. By means of the method in the invention, the high-quality H[beta] molecular sieve being 6-200 in the silicon-aluminum ratio can be synthesized with a low cost. The H[beta] molecular sieve can be used in conversion of hydrocarbons, and especially can be used as an excellent catalyst component in catalytic cracking, hydroisomerization and hydrocracking.
Description
Technical field
The invention belongs to inorganic chemistry, physical chemistry, materials chemistry, catalytic chemistry and field of chemical engineering, be related specifically to the method without organic formwork synthesizing high-silicon aluminum ratio H beta-zeolite molecular sieve.
Background technology
β zeolite is the high silica alumina ratio mesoporous molecular sieve (USP3308069) of a kind of aperture between the faujusite and the ZSM-5 zeolite of mesopore of macropore, and bore dia is about 0.6nm.Be widely used in hydrocracking (as USP3923641, EP94827), hydrofining (as USP4560655), gently aliphatic hydrocarbon are converted in many catalyzed reactions such as aromatic hydrocarbons (as USP3760024), benzene alkylation (as USP4891458), cracking (as USP4423265), isomerization (as USP4471145).
Conventional beta molecular sieve is prepared under the organic formwork existent condition such as TEA+, and silica alumina ratio is 25 ~ 500, there is obviously shortcoming: the price being first organic formwork agent is very high, causes molecular sieve cost too high, affects its widespread use; Secondly usually using the method for high temperature sintering when removing the organic formwork agent in molecular sieve, molecular sieve crystallinity can be caused so obviously to reduce, and produce a large amount of obnoxious flavour contaminate environment.
The people such as Xiao Fengshou successfully synthesize beta-zeolite molecular sieve (CN200810050456.3 under organic-free template condition, 201110224388.X, CN201110154662.0), the shortcoming of the method is, the silica alumina ratio of synthesized beta-molecular sieve product is lower, usual SiO
2/ A1
2o
3be less than 10, molecular sieve applied and is extremely restricted.Although the method avoids the use of organic formwork in addition, reduce production cost, its drawback is silicon source utilization ratio low (25 ~ 35%), and the consumption of water is higher, and (feed intake H
2o/SiO
2=8 ~ 100), cause single-autoclave yield rate very low, restriction production efficiency.
Bibliographical information is had with the method improving silica alumina ratio with acid treatment zeolite, as proposition mineral acid in CN88108552.9 carries out extracting to remove part framework aluminum to β zeolite, in CN96119899.0, the process of proposition silicofluoric acid pumps part framework aluminum, makes molecular sieve silica alumina ratio be greater than 50; In CN200910181073.4, proposition sulfuric acid, nitric acid or hydrochloric acid are to SiO
2/ Al
2o
3mol ratio is that the H beta-molecular sieve after the roasting demoulding of 30 ~ 100: 1 carries out dealuminzation, and acid concentration is 0.05 ~ 0.5mol/L, or with acetic acid, oxalic acid, the third three acid, citric acid, acid concentration is 0.05 ~ 1.0mol/L.Propose a dealumination process in US5310534A, comprise carrying out acidleach containing template zeolite materials, acid used comprises formic acid, trichoroacetic acid(TCA) or trifluoroacetic acid at interior organic acid and hydrochloric acid, nitric acid and sulfuric acid at interior mineral acid.This patent is directly introduced in the synthetic medium of molecular sieve acid, and its deficiency is: because molecular sieve synthesis mother liquid is strong basicity, acid directly introduced, and can consume a large amount of acid, technique is unreasonable.
Summary of the invention
The technical problem to be solved in the present invention is, first overcome conventional beta molecular sieve and synthesize the expensive deficiency of beta-molecular sieve under the organic formwork existent condition such as TEA+, it is low that next overcomes prior art silica alumina ratio, the deficiency that single-autoclave yield rate is low.
