CN1324762A - Synthesis of small-crystallite beta zeolite - Google Patents
Synthesis of small-crystallite beta zeoliteInfo
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- CN1324762A CN1324762A CN 00107486 CN00107486A CN1324762A CN 1324762 A CN1324762 A CN 1324762A CN 00107486 CN00107486 CN 00107486 CN 00107486 A CN00107486 A CN 00107486A CN 1324762 A CN1324762 A CN 1324762A
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Abstract
A synthesis method of small crystal grain beta-zeolite includes the following steps: dissolving aluminium source, tetraethyl ammonium cation source and alkali source in water to prepare a working solution, using silica-gel granules with 20-300 meshes granularity as silicone source, mixing the said silicone source and the above-mentioned working solution to obtain a reactive mixture, then adopting the hydrothermal crystallization process according to conventional condition and recovering the invented product. It is characterized by that in the described reactive mixture an organic additive is contained, and said organic additive is polyol type non-ionic surfactant or polyether-like lubricating oil or their mixture, the dosage of the said additive is 0.05-8% of weight of SiO2 being in reactive mixture.
Description
The invention relates to the synthetic method of crystal silicon-aluminate zeolite, specifically, is the synthetic method about beta zeolite in small crystal grain.
The β zeolite is (USP3,308,069) that U.S. Mobile company synthesized with classical hydrothermal crystallization method first in 1967.This zeolite has unique three-dimensional (or two dimension) pore passage structure, have very high hydrocracking, hysomer, and the catalytic activity of heavy oil cracking, behind modification or some metal constituent element of load, can be used for refining of petroleum and petrochemical process such as hydrocracking, hysomer, hydrofining and Hydrodewaxing, diesel oil pour point depression, cracking hydrocarbon, alkylation, olefin hydration.According to the disclosed method of this patent, the β zeolite is such synthetic: will contain Na
2O, Al
2O
3, TEAOH (being tetraethyl ammonium hydroxide), SiO
2Make slurries with the mixture of water, 75～200 ℃ of crystallizations are 3～60 days in autoclave.The molar ratio of this reaction system is: SiO
2/ Al
2O
3=10～200, Na
2O/TEAOH=0.0～0.1, TEAOH/SiO
2=0.1～1.0, H
2O/TEAOH=20～75.Because the silicon source of adopting in this method is a silicon sol, water content is big, thereby causes template tetraethyl ammonium hydroxide large usage quantity.Therefore and organic formwork agent costs an arm and a leg, and produces β zeolite cost height with this method, is unfavorable for that it commercially produces, simultaneously again owing to entire reaction solution bulky, crystallization time is long, thereby brought the low problem of production efficiency.Do not mention the granularity of the beta-molecular sieve that synthesizes in this patent, but according to said method its granularity of synthetic molecular sieve is 300-500nm.The molecular sieve particle size reduction can improve catalyst efficiency, improves catalytic performance, is particularly suited for macromolecular catalyzed reaction.
Relevant small-particle beta-molecular sieve synthetic report has: WO93/08125 carries out the oil bath heating in flask, synthetic beta-molecular sieve, and product granularity is 70nm, but the ammonium-silicon ratio of reaction system is up to ((TEA)
2/ SiO
2) 0.279, crystallization time is 25 days.(Surface Science andCatalysis, Vol.105 p341) under the alkali free metal ion condition, synthesized beta-molecular sieve in crystallization 8-30 days to M.A.Camblor in the 60ml still, product granularity is 10-100nm, and molar ratio is SiO
2/ Al
2O
3=14-400, (TEA)
2O/SiO
2=0.26-0.33, H
2O/SiO
2=15.These methods of producing the small-particle beta-molecular sieve all are difficult to the small-particle molecular sieve of large-scale commercial production homogeneous grain diameter.
