CN1308238C - Double microporous zeolite molecular sieves and preparing method thereof - Google Patents
Double microporous zeolite molecular sieves and preparing method thereof Download PDFInfo
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- CN1308238C CN1308238C CNB2004100123332A CN200410012333A CN1308238C CN 1308238 C CN1308238 C CN 1308238C CN B2004100123332 A CNB2004100123332 A CN B2004100123332A CN 200410012333 A CN200410012333 A CN 200410012333A CN 1308238 C CN1308238 C CN 1308238C
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Abstract
The present invention relates to a double micropore zeolite molecular sieve and a preparation method thereof, particularly to a preparation method of a compound molecular sieve, which belongs to the field of fine chemical industry. The preparation method is characterized in that firstly, primarily synthesizing sodium silicate, silicasol, sodium metaaluminate, distilled water, sodium hydroxide and concentrated sulphuric acid used as raw materials in a certain proportion with an ordered synthesis method into Y type zeolite, the Y type zeolite is mixed with a bromination amine tetraethyl solution dissolved with ammonia water, and finally a certain amount of silicasol is added and fully stirred for uniformity; after being crystallized for four to seven days at the temperature of 130 DEG C to 140 DEG C, the mixture is washed, dried and roasted to remove a template agent, and a compound zeolite molecular sieve with a Y/beta double micropore structure is obtained. The double micropore molecular sieve prepared with the method reduces the synthetic cost of a beta molecular sieve, and acidity, hydrothermal stability, and the like are all enhanced. The catalytic performance can also be improved, and double micropore zeolite molecular sieve has potential application prospect in the aspects of fine chemical industry, petrochemical industry, etc.
Description
One, technical field
Double-micropore zeolites molecular sieve of the present invention and preparation method are about the preparation method of a kind of inorganic hole catalytic material, belong to field of fine chemical, more particularly, are the preparation methods about the two micropore composite zeolite molecular sieves of a kind of Y/ β.
Two, technical background
Y-type zeolite is connected mutually along three crystalline axis direction by twelve-ring by octahedral zeolite cage and forms, and is a kind of good catalyzer, and not only cracking activity height, and selectivity is good.Utilizing REY to substitute the amorphous silicon aluminium microballoon rises gasoline output as catalyzer significantly.The production of USY zeolite has been satisfied and is carried out white gasoline in the world and keep high-octane requirement.Therefore the invention of y-type zeolite has epoch making significance in the catalytic cracking field.
The β zeolite is synthetic first in 1967 by Mobil company, owing to fail to solve its structure determination problem for a long time, the ZSM series zeolite synthesizes and successful Application in addition, therefore fail to cause enough attention of people, disclosed its distinctive Three Dimensions Structure until 1988, the β zeolite causes people's interest heavily again, it has good heat and hydrothermal stability, acidity and the acid acceptance and the hydrophobicity of appropriateness, and be unique macropore supersiliceous zeolite with intersection twelve-ring channel system, its catalytic applications shows the characteristics that hydrocarbon reaction is difficult for coking and long service life, at hydrocarbons hydrogenation cracking, hydroisomerization, alkane aromatization, aspect such as alkylation and transalkylation reaction shows excellent catalytic performance, is crucial catalytic material.H β zeolite is the catalyzer that a kind of good alternative Amberlyst-15 prepares MTBE.In the gas phase system, the activity that not only makes the H beta-zeolite catalyst has improved three times, and the while has also effectively reduced the loss of active ingredient, suppressed SO42-to the corrosion of equipment with to pollution (the F.Collingnon and G.Poncelet of environment, Stud.Surf.Sci.Catal., 135 (2001)) environment friendly that, has shown H β zeolite.In addition, H β zeolite shows very high activity in the reaction of dimethylbenzene isopropylation generation dimethyl cumene, selectivity and stability (C.R Patra, S.Kartikeyan and R.Kumar, Stud.Surf.Sci.Catal., 135 (2001)), the wherein active 80-90% that reaches theoretical value, selectivity reaches 90-99%.Particularly people such as Davis has synthesized chirality β zeolite (M.E.Davis, Chem.Mater., 4 (1992) 756.) by adding structure chirality directed agents, and this is unique zeolite molecular sieve with chiral structure of finding at present.Find that by the optical activity experiment institute's synthetic β zeolite can make 5% R, R-phenylbenzene glycol, this just shows that this zeolite has great potential using value.