The solution that the present invention proposes is:
Improve a preparation method for the H beta-molecular sieve of silica alumina ratio, comprise step below:
(1) silica source, alumina source, sodium hydroxide and water are mixed, stir and generate Primogel; Add beta-molecular sieve crystal seed, at 100 ~ 180 DEG C of temperature, hydrothermal crystallizing 12 ~ 130 hours, is separated and uses deionized water wash, filters, obtains Na beta-molecular sieve; The proportioning raw materials of Primogel is SiO
2/ Al
2o
3=5 ~ 25, Na
2o/SiO
2=0.18 ~ 0.5, H
2o/SiO
2=1 ~ 6; The SiO of beta-molecular sieve crystal seed
2/ Al
2o
3=11 ~ 70, add-on is 0.5 ~ 5% of silica source by quality;
(2) add water the Na beta-molecular sieve that step (1) obtains making beating, adds ammonium salt and acid, reacts 0.5 ~ 24 hour at 20 ~ 120 DEG C of temperature, filters, and with deionized water wash, dry, at 500 ~ 800 DEG C, process 0 ~ 10 hour in 100% steam.
In the present invention, obtain Na beta-molecular sieve process and be preferably:
Alkalimetal oxide source, alumina source are dissolved in water, then add silica source, 20 ~ 60 DEG C are uniformly mixed 5 ~ 10 hours and form alumino silica gel, and continue to be stirred to dry glue; Control the add-on of each reactant, make in alumino silica gel, to possess following molar ratio relation: Na
2o/SiO
2=0.188 ~ 0.376, SiO
2/ Al
2o
3=6 ~ 15, H
2o/SiO
2=1 ~ 6; SiO is added again by the amount of silicon-dioxide source quality 0.5 ~ 5.0%
2/ Al
2o
3the beta-molecular sieve of (mol ratio)=11 ~ 70 is as crystal seed, and crystallization 12 ~ 130 hours under 100 ~ 180 DEG C of conditions, synthesizes beta-molecular sieve; Being cooled to 25 DEG C ~ 80 DEG C after crystallization completes, being separated by solid crystallized product with mother liquor, is that 9 ~ 10,100 ~ 120 DEG C of dryings obtain beta-molecular sieve powder with deionized water wash to pH.
The present invention can be industrial β zeolite (as the industrial β zeolite that Tianjin Nankai university catalyst plant provides) as the beta-molecular sieve of crystal seed, also can be the beta-molecular sieve of other baked or non-roasting, the SiO of crystal seed
2/ A1
2o
3(mol ratio)=11 ~ 70, the amount of the beta-molecular sieve crystal seed added is preferably 0.5 ~ 5% of silica source by mass.Select SiO
2/ A1
2o
3different β zeolites does crystal seed, little on the silica alumina ratio of the finished product, degree of crystallinity impact.
Crystallization temperature of the present invention can be the crystallization temperature of usual synthesis of molecular sieve, and as 130 ~ 180 DEG C of background technology, preferred crystallization temperature is 105 ~ 150 DEG C, and preferred crystallization time is 24 ~ 120 hours.
In the present invention, described alumina source is Universal aluminium source, this area, as being Tai-Ace S 150, aluminum nitrate, sodium aluminate, aluminum isopropylate, can be wherein one or more.
In the present invention, described silica source is general silicon source, this area, as can be silica gel and/or White Carbon black.
Next is step (2), carries out modification to Na beta-molecular sieve, makes Na beta-molecular sieve become H beta-molecular sieve, and improve silica alumina ratio, can adopt current techique, the method for recommendation is:
Add water above-mentioned Na beta-molecular sieve making beating, adds ammonium salt and acid, reacts 0.5 ~ 24 hour at 20 ~ 120 DEG C of temperature, filters, and with deionized water wash, dry, and at 500 ~ 800 DEG C of temperature, process 0.5 ~ 24 hour in 100% steam, optimum is 2 ~ 4 hours.
The condition of recommending is: the solid-to-liquid ratio of reaction system is 5.0 ~ 20.0, and the mass concentration of ammonium salt is 1 ~ 40wt%, and the volumetric molar concentration of acid is 0.05 ~ 1.5mol/L, and system pH is 0.1 ~ 6.Preferably repeat 2 ~ 4 times; Bake out temperature is 40 ~ 200 DEG C.