About the existing more report of the synthetic method of conventional β zeolite.Exxon Corporation in 1986 disclose a kind of new synthetic β zeolite technology (EP187,522A2), i.e. " single solution is synthetic " technology.Its concrete grammar is: with SiO
2, Al
2O
3And Na
2Mix with tetraethyl ammonium hydroxide solution again after the solid material of the precursor of O mixes,, carry out crystallization under the condition that has or do not have the β zeolite seed crystal to exist at 75～150 ℃.The molar ratio of this system is SiO
2/ Al
2O
3=10～200, Na
2O/TEA
2O=0.01～0.1, TEA
2O/SiO
2=0.01～0.1, H
2O/TEA
2O=25～150.Because having only tetraethyl ammonium hydroxide in the reaction system is that form with solution adds, avoided too much water to introduce system, thereby reduced the consumption of water and tetraethyl ammonium hydroxide in the building-up process, production cost and production efficiency all might be improved, but adopt this method can not obtain the small-particle β zeolite of crystal grain less than 100 nanometers.
Mobile company disclosed a kind of improved synthetic β zeolite technology (US4 again in 1989,847,055), used a kind of silicon source special, that have certain particle size in this technology, this silicon source adds precipitation agent under certain condition by soluble silicon source solution and makes.In synthetic system of zeolite, then used tetraethylammonium bromide to be template, and the solid content of synthetic system material is at least 15%, under the situation that crystal seed exists, carries out crystallization.Yet this technology is the problem of unresolved industrial-scale production also also, and this is owing to be easy to generate the large usage quantity of mordenite and ZSM-5 stray crystal, tetraethylammonium bromide in the preparation process complexity in this silicon source, crystallization system, has only the TEA of working as
2O/SiO
2＞0.14 is TEAOH/SiO
2＞0.28 o'clock could reduce the growing amount of stray crystal.Simultaneously, adopt this method can not obtain the small-particle β zeolite of crystal grain less than 100 nanometers.
In addition, other a series of patent (EP164 of Mobile company application, 939, US4,923,690, US5,164,169 etc.) be applicable to the β zeolite of synthesizing high-silicon aluminum ratio, but the consumption of its tetraethylammonium cation is more high than synthesizing low silicon aluminum ratio β zeolite, for example, desire synthesizing Si-Al than greater than 100 β zeolite the time, the mol ratio of tetraethylammonium cation and silicon-dioxide need are more than 0.5 in the synthetic system, top condition then will reach more than 0.7, and this just makes that the cost of high silica alumina ratio β zeolite is more high than low silica-alumina ratio beta zeolite.Adopt this method can not obtain the small-particle β zeolite of crystal grain equally less than 100 nanometers.
In order to solve the problem that exists in the aforesaid method, CN1108213A and CN1108214A have proposed a kind of new method for synthesis of beta-zeolite, it is wetting crystallization method (or claiming surperficial method of enrichment), this method adopts solid silicone as the silicon source, in the building-up process silicon source joined in the working solution of being made up of aluminium source, sodium source, tetraethylammonium cation, water and mix, make silica gel particle surface wetting, and, promptly get the β zeolite in 140～170 ℃ of following crystallizations 10～60 hours by this working solution.This method is only used a spot of water, thereby is greatly reduced the consumption of water and tetraethylammonium cation owing to adopted solid silicone to do the silicon source, has reduced production cost, has improved single-autoclave yield rate, has accelerated crystallization rate simultaneously.But adopt its product grains of this method synthetic β zeolite size＞100nm.
For further reducing the synthetic cost of β zeolite, CN1154341A has disclosed a kind of fractional crystallization method, this method is on the basis of the wetting crystallization method of CN1108213A, the crystallization condition is further optimized segmentation, thereby effectively utilize template, reduce its consumption, the reaction system mol ratio is in this method: SiO
2/ Al
2O
3=20～600, TEAOH/SiO
2=0.02～0.20, Na
2O/SiO
2=0.01～0.1, H
2O/SiO
2=2.0～10.
In plant-scale actual production, even in order to make reaction system, reaction must be carried out under whipped state, and because the needs that stir, needed water content is higher in the reaction mass, has reduced the concentration of template, has influenced its service efficiency.In general, under the situation that the existence of stirring is arranged, the H of reaction system
2O/SiO
2Can not be lower than 6.5, particularly in the high silica alumina ratio β zeolite synthesis, H
2O/SiO
2Require highlyer,,, just must solve the stirring problem under the low wash water reaction system with the cost of further reduction β zeolite in order further to reduce the consumption of tetraethylammonium cation in the β zeolite synthesis process.