Above-mentioned y-type zeolite and the β zeolite of showing all has important purposes at petrochemical industry.If can successfully prepare the matrix material of y-type zeolite and β zeolite, organically combine the characteristics of the two, will great application prospect be arranged in petrochemical complex and field of fine chemical.This is because prepared matrix material not only has the performance of y-type zeolite, also has simultaneously the performance of β zeolite, thereby polystep reaction is carried out simultaneously in a reactor, not only can reduce cost greatly, and because the existence of double-pore structure, acidity, hydrothermal stability and to water absorption can mediation, can improve catalytic performance.
Three, summary of the invention
Double-micropore zeolites molecular sieve of the present invention and preparation method's purpose is the advantage that organically combines y-type zeolite and β zeolite, and two micropore composite zeolite molecular sieves of a kind of Y/ of having β and preparation method are provided.The two micro porous molecular sieves that make all increase at aspects such as acidity, heat and hydrothermal stabilities, will the potential application prospect be arranged at aspects such as fine chemistry industry, petrochemical compleies.
The preparation method of a kind of double-micropore zeolites molecular sieve of the present invention is characterized in that described method step is in the following order carried out by the method for the synthetic Y/ β double-micropore zeolites molecular sieve of two step crystallization:
I. use water glass, sodium metaaluminate, the vitriol oil, water, sodium hydroxide to be raw material, in molar ratio (2-4) Na
2O: (3-8) SiO
2: Al
2O
3: (220-280) H
2The system proportioning of O, and add the directed agents of 3-4% (volume) amount evenly is loaded on each mixing of materials in the stainless steel cauldron behind 80-90 ℃ of crystallization 20-30h, tentatively synthesizes Y zeolite, and the mole proportioning of each material is in the used directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O;
II. the tetraethyl-amine bromide is dissolved in the distilled water, and adds ammoniacal liquor, mix;
III. the y-type zeolite that I is tentatively synthesized mixes with II solution after leaching supernatant liquid, and continues to stir;
IV. in III, add silicon sol, be mixed into white jelly after, finally be (1.5-3.0) Na in molar ratio
2O: (10-30) SiO
2: Al
2O
3: (1.0-5.0) (TEA)
2O: (200-360) H
2The system proportioning of O was loaded in the stainless steel cauldron in 130-140 ℃ of crystallization 4-7 days, took out after scouring to neutrality and dried, obtained sample;
V. the sample after will drying obtains the finished product in 550 ℃ of roasting 4-5h.
The double-micropore zeolites molecular sieve of above-mentioned preparation method's preparation.
Four, description of drawings
The XRD diffractogram of Fig. 1 Y/ β double-micropore zeolites sieve sample
Five, embodiment
Embodiment 1
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 5 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.Spectrogram as shown in Figure 1.
Embodiment 2
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 6 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.
Embodiment 3
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 7 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain the mixture of y-type zeolite and sodalite through XRD analysis.
Embodiment 4
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 1.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite:
Then with 30ml distilled water, 12gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 42ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 3 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain having only the sample of y-type zeolite molecular sieve through XRD analysis.
Embodiment 5
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 1.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 12gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 42ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 4 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.
Embodiment 6
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 10.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 18gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, took out in 6 days in 140 ℃ of following crystallization, wash solution and be the oven dry of neutral back, again with sample in 550 ℃ of roasting 5h, obtain being mixed with the Y/ β double-micropore zeolites sieve sample of stray crystal through XRD analysis.
Embodiment 7
First with 280ml distilled water, the 5ml vitriol oil, 100ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 37.5ml sodium aluminate solution ([Al
2O
3]=2.56mol/L, [OH]=9.98mol/L), (its constitutive molar ratio is the 12ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 500ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 25h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 100ml distilled water, 45gTEABr (tetraethyl-amine bromide), 15mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 70ml silicon sol ([SiO
2]=6.05mol/L), adding divides in the 500ml stainless steel cauldron of packing into after being mixed into even white thing successively, takes out in 5 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain β+P type zeolite molecular sieve sample through XRD analysis.
Embodiment 8
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 18gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 8 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain having only the zeolite molecular sieve sample of beta structure through XRD analysis.