The H beta-molecular sieve silica alumina ratio applying method of the present invention acquisition can reach 100 or higher, and the H β of the more conventional equal silica alumina ratio prepared under the organic formwork existent condition such as TEA+ of cost is low more than at least 60%.In the present invention, ammonium salt can be the general ammonium salt in this area, as being ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate etc., can be wherein one or more.Acids used can be hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid at interior mineral acid and oxalic acid, acetic acid etc. at interior organic acid, can be wherein one or more, the preferred oxalic acid of acids, hydrochloric acid.The solid-to-liquid ratio of reaction system is preferably 5.0 ~ 10.0, the mass concentration of ammonium salt is preferably 1 ~ 40wt%, and the volumetric molar concentration of acid is preferably 0.05 ~ 1.5mol/L, and system pH is preferably 0.1 ~ 6, the volumetric molar concentration optimum of acid is 0.1 ~ 1.0mol/L, and system pH optimum is 1 ~ 3.Best reaction repeated 2 ~ 4 times; Bake out temperature is 40 ~ 200 DEG C.
The invention has the beneficial effects as follows:
First do not need to add organic formwork agent, avoid and to damage framework of molecular sieve when removing organic formwork agent and to environment; Secondly by optimum synthesis condition, broken traditional method, will feed intake H
2o/SiO
2be reduced to best, be obviously reduced to 1 ~ 6 from 13 ~ 50, thus substantially increase single-autoclave yield rate (bring up to from 2 ~ 10% and reach as high as 30%), improve production efficiency, make the technology without organic formwork synthesis beta-molecular sieve more meet the requirement of suitability for industrialized production.The H β of the equal silica alumina ratio of H β cost more traditional organic formwork agent method synthesis of the 3rd silica alumina ratio 6 ~ 200 adopting post-modification to obtain is cheap.The present invention is except the H that feeds intake
2o/SiO
2=1 ~ 6 reduce, SiO
2/ Al
2o
3=6 ~ 15, Na
2o/SiO
2=0.188 ~ 0.376 all obviously reduces thereupon, and result is that single-autoclave yield rate improves, so cost of the present invention can reduce more, and Here it is superiority place of the present invention.
H β zeolite of the present invention can be used as catalyzer separately or/and sorbent material, also can with binding agent as clay, and aluminum oxide, silicon oxide or silica-alumina etc. make spherical catalyst or extruded catalyst.It equally also can use with another kind of combination of zeolites.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the Na beta-molecular sieve that the embodiment of the present invention 1 is synthesized.
Fig. 2 is the XRD spectra of the Na beta-molecular sieve of the 2-in-1 one-tenth of the embodiment of the present invention.
Fig. 3 is the XRD spectra of the Na beta-molecular sieve that the embodiment of the present invention 3 is synthesized.
Fig. 4 is the XRD spectra of the Na beta-molecular sieve that the embodiment of the present invention 4 is synthesized.
Fig. 5 is the XRD spectra of the Na beta-molecular sieve that the embodiment of the present invention 5 is synthesized.
Fig. 6 is the XRD spectra of the Na beta-molecular sieve that the embodiment of the present invention 6 is synthesized.
Fig. 7 is the XRD spectra of H beta-molecular sieve prepared by the embodiment of the present invention 10.
Fig. 8 is the XRD spectra of Na beta-molecular sieve prepared by comparative example 1.
Embodiment
The following examples will be described further feature of the present invention, but protection scope of the present invention is not by the restriction of these embodiments.
Main Analysis evaluation method in example:
X-ray diffraction: the D/MAX2550 adopting Rigaku company to produce measures, and test condition is: CuK alpha-ray, Ni filtering, pipe pressure 40kV, pipe stream 30mA, sweep velocity is 1 °/min, collects the diffraction spectrogram that 2 θ are 4 ~ 40 °.