USP5,164, a kind of method of synthetic β zeolite is disclosed in 169, the characteristics of this method are to add a kind of organic sequestering agent to improve the mobile water yield that feeds intake that also reduces of synthetic colloidal in synthesis reaction mixture, use precipitation silica gel to be the silicon source simultaneously, wherein used organic sequestering agent is organic compounds containing nitrogen (seeing the 5th hurdle in this patent specification), is mainly alkanolamine; This its grain size range of synthetic β of method institute zeolite is 0.1-3.0 micron (claims), all is 0.3-1.0 micron (300-1000 nanometer) among the embodiment.
The objective of the invention is on the prior art basis of above-mentioned synthetic β zeolite, a kind of synthetic method of beta zeolite in small crystal grain is provided, this method can improve the nucleation rate of crystallization system when reducing production costs, enhancing productivity, make the zeolite that obtains have less grain fineness number.
According to method provided by the invention, beta zeolite in small crystal grain is such synthetic: aluminium source, tetraethylammonium cation (are used TEA
+Expression) source and alkali source (are used Na
2O represents) working solution that is made into soluble in water, with granularity is that 20～300 purpose silica gel particles are the silicon source, and this silicon source is mixed with said working solution, makes silica gel particle surface wetting by this working solution, obtain a kind of reaction mixture, the mole proportioning of each raw material is SiO in this reaction mixture
2/ Al
2O
3=20～600, Na
2O/SiO
2=0.01～0.10, TEA
+/ SiO
2=0.01～0.20, H
2O/SiO
2=2～10, then with said reaction mixture according to the normal condition hydrothermal crystallizing and reclaim product; It is characterized in that also containing a kind of organic additive in the said reaction mixture, said organic additive is: contain-(CH in (1) molecular composition
2CH
2O)
n-polyol-based non-ionic surfactant, wherein n is 15-30, its HL β value is 8-15, molecular weight is 800-1500, as tween-80, tween-85, tween-60, tween-65 etc.; (2) contain O (CH in the molecular composition
2-CH
2-O)
x-(CH
2-CH (CH
3))-O-]
n-, molecular weight is the polyalkylene ether class lubricating oil of 800-1500, n=15-30 in the formula, and the value of x is so that polyoxyethylene groups shared weight ratio in said polyalkylene ether is 15-40% is standard, for example viscosity grade is the lubricating oil of 40-70 such as vacuum pump oil, polyethers wet goods; Perhaps (3) their mixture; The consumption of said additive is SiO in the said reaction mixture
20.05～8% of weight.
Used aluminium source is selected from one or more in alkali metal aluminate (as sodium metaaluminate), hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325, the pseudo-boehmite in the method provided by the invention, alkali metal aluminate preferably wherein, most preferred is sodium metaaluminate; Alkali source is sodium hydroxide or alkali metal aluminate or their mixture, and sodium ion wherein can be replaced by other basic metal or alkaline-earth metal ions that does not influence reaction; Said Na
2O represents the basicity of reaction mixture; Used tetraethylammonium cation source is selected from one or more in tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, the tetraethyl ammonium iodide, wherein preferably tetraethyl ammonium hydroxide or tetraethylammonium bromide; Used silica gel be comprise gross porosity, mesopore or Kiselgel A any aperture, granularity is 20～300 purpose silica gel.
Said hydrothermal crystallizing carries out according to condition of the prior art in the method provided by the invention, and the present invention has no particular limits it; Can keep 5～120 hours in constant temperature under 120～200 ℃ and the autogenous pressure condition; Perhaps earlier under 80～138 ℃ and autogenous pressure condition constant temperature kept 5～72 hours, constant temperature kept 5～72 hours under 142～200 ℃ and autogenous pressure condition again.
The zeolite that makes with method provided by the invention has X-ray diffraction (XRD) spectrogram of typical β zeolite, and the d value (nanometer) of its main spectral line is as follows:
1.14±0.02
0.74±0.02
0.67±0.02
0.425±0.01
0.397±0.01
0.30±0.01
0.22±0.01
β zeolite with method preparation provided by the invention can also can use with forming Hydrogen through roasting again after the ammonium salt solution exchange through the roasting removed template method after pickling transformation is a Hydrogen.Can be by ion-exchange, dipping or other method with various metals or its compound, introduce wherein as element such as basic metal, alkaline-earth metal, rare earth element Pt, Pd, Re, Sn, Ni, W, Co or its compound, make it to become the zeolite that contains various different metals; Also can introduce the compound of elements such as different compounds such as P, Ga, Ti, B, make it to become zeolite with special purpose; Can also make it to have higher silica alumina ratio by the part aluminium that methods such as pickling, chemical extracting are sloughed on the zeolite framework.Can be with present method synthetic β zeolite and modified version thereof as catalyzer, catalyst aid and the sorbent material etc. of multiple refining of petroleum and petrochemical process.