Claims (2)
1, a kind of preparation method of double-micropore zeolites molecular sieve is characterized in that described method step is in the following order carried out by the method for the synthetic Y/ β double-micropore zeolites molecular sieve of two step crystallization:
I. use water glass, sodium metaaluminate, the vitriol oil, water, sodium hydroxide to be raw material, in molar ratio (2-4) Na
2O: (3-8) SiO
2: Al
2O
3: (220-280) H
2The system proportioning of O, and add the directed agents of 3-4% (volume) amount evenly is loaded on each mixing of materials in the stainless steel cauldron behind 80-90 ℃ of crystallization 20-30h, tentatively synthesizes Y zeolite, and the mole proportioning of each material is in the used directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O;
II. the tetraethyl-amine bromide is dissolved in the distilled water, and adds ammoniacal liquor, mix;
III. the y-type zeolite that I is tentatively synthesized mixes with II solution after leaching supernatant liquid, and continues to stir;
IV. in III, add silicon sol, be mixed into white jelly after, finally be (1.5-3.0) Na in molar ratio
2O: (10-30) SiO
2: Al
2O
3: (1.0-5.0) (TEA)
2O: (200-360) H
2The system proportioning of O was loaded in the stainless steel cauldron in 130-140 ℃ of crystallization 4-7 days, took out after scouring to neutrality and dried, obtained sample;
V. the sample after will drying obtains the finished product in 550 ℃ of roasting 4-5h.
2, the double-micropore zeolites molecular sieve of a kind of preparation method of claim 1 preparation.
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| CN1308238C true CN1308238C (en) | 2007-04-04 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8562941B2 (en) * | 2005-12-20 | 2013-10-22 | Exxonmobil Research And Engineering Company | Perturbed synthesis of materials |
| CN101343561B (en) * | 2007-07-09 | 2012-07-18 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparing process |
| CN101343560B (en) * | 2007-07-09 | 2011-12-21 | 中国石油化工股份有限公司 | Process for preparing hydrocracking catalyst of high activity |
| CN101343559B (en) * | 2007-07-09 | 2011-12-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation thereof |
| CN101376505B (en) * | 2007-08-27 | 2010-09-15 | 中国石油化工股份有限公司 | Preparation of composite double microporous material |
| CN101723395B (en) * | 2008-10-29 | 2011-04-20 | 中国石油化工股份有限公司 | Method for preparing double-micropore composite molecular sieve |
| CN101585546B (en) * | 2009-06-19 | 2011-05-18 | 北京工业大学 | Composite zeolite molecular sieve preparing method containing Y and Beta zeolite structures |
| CN102553637B (en) * | 2010-12-17 | 2014-11-19 | 中国石油天然气股份有限公司 | Medium oil type hydrocracking catalyst, preparation and application thereof |
| CN103058215B (en) * | 2011-10-24 | 2014-05-21 | 中国石油化工股份有限公司 | Synthesis method of beta/Y composite molecular sieve |
| CN103058216A (en) * | 2012-11-05 | 2013-04-24 | 新疆大学 | Method for preparing mesoporous molecular sieve having crystal microporous wall |
| CN104591219B (en) * | 2013-11-04 | 2017-09-22 | 中国石油化工股份有限公司 | A kind of Beta Y compound molecular sieves and its synthetic method |
| CN103818919A (en) * | 2013-12-08 | 2014-05-28 | 北京工业大学 | Synthetic method for preparing Beta zeolite |
| CN105384180B (en) * | 2014-09-05 | 2017-08-08 | 北京安耐吉能源工程技术有限公司 | YB molecular sieves and its preparation method and application and diesel oil hydrogenation modification catalyst carrier and its application |
| CN106587093B (en) * | 2015-10-15 | 2018-09-14 | 中国石油化工股份有限公司 | The preparation method of Y-Beta composite molecular screens |
| CN106669807B (en) * | 2015-11-09 | 2019-09-10 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst improving hydrocracking tail oil viscosity index (VI) |
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| US5695736A (en) * | 1993-12-23 | 1997-12-09 | Arco Chemical Technology, L.P. | Tiatanium containing molecular sieve having a zelite beta structure |
| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN1397493A (en) * | 2002-06-03 | 2003-02-19 | 刘希尧 | Diphase symbiotic molecular sieve and its synthesizing process |
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2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5695736A (en) * | 1993-12-23 | 1997-12-09 | Arco Chemical Technology, L.P. | Tiatanium containing molecular sieve having a zelite beta structure |
| CN1354134A (en) * | 2001-10-19 | 2002-06-19 | 中国石油化工股份有限公司 | Method for synthesizing small-grain Y-type molecular sieve |
| CN1397493A (en) * | 2002-06-03 | 2003-02-19 | 刘希尧 | Diphase symbiotic molecular sieve and its synthesizing process |
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