CN1074750C - Method for prepn. of super macroporous molecular sieve - Google Patents
Method for prepn. of super macroporous molecular sieve Download PDFInfo
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- CN1074750C CN1074750C CN98101644A CN98101644A CN1074750C CN 1074750 C CN1074750 C CN 1074750C CN 98101644 A CN98101644 A CN 98101644A CN 98101644 A CN98101644 A CN 98101644A CN 1074750 C CN1074750 C CN 1074750C
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- molecular sieve
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Abstract
The present invention relates to a method for preparing a super macroporous molecular sieve. The present invention is characterized in that the method comprises that (1) according to a method in the prior art, a synthesized super macroporous molecular sieve raw material colloid is prepared; (2) an alkaline mixture with a molecular sieve or an octahedral zeolite guiding agent is used as a crosslinking agent which is evenly mixed with raw material colloid mentioned in the step (1); (3) a pH value of a mixture obtained by the step (2) is adjusted from 9.5 to 12.0, and the mixture is processed with hydrothermal crystallization. By adopting a method provided by the present invention, a super macroporous molecular sieve with good thermal stability can be synthesized at a low template agent dosage (Q/SiO2 is from 0.1 to 0.2). An obtained molecular sieve can keep an X-ray diffraction (XRD) characteristic peak for directly roasting for 4 hours without the protection of an air current at a temperature of 800 DEG C.
Description
Present method relates to a kind of preparation method of super macroporous molecular sieve.
Super macroporous molecular sieve is the novel molecular sieve (J.S.Beck etc. that a class is succeeded in developing in 1992 by the Mobil oil company, J.Ame.Chem.Soc., 14 (1992), the 10834th page), that has reported at present has types such as MCM-41 and MCM-48, its aperture can be in 15-100 scope modulation, broken through the limitation that conventional molecular sieve bore diameter can not surpass 12 .Because this molecular sieve analog has the one-dimensional tunnel structure of big homogeneous, have broad prospects as the catalyzer of macromolecular reaction.But the pore wall thickness of this super macroporous molecular sieve generally only is (about two layers of silicon monolayers thick) about 5 , and hole wall very easily penetrates because of local hydrolysis or heat effect, causes its thermostability and hydro-thermal thermostability very poor.Thereby restricted the industrial application of super macroporous molecular sieve.
The Mobil oil company is at its patent USP5, announced a kind of post-modification method of super macroporous molecular sieve in 126,829, the crystallization reservation degree in the time of can effectively improving molecular sieve and take off amine.This method adopts the alkoxy compound of a kind of silicon, aluminium, titanium as the skeleton propping agent super macroporous molecular sieve to be modified to improve its structural stability.
People such as Nicole (J.Chem.Soc., Chem.Commun., 1994 (8), 967-968) by control synthesis condition such as OH
-/ Si, H
2O/Si, factor such as aging makes the super macroporous molecular sieve pore wall thickness that synthesizes adjustable in 4～16 scopes.The super macroporous molecular sieve wall thickness increases, and also can effectively improve its thermostability.
People such as R.Ryoo (J.Chem.Soc., Chem.Commun., 1995 (2), 155-156) add chemical equilibrium that acid comes the disturbance reaction system to reach the thermostability that improves super macroporous molecular sieve and the purpose of hydrothermal stability by one or many in crystallization process.It is thick that its ultimate principle also can ascribe the raising hole wall to.
A kind of method of synthesis of titanium silicon super macroporous molecular sieve has been proposed among the CN1137023A, this method uses a kind of quaternary ammonium salt or alkali that contains a chain alkyl and a benzyl to be organic formwork agent, can improve the structure thermal stability of institute's synthetic Ti-Si ultra macroporous molecular sieve.
In order to improve the industrial applicibility of super macroporous molecular sieve, except that improving its structural stability, also should further reduce its manufacturing cost, and the key that reduces cost is to reduce the consumption of organic formwork agent.
The purpose of this invention is to provide a kind of method for preparing super macroporous molecular sieve, make under lower template consumption, can synthesize super macroporous molecular sieve with higher structural stability.
The method for preparing super macroporous molecular sieve provided by the present invention comprises:
(1). prepare a kind of raw material colloid of synthetizing ultramacropore molecular sieve by the method for prior art, this raw material colloidal mole is formed and can is:
RNaO
2: SiO
2: xM
2O
n: yQ: zH
2O is r=0.1-0.5 wherein; X=0-0.1; Y=0.1-0.2; Z=20-100; M is a kind of in the elements such as Al, B, Ti, Cr, V, wherein preferably Al and Ti; Q is an organic formwork agent;
(2). a kind of alkaline mixt or a kind of faujusite directed agents that contains molecular sieve mixed as linking agent and the said raw material colloid of step (1); The said solid content that contains the alkaline mixt of molecular sieve is the heavy % of 5-50, OH
-/ Si mol ratio is 0.1-2.0;
(3). with pH regulator to 9.5～12.0 of (2) gained mixture, hydrothermal crystallizing according to a conventional method then, perhaps earlier will (1) gained raw material colloid hydrothermal crystallizing, adding (2) said linking agent in crystallization process then according to a conventional method, regulate after pH to 9.5～12.0, continue crystallization.
The said raw material colloid of step in the method provided by the invention (1) prepares according to prior art, and its proportioning and metal M and template Q can select by prior art, and the present invention has no particular limits it, but the present invention can adopt lower template consumption.According to prior art, said template Q contains a quaternary ammonium salt or the alkali with alkyl of 10～16 carbon atoms, or contains one and have the alkyl of 10～16 carbon atoms and the quaternary ammonium salt or the alkali of a benzyl.