Key of the present invention is, in crystallization process, space repulsion with certain hydrophilic additive has reduced the high surface energy of synthesis material, template is improved in the silica gel particle surface speed of " nibbling ", thereby improved nucleus nucleation rate or rate of crystal growth, made the molecular sieve particle size reduction, compared with surperficial method of enrichment simultaneously, crystallization time further shortens, and production efficiency is improved.In addition, method provided by the invention is owing to added organic additive in becoming the glue reaction mixture, make before the crystallization become colloidal viscosity to reduce significantly, improved the colloidal whipping performance, thereby institute's water requirement and template (tetraethylammonium cation) consumption is further reduced, and can be under the condition of low tetraethylammonium cation consumption the β zeolite of synthesizing high-silicon aluminum ratio.
Fig. 1 is X-ray diffraction (XRD) figure of the embodiment of the invention 1 resulting β zeolite.
Fig. 2 is the stereoscan photograph of the embodiment of the invention 1 resulting β zeolite.
Fig. 3 is the stereoscan photograph of Comparative Examples 1 resulting β zeolite.
Fig. 4 is the stereoscan photograph of Comparative Examples 3 resulting β zeolites.
The following examples will the present invention will be further described, and wherein all percentage compositions all are benchmark with weight.
The relative crystallinity of β zeolite product is measured with X-ray diffraction method, and granular size is measured with scanning electronic microscope.
Additive used among each embodiment is respectively:
Additive 1: vacuum pump oil (commercial goods, trade mark is called SY1634-70, and seven factories of Dalian Petrochemical Industry Company produce, molecular weight 800-1000, polyoxyethylene groups shared weight ratio in said polyalkylene ether is 25%)
Additive 2: polyether oil 50HB-260 (commercial goods, U.S. combinating carbide company, molecular weight 1000-1200, polyoxyethylene groups shared weight ratio in said polyalkylene ether is 35%)
Additive 3:Tween-80 (Farco company commodity, molecular weight 1200-1400, HLB=15)
Additive 4:Tween-60 (Farco company commodity, molecular weight 800-1000, HLB=14.9)
Additive 5:SY1634-70 (70 weight %)+Tween-85 (30 weight %) (wherein Tween-85 is Farco company commodity, molecular weight 1200-1400, HLB=11)
Additive 6:SY1634-70 (50 weight %)+Tween-85 (50 weight %) (wherein Tween-85 is Farco company commodity, molecular weight 1200-1400, HLB=11)
Additive 7:SY1634-70 (50 weight %)+Tween-65 (50 weight %) (wherein Tween-65 is Farco company commodity, molecular weight 800-1000, HLB=10.5)
Comparative Examples 1
This Comparative Examples is according to USP3, and the disclosed method of embodiment in 308,069 does not use crystal seed to prepare the β zeolite.
With 2 gram sodium aluminate (Shanghai reagent two factory's product, wherein Al
2O
3Content 45%, Na
2O content 55%) be dissolved in 30 milliliters of tetraethyl ammonium hydroxide solution (Beijing Chemical Plant's product, concentration 2.958N), (Changhong chemical plant, Beijing produces, wherein SiO with 81 gram silicon sol again
2Content is 24.7%) to mix, high degree of agitation is made slurries.The mol ratio of each component is SiO in these slurries
2/ Al
2O
3=37.8, Na
2O/SiO
2=0.053, TEAOH/SiO
2=0.266, H
2O/SiO
2=13.1; Above-mentioned slurries 150 ℃ of following crystallization in sealed reactor are taken out cooling after three days, after filtration, wash with water, 110 ℃ be drying to obtain the β zeolite sample, the globule size of this sample is the 500nm (see figure 3).