In embodiment, said relative crystallinity is the result compared with X-ray diffraction (XRD) the chromatogram characteristic peak of standard specimen beta-molecular sieve with products therefrom beta-molecular sieve, namely with the peak area of the characteristic diffraction peak of product beta-molecular sieve near 21.5 ° and 22.5 ° and be proportional to the characteristic diffraction peak of standard specimen beta-molecular sieve near 21.5 ° and 22.5 ° peak area and, be used as the relative crystallinity of sample with its ratio (per-cent).The high-quality beta-molecular sieve industrial goods that standard specimen adopts Fushun catalyst plant to provide, are decided to be 99% its relative crystallinity.
XRF fluorescent element analyser: carry out chemical composition analysis to sample, adopts ZSX Primus type x-ray fluorescence spectrometry instrument of science.Condition determination: CuK ray, method is EZ full scan.
Raw materials used specification in example
| Medicine, reagent | Specification | Manufacturer |
| Sodium hydroxide | Analytical pure | Beijing chemical reagents corporation |
| White Carbon black | Analytical pure | Shenyang Chemical Co., Ltd. |
| Silicon-dioxide | Technical grade | Qingdao silica gel factory produces |
| Sodium metaaluminate | Analytical pure | Beijing Yili Fine Chemicals Co., Ltd. |
| β crystal seed | Analytical pure | Tianjin Nankai university catalyst plant |
| Tetraethyl ammonium hydroxide | Industrial goods, 25wt% | Hangzhou Greenda Chemical Co., Ltd. |
| Ammonium sulfate | Analytical pure | Beijing chemical reagents corporation |
| Ammonium chloride | Analytical pure | Beijing chemical reagents corporation |
| Oxalic acid | Analytical pure | Beijing chemical reagents corporation |
| Hydrochloric acid | Analytical pure | Beijing chemical reagents corporation |
Embodiment 1 is without synthesis Na beta-molecular sieve efficient under organic formwork condition
Material molar ratio is as follows: 10SiO
2/ 1.00A1
2o
3/ 2.50Na
2o/30H
2o, here H
2o/SiO
2be 3.Concrete building-up process is as follows: 10.75gAlNO
37H
2o and 2.9gNaOH is dissolved in the H of 9.5ml
2in O, after to be dissolved, 10.1g silica gel is joined in above-mentioned solution.After stirring about 5 ~ 10h, formed dry gluey, add 0.5g beta-molecular sieve crystal seed, continue stirring 10 ~ 15 minutes.Afterwards, above-mentioned dry glue is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 150 DEG C of conditions, stirs crystallization 24h.After cooling, filter, 105 DEG C of dryings 12 hours, can obtain product.Obtain through x-ray diffractometer and know, product is the beta-molecular sieve that degree of crystallinity is very high, as Fig. 2.Silicon source utilization ratio 85%, single-autoclave yield rate 24.2%.
XRF records Na
2o is 10.5%, SiO
2/ A1
2o
37.4.
Embodiment 2 is without synthesis Na beta-molecular sieve efficient under organic formwork condition
Material molar ratio is as follows: 10SiO
2/ 1.00A1
2o
3/ 1.88Na
2o/20H
2o, here H
2o/SiO
2be 2.Concrete building-up process is as follows: 10.2g aluminum isopropylate and 2.2gNaOH are dissolved in the H of 6.3ml
2in O, after to be dissolved, 10.1g silica gel is joined in above-mentioned solution.Formed dry gluey, after stirring about 5 ~ 10h, add 0.5g beta-molecular sieve crystal seed, continue stirring 10 ~ 15 minutes.Afterwards, above-mentioned dry glue is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 DEG C of conditions, stirs crystallization 3 days.After cooling, filter, 115 DEG C of dryings 12 hours, can obtain product.Obtain through x-ray diffractometer and know, product is the beta-molecular sieve that degree of crystallinity is very high, as Fig. 4.Silicon source utilization ratio 75%, single-autoclave yield rate 23.8%.XRF records SiO
2/ A1
2o
3be 7.3.