Comparative Examples 2
Add additive 1 on Comparative Examples 1 described basis, raw materials used composition (mol ratio) is as described in the Comparative Examples 1, and wherein the consumption of additive 1 is additive 1/SiO
2=0.05 weight %, result show that the degree of crystallinity of gained β zeolite descends, and produce the ZSM-5 stray crystal, and grain size does not diminish.The explanation of this Comparative Examples adds organic additive of the present invention and can not reach purpose of the present invention in the synthetic system of liquid starting material.
Comparative Examples 3
This Comparative Examples is according to the synthetic β zeolite of the surperficial method of enrichment of CN1108231A.
Pseudo-boehmite (is contained Al
2O
356.5 heavy %, the Zhou village catalyst plant), sodium hydroxide (chemical pure, Beijing Chemical Plant), tetraethyl ammonium hydroxide (2.633N, emerging good fortune fine chemistry industry institute product is gone in in a big way in Beijing) add in the deionized water, heating for dissolving, stir, make working solution, with silochrom (80～120 orders, igloss 3.7%, Haiyang Chemical Plant, Qingdao) mix with above-mentioned working solution, make the silica gel surface wetting by working solution, the mol ratio of each component is SiO
2/ Al
2O
3=30, Na
2O/SiO
2=0.075, TEAOH/SiO
2=0.09, H
2O/SiO
2=6.5; With gained mixture 120 ℃ of crystallizations 24 hours in autoclave, be warming up to 140 ℃ of reactions 48 hours again, isolate solid product after the reaction, wash with water, 110 ℃ are drying to obtain the β zeolite.This product granularity is greater than the 100nm (see figure 4), with the standard substance (promptly set its degree of crystallinity be 100%) of this β zeolite as the mensuration relative crystallinity.
Embodiment 1-8
These embodiment add the synthetic β zeolite of additive, raw materials used composition (mol ratio), additive amount (additive/SiO on the basis of Comparative Examples 3 described surperficial method of enrichment
2, weight %), crystallization temperature (℃), crystallization time (hour), and product relative crystallinity (%), granularity (nm) all list in the table 1.
Table 1 is the result show, under condition of the present invention, adding additive does not influence the molecular sieve crystallization, and can obtain the beta-molecular sieve of granularity less than 100 nanometers, and crystallization time further shortens, and can carry out commercial scale production.Table 1
| Comparative Examples 1 | Comparative Examples 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Raw material constitutive molar ratio SiO 2/Al 2O 3?Na 2O/SiO 2?TEAOH/SiO 2?H 2O/SiO 2 | ?37.8 ?0.053 ?0.266 ?13.1 | ?30 ?0.075 ?0.09 ?6.5 | ?30 ?0.075 ?0.09 ?6.0 | ?30 ?0.065 ?0.10 ?6.5 | ?30 ?0.075 ?0.08 ?6.5 |
| Additive | ?— | ?— | Additive 1 | Additive 2 | Additive 3 |
| Additive/SiO 2(heavy %) | ?— | ?— | ?0.5 | ?0.8 | ?1.5 |
| Second section crystallization time of second section crystallization temperature of first section crystallization time of first section crystallization temperature | 150 ℃ 72 hours | 120 ℃ 24 hours 148 ℃ 48 hours | 120 ℃ 24 hours 148 ℃ 48 hours | 120 ℃ 20 hours 148 ℃ 40 hours | 150 ℃ 72 hours |
| Product relative crystallinity (%) | ?100 | ?100 | ?80.2 | ?89.6 | ?88.5 |
| Granularity (nm) | ?500 | ?＞100 | ?50-60 | ?70-80 | ?70-80 |
Continuous table 1
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Raw material constitutive molar ratio SiO 2/Al 2O 3Na 2O/SiO 2TEAOH/SiO 2H 2O/SiO 2 | ?30 ?0.075 ?0.09 ?6.5 | ?30 ?0.068 ?0.09 ?5.5 | ?30 ?0.068 ?0.09 ?5.5 | ?30 ?0.075 ?0.09 ?6.5 | ?100 ?0.07 ?0.12 ?6.5 |
| Additive | Additive 4 | Additive 5 | Additive 6 | Additive 7 | Additive 1 |
| Additive/SiO 2(heavy %) | ?1.5 | ?2.0 | ?2.0 | ?2.5 | ?0.5 |
| Second section crystallization time of second section crystallization temperature of first section crystallization time of first section crystallization temperature | 120 ℃ 18 hours 148 ℃ 42 hours | 118 ℃ 22 hours 145 ℃ 38 hours | 118 ℃ 20 hours 145 ℃ 40 hours | 120 ℃ 20 hours 148 ℃ 40 hours | 120 ℃ 24 hours 148 ℃ 48 hours |
| Product relative crystallinity (%) | ?86.7 | ?78.5 | ?75.6 | ?80.2 | ?89.6 |
| Granularity (nm) | ?70-80 | ?50-60 | ?50-60 | ?50-60 | ?80-90 |
Embodiment 9
The catalytic activity of present embodiment explanation variable grain degree molecular sieve.
With embodiment 1-8 and 3 synthetic molecular sieves of Comparative Examples at 60 ℃, the NH of 1.0N
4Exchange is 4 times in the Cl aqueous solution, each 2 hours, 110 ℃ of dryings 2 hours, in the 100ml of water bath with thermostatic control and magnetic agitation there-necked flask, carry out the alkylated reaction of benzene and laurylene-1 after 550 ℃ of roastings activation in 3 hours, react after 30 minutes and analyze on the GC8000 chromatographic instrument that CE company produces with syringe sampling, reaction conditions is: 80 ℃ of temperature of reaction, normal pressure, benzene/alkene=5: 1 (volume ratio), alkene/agent are than=3.3: 1 (ml/g).Be calculated as follows the transformation efficiency (X%) of laurylene-1:
X%=(weight of laurylene in the weight/charging of reaction consumes laurylene) * 100%
The specific activity of table 2 variable grain degree molecular sieve
| Molecular sieve | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The transformation efficiency of laurylene-1 (%) | 32.96 | ?29.46 | ?30.78 | ?28.12 |
| Molecular sieve | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 3 |
| The transformation efficiency of laurylene-1 (%) | 31.95 | ?32.78 | ?33.06 | ?15.71 |
Embodiment 10
The stability of present embodiment explanation variable grain degree molecular sieve.
With embodiment 1 and 3 synthetic molecular sieves of Comparative Examples at 60 ℃, the NH of 1.0N
4Exchange is 4 times in the Cl aqueous solution, each exchange 2 hours, 110 ℃ of dryings 2 hours, in the 100ml of water bath with thermostatic control and magnetic agitation there-necked flask, carry out the alkylated reaction of benzene and laurylene-1 after 550 ℃ of roastings activation in 3 hours, react after 30 minutes, left standstill 10 minutes, to molecular sieve and liquid layering, take out liquid, behind benzene washing molecular sieve, add fresh material and continue reaction.Sample analysis and reaction conditions are as described in the embodiment 9.The result shows, improves by the beta-molecular sieve of the present invention's preparation is active, and stability improves.
Table 3 granularity is to the stability of catalyzer
| Activity stability % | ||||||
| Reaction times | 1 | ?2 | ?3 | ?4 | ?5 | ?6 |
| Embodiment 1 molecular sieve activity | 32.96 | ?20.87 | ?18.94 | ?16.56 | ?13.57 | ?9.87 |
| Comparative Examples 3 molecular sieve activity | 15.71 | ?8.74 | ?7.56 | ?5.47 | ?3.70 | |
Claims (9)
1, a kind of synthetic method of β zeolite, this method is with aluminium source, tetraethylammonium cation source and the alkali source working solution that is made into soluble in water, with granularity is that 20～300 purpose silica gel particles are the silicon source, this silicon source is mixed with said working solution, make silica gel particle surface wetting by this working solution, obtain a kind of reaction mixture, the mole proportioning of each raw material is SiO in this reaction mixture
2/ Al
2O
3=20～600, Na
2O/SiO
2=0.01～0.10, TEA
+/ SiO
2=0.01～0.20, H
2O/SiO
2=2～10, then with said reaction mixture according to the normal condition hydrothermal crystallizing and reclaim product; It is characterized in that also containing a kind of organic additive in the said reaction mixture, said organic additive is: contain-(CH in (1) molecular composition
2CH
2O)
n-polyol-based non-ionic surfactant, wherein n is 15-30, its HLB value is 8-15, molecular weight is 800-1500; (2) contain O-[(CH in the molecular composition
2-CH
2-O)
x-(CH
2-CH (CH
3))-O-]
n-, molecular weight is the polyalkylene ether class lubricating oil of 800-1500, n=15-30 in the formula, and the value of x is so that polyoxyethylene groups shared weight ratio in said polyalkylene ether is 15-40% is standard; Perhaps (3) their mixture; The consumption of said additive is SiO in the said reaction mixture
20.05～8% of weight.