Embodiment 3 is without synthesis Na beta-molecular sieve efficient under organic formwork condition
Material molar ratio is as follows: 5SiO
2/ 1.00A1
2o
3/ 1.88Na
2o/10H
2o, here H
2o/SiO
2be 2.Concrete building-up process is as follows: 4.1gNaAlO
2the H of 3.2ml is dissolved in 2.15gNaOH
2in O, after to be dissolved, 5.1g silica gel is joined in above-mentioned solution.After stirring about 5 ~ 10h, formed dry gluey, add 0.25g beta-molecular sieve crystal seed, continue stirring 10 ~ 15 minutes.Afterwards, above-mentioned dry glue is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 DEG C of conditions, stirs crystallization 2.5 days.After cooling, filter, 110 DEG C of dryings 12 hours, can obtain product.Obtain through x-ray diffractometer and know, product is beta-molecular sieve, as Fig. 5.Silicon source utilization ratio 90%, single-autoclave yield rate 36.6%.XRF records SiO
2/ A1
2o
3be 4.8.
Embodiment 4 is without synthesis Na beta-molecular sieve efficient under organic formwork condition
Material molar ratio is as follows: 8SiO
2/ 1.00A1
2o
3/ 1.83Na
2o/48H
2o, here H
2o/SiO
2be 6.Concrete building-up process is as follows: 4.1gNaAlO
2the H of 15ml is dissolved in 1.3gNaOH
2in O, after to be dissolved, 8.1g silica gel is joined in above-mentioned solution.After stirring about 5 ~ 10h, formed dry gluey, then add 0.3g beta-molecular sieve crystal seed, continue stirring 10 ~ 15 minutes.Afterwards, above-mentioned dry glue is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 130 DEG C of conditions, stirs crystallization 2.5 days.After cooling, filter, 120 DEG C of dryings 12 hours, can obtain product.Obtain through x-ray diffractometer and know, product is the beta-molecular sieve that degree of crystallinity is very high, as Fig. 6.Silicon source utilization ratio 85%, single-autoclave yield rate 25%.XRF records SiO
2/ A1
2o
3be 6.9.
Embodiment 5 prepares H beta-molecular sieve
(1) the Na β zeolite 301g of Example 1 synthesis, adds the making beating of 3L deionized water, adds ammonium chloride 165g, use 1:1 hydrochloric acid, adjust pH to be 3.0, at 60 DEG C of temperature, react 4 hours, filtration washing, drying.Sample step (1) obtained, at 600 DEG C of temperature, processes 2 hours in 100% steam.It is that 90%, XRF records Na that XRD records sample crystallinity (the Na β that relative embodiment 1 is synthesized)
2o is 0.54%, SiO
2/ A1
2o
3be 17.
Embodiment 6 prepares H beta-molecular sieve
(1) the Na β zeolite 310g of the 2-in-1 one-tenth of Example, adds the making beating of 2.8L deionized water, adds ammonium sulfate 300g, 150g oxalic acid, adjust pH to be 1.5, at 80 DEG C of temperature, react 2 hours, filtration washing, drying.(2) sample that step (1) obtains is added the making beating of 2.8L deionized water, add ammonium sulfate 150g, 150g oxalic acid, adjust pH to be 2.5, at 80 DEG C of temperature, react 1 hour, filtration washing, drying.So 2 times repeatedly.(3) sample step (2) obtained, at 500 DEG C of temperature, processes 2 hours in 100% steam.It is that 88%, XRF records Na that XRD records sample crystallinity (the Na β relative to the 2-in-1 one-tenth of embodiment)
2o is 0.05%, SiO
2/ A1
2o
3be 48.
Embodiment 7 prepares H beta-molecular sieve
(1) the Na β zeolite 310g of the 2-in-1 one-tenth of Example, adds the making beating of 2.8L deionized water, adds ammonium sulfate 300g, 150g oxalic acid, adjust pH to be 1.5, at 80 DEG C of temperature, react 2 hours, filtration washing, drying.(2) sample that step (1) obtains is added the making beating of 2.8L deionized water, add ammonium sulfate 150g, 150g oxalic acid, adjust pH to be 1.5, at 90 DEG C of temperature, react 1 hour, filtration washing.(3) wetcake sample step (2) obtained at 600 DEG C of temperature, roasting 2 hours in air.(4) get the sample 100g that step (3) obtains, add the making beating of 900mL deionized water, add ammonium sulfate 80g, 60g oxalic acid, adjust pH to be 1.5, at 90 DEG C of temperature, react 2 hours, filtration washing, drying.It is that 94%, XRF records Na that XRD records sample crystallinity (the Na β relative to the 2-in-1 one-tenth of embodiment)
2o is 0.06%, SiO
2/ A1
2o
3be 51.
Embodiment 8 prepares H beta-molecular sieve
(1) the Na β zeolite 305g of Example 4 synthesis, adds the making beating of 3L deionized water, adds ammonium nitrate 30g, 68g oxalic acid, adjust pH to be 1.0, at 90 DEG C of temperature, react 1 hour, filtration washing, drying.(2) sample that step (1) obtains is added the making beating of 3L deionized water, add ammonium nitrate 30g, 34g oxalic acid, adjust ph to be 1.0 at 80 DEG C of temperature, react 0.5 hour, filtration washing, drying.So repeated multiple times.(3) sample step (2) obtained, at 800 DEG C of temperature, processes 4 hours in 100% steam.It is that 70%, XRF records Na that XRD records sample crystallinity (the Na β that relative embodiment 4 is synthesized)
2o is 0.02%, SiO
2/ A1
2o
3be 106.
Embodiment 9 prepares H beta-molecular sieve
(1) the Na β zeolite 310g of Example 3 synthesis, adds the making beating of 3L deionized water, adds ammonium sulfate 300g, 90g oxalic acid, adjust pH to be 2.5, at 30 DEG C of temperature, react 48 hours, filtration washing, drying.(2) sample step (1) obtained, at 550 DEG C of temperature, processes 4 hours in air.It is 85% that XRD records sample crystallinity (the Na β that relative embodiment 3 is synthesized), as Fig. 7.XRF records Na
2o is 0.41%, SiO
2/ A1
2o
3be 33.
Comparative example 1
With reference to the method for CN201110154662.0, material molar ratio is as follows: 20.08SiO
2/ 1.00A1
2o
3/ 7.56Na
2o/160H
2o, here H
2o/SiO
2be 8.Concrete building-up process is as follows: 0.60gAl
2(SO
4)
3: be dissolved in the H of 5.06ml with 1.06gNaOH
2in O, after to be dissolved, 2.11g silica gel is joined in above-mentioned solution.After stirring about 1 ~ 3h, 0.1gBeta molecular sieve crystal seed is joined in above-mentioned solution, continue stirring at room temperature 10 ~ 15 minutes.Afterwards, above-mentioned gel is incorporated with in the stainless steel cauldron of polytetrafluoroethylkettle kettle lining, under 120 DEG C of conditions, crystallization 5d.After cooling, filter in room temperature, obtain mother liquor separately and product.Product 100 DEG C of dried overnight, can obtain product.Obtain through x-ray diffractometer and know, product is Beta molecular sieve, as Fig. 8.Silicon source utilization ratio 38%, single-autoclave yield rate 7%.XRF records Na
2o is 10.9%, SiO
2/ A1
2o
3be 7.4.
This comparative example is corresponding with embodiment, visible, and difference is that the present invention feeds intake SiO
2/ Al
2o
3=6 ~ 15, H
2o/SiO
2=1 ~ 6, all obviously reduce, Na2O consumption also obviously reduces, and result is that crystallization time of the present invention shortened to 3 ~ 2.5 days by 5 days, and single-autoclave yield rate improves, so cost of the present invention can reduce more.