2, according to the process of claim 1 wherein that said aluminium source is selected from one or more in alkali metal aluminate, hydrated aluminum oxide, aluminium hydroxide, Wickenol CPS 325, the pseudo-boehmite; Said alkali source is sodium hydroxide or alkali metal aluminate or their mixture; Said tetraethylammonium cation source is to be selected from tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, the tetraethyl ammonium iodide one or more.
3, according to the method for claim 2, wherein said aluminium source is alkali metal aluminate or hydrated aluminum oxide; Said tetraethylammonium cation source is tetraethyl ammonium hydroxide or tetraethylammonium bromide.
4, according to the method for claim 3, wherein said aluminium source is a sodium metaaluminate; Said tetraethylammonium cation source is a tetraethyl ammonium hydroxide.
5, according to the process of claim 1 wherein that said hydrothermal crystallizing is that constant temperature kept 5～120 hours under 120～200 ℃ and autogenous pressure condition.
6, according to the process of claim 1 wherein that said hydrothermal crystallizing is that constant temperature kept 5～72 hours under 80～138 ℃ and autogenous pressure condition, constant temperature kept 5～72 hours under 142～200 ℃ and autogenous pressure condition again.
7, contain-(CH in the said molecular composition according to the process of claim 1 wherein
2CH
2O)
n-polyol-based non-ionic surfactant be tween-80, tween-85, tween-60 and/or tween-65.
8, contain O (CH according to the process of claim 1 wherein in the said molecular composition
2-CH
2-O)
x-(CH
2-CH (CH
3))-O-]
n-, molecular weight is that the polyalkylene ether class lubricating oil of 800-1500 is that viscosity grade is the lubricating oil of 40-70.
9, according to the process of claim 1 wherein that the consumption of said additive is SiO in the said reaction mixture
20.1～5% of weight.
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| CN1325375C (en) * | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | Beta zeolite granule possessing multiple grade pore passage and its preparation method |
| CN103073018A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing beta molecular sieve with non-alkali-metal ion system |
| CN109701614A (en) * | 2018-12-24 | 2019-05-03 | 大连理工大学 | A kind of preparation method of hud typed Beta molecular sieve catalyst |
| CN110668459A (en) * | 2019-10-25 | 2020-01-10 | 吉林大学 | Nano Beta molecular sieve with wider silicon-aluminum ratio range and preparation method thereof |
| CN113891762A (en) * | 2019-07-03 | 2022-01-04 | 三井金属矿业株式会社 | Beta-zeolite and catalyst containing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923690A (en) * | 1984-06-11 | 1990-05-08 | Mobil Oil Corporation | Method for producing highly siliceous zeolites |
| US5164169A (en) * | 1991-06-14 | 1992-11-17 | Mobil Oil Corporation | Zeolite Beta |
| CN1035668C (en) * | 1994-03-11 | 1997-08-20 | 中国石油化工总公司 | Method No.1 for synthesizing beta zealite |
| CN1048697C (en) * | 1996-01-11 | 2000-01-26 | 中国石油化工总公司 | Method for synthesis of beta-zeolite |
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2000
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325375C (en) * | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | Beta zeolite granule possessing multiple grade pore passage and its preparation method |
| CN103073018A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing beta molecular sieve with non-alkali-metal ion system |
| CN103073018B (en) * | 2011-10-26 | 2016-07-20 | 中国石油化工股份有限公司 | A kind of method of alkali free metal ion system synthesis Beta molecular sieve |
| CN109701614A (en) * | 2018-12-24 | 2019-05-03 | 大连理工大学 | A kind of preparation method of hud typed Beta molecular sieve catalyst |
| CN113891762A (en) * | 2019-07-03 | 2022-01-04 | 三井金属矿业株式会社 | Beta-zeolite and catalyst containing same |
| CN110668459A (en) * | 2019-10-25 | 2020-01-10 | 吉林大学 | Nano Beta molecular sieve with wider silicon-aluminum ratio range and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1100004C (en) | 2003-01-29 |
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