Claims (10)
1. a preparation method for H beta-molecular sieve, comprises step below: silica source, alumina source, sodium hydroxide and water mix by (1), stirs and generates Primogel and continue to be stirred to dry glue; Add beta-molecular sieve crystal seed, at 100 ~ 180 DEG C of temperature, hydrothermal crystallizing 12 ~ 130 hours, is separated and uses deionized water wash, filters, obtains Na beta-molecular sieve; The proportioning raw materials of Primogel is SiO
2/ Al
2o
3=5 ~ 25, Na
2o/SiO
2=0.18 ~ 0.5, H
2o/SiO
2=1 ~ 6; The SiO of beta-molecular sieve crystal seed
2/ Al
2o
3=11 ~ 70, add-on is 0.5 ~ 5% of silica source by quality; (2) add water the Na beta-molecular sieve that step (1) obtains making beating, adds ammonium salt and acid, reacts 0.5 ~ 24 hour at 20 ~ 120 DEG C of temperature, to filter, and with deionized water wash, 80 ~ 120 DEG C of dryings 2 ~ 6 hours, at 500 ~ 800 DEG C of temperature, in 100% steam, process 0 ~ 10 hour.
2. preparation method according to claim 1, is characterized in that alumina source is one or more in Tai-Ace S 150, aluminum nitrate, sodium aluminate, aluminum isopropylate.
3. preparation method according to claim 1, is characterized in that described silica source is White Carbon black and/or silica gel.
4. preparation method according to claim 1, is characterized in that sodium hydroxide, alumina source being dissolved in water in step 1, then adds silica source, is uniformly mixed 5 ~ 10 hours and forms Primogel.
5. preparation method according to claim 4, is characterized in that in step 1, and the proportioning raw materials of Primogel is Na
2o/SiO
2=0.188 ~ 0.376, SiO
2/ Al
2o
3=6 ~ 15, H
2o/SiO
2=3 ~ 6.
6. preparation method according to claim 1, is characterized in that the beta-molecular sieve crystal seed added in step 1, its SiO
2/ Al
2o
3mol ratio is 20 ~ 60.
7. preparation method according to claim 1, is characterized in that ammonium salt used in step 2 is one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate; Acid is mineral acid or organic acid.
8. preparation method according to claim 7, it is characterized in that mineral acid be in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid one or more; Organic acid is oxalic acid or acetic acid.
9. preparation method according to claim 1, is characterized in that the solid-to-liquid ratio of reaction system in step 2 is 5.0 ~ 20.0, and the mass concentration of ammonium salt is 1 ~ 40wt%, and the concentration of acid is 0.05 ~ 1.5mol/L, and system pH is 0.1 ~ 6.
10. the preparation method according to claims 1, is characterized in that, in step (2), the volumetric molar concentration of acid is 0.05 ~ 1.0mol/L, and system pH is 1 ~ 3.
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| CN107028218A (en) * | 2017-05-25 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of method for preparing geranyl acetone slow-release material |
| CN111825102A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Dry glue conversion synthesis method of high-silicon Y molecular sieve |
| CN112919492A (en) * | 2021-02-23 | 2021-06-08 | 浙江浙能技术研究院有限公司 | Preparation method of hollow-structure hierarchical pore Beta molecular sieve |
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| CN107028218A (en) * | 2017-05-25 | 2017-08-11 | 云南中烟工业有限责任公司 | A kind of method for preparing geranyl acetone slow-release material |
| CN107028218B (en) * | 2017-05-25 | 2019-10-11 | 云南中烟工业有限责任公司 | A method of preparing geranyl acetone slow-release material |
| CN111825102A (en) * | 2019-04-18 | 2020-10-27 | 中国科学院大连化学物理研究所 | Dry glue conversion synthesis method of high-silicon Y molecular sieve |
| CN112919492A (en) * | 2021-02-23 | 2021-06-08 | 浙江浙能技术研究院有限公司 | Preparation method of hollow-structure hierarchical pore Beta molecular sieve |
| CN112919492B (en) * | 2021-02-23 | 2022-03-22 | 浙江浙能技术研究院有限公司 | Preparation method of hollow-structure hierarchical pore Beta molecular sieve |
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