The said alkaline mixt that contains molecular sieve of step in the method provided by the invention (2) is made up of molecular sieve and a kind of alkaline matter that is selected from sodium hydroxide, water glass or alkaline silica sol; Said molecular sieve is faujusite or ZSM-5 zeolite, wherein rare earth Y type molecular sieve preferably.
The said faujusite directed agents of step in the method provided by the invention (2) is an existing faujusite directed agents in the prior art, and its mole composition is generally (11～18) Na
2OAl
2O
3(10～17) SiO
2(100～350) H
2O, this directed agents can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, for example according to USP3,639,099, USP3,671,191, USP4,166,099, the method for preparing directed agents that is proposed among CN85102733A and the CN1081425A prepares.
SiO in the linking agent that adds in the step in the method provided by the invention (2)
2Content accounts for totally middle mutually SiO
2The heavy % of the 2-30 of content wherein is preferably the heavy % of 5-20.
The condition of the said crystallization of step in the method provided by the invention (3) is the conventional crystallization condition of preparation super macroporous molecular sieve, generally is 80～140 ℃ of crystallization 10～60 hours.
Adopt method provided by the invention can be under lower template consumption (Q/SiO
2=0.1-0.2) synthesize the super macroporous molecular sieve of good heat stability; the gained molecular sieve can still can keep its X-ray diffraction (XRD) characteristic peak in 4 hours without the air-flow protection direct roasting under up to 800 ℃ temperature, illustrate that the inventive method can improve the structural stability of the super macroporous molecular sieve that synthesizes effectively.
Fig. 1 is the XRD figure of Comparative Examples 1 gained sample, (a) the unfired sample that synthesizes of expression, and (b) expression is through the sample of 550 ℃ of air atmosphere direct roasting after 4 hours.
Fig. 2 is the XRD figure of embodiment 3 gained samples, (a) the unfired sample that synthesizes of expression, and (b) expression is through the sample of 550 ℃ of air atmosphere direct roasting after 4 hours, and (c) expression is through the sample of 800 ℃ of air atmosphere direct roasting after 4 hours.
The following examples will the present invention is described further.In following embodiment and Comparative Examples, with the strongest diffraction peak ratio of peak (I of X-ray diffraction (100) crystal face after the molecular sieve roasting and before the roasting
c/ I) characterize the structural stability of the molecular sieve that synthesizes, wherein relative crystallinity is 100% benchmark with the unfired super macroporous molecular sieve of Comparative Examples 1 gained.
Embodiment 1
The present embodiment explanation prepares linking agent with Rare Earth Y (REY) molecular sieve and water glass.
10 gram water are joined 10 gram REY molecular sieves, and (Chang Ling oil-refining chemical factory catalyst plant is produced, and burning residual solid content is 78.3 heavy %, RE
2O
3Content is 18 heavy %, Al
2O
3Content is 12 heavy %) in, fully be ground to particle diameter less than 10 microns, (Qilu Petrochemical company Zhou village catalyst plant is produced, d to wherein adding 20 gram water glass
4 20=1.26g/ml, SiO
2Content 265g/L, Na
2O content 86.4g/L), stirred 30 minutes, the stainless steel sealed reactor of packing into was then placed 2 hours down in 110 ℃, and taking-up is cooled to room temperature and promptly gets linking agent, wherein SiO
2Content is 23.7 heavy %.
Embodiment 2
The raw material colloidal preparation of the said synthetizing ultramacropore molecular sieve of present embodiment explanation the present invention.
With 11.2 gram Al
2(SO
4)
318H
2(Henan Nan Zhao chemical plant produces O, analytical pure) is dissolved in the 60 gram water, under agitation condition, this alum liquor is added dropwise in the 150 gram water glass then, stir after 30 minutes, under agitation in the gained mixture, add 60 gram dodecylbenzyl alkyl dimethyl ammonium chloride (popular name 1227Cl, the production of Gaochun, Nanjing water quality stabilizer factory) concentration is the aqueous solution of 45 heavy %, promptly gets the raw material colloid of the said synthetizing ultramacropore molecular sieve of the present invention after stirring.This raw material colloidal mole proportioning is: 0.18Na
2O: 0.16 1227Cl: SiO
2: 0.033 Al
2O
3: 22H
2O
Comparative Examples 1
The explanation of this Comparative Examples does not add the effect of linking agent synthetizing ultramacropore molecular sieve of the present invention according to a conventional method.
Get gained raw material colloidal 1/3rd among the embodiment 2, pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 11.2, the stainless steel sealed reactor of packing into after stirring, in 98 ℃ of following crystallization 20 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom is indicated as the MCM-41 structure shown in Fig. 1 (a), defining its relative crystallinity is 100%.
Gets the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams and place muffle furnace, but the XRD analysis of sample shows the structure avalanche of this molecular sieve after the roasting that its XRD analysis the results are shown in Figure 1 (b) in 550 ℃ of direct roasting 4 hours.
Embodiment 3
Get gained raw material colloidal 1/3rd among the embodiment 2, under agitation add the linking agent 10 gram (SiO in the linking agent of gained among the embodiment 1
2Account for totally middle mutually SiO
27 heavy %), pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 11.2, the stainless steel sealed reactor of packing into after stirring, in 98 ℃ of following crystallization 20 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom is indicated as the MCM-41 structure shown in Fig. 2 (a), its relative crystallinity is 107%.
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams and place muffle furnace in 550 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, and its relative crystallinity is 131%, I
c/ I=1.22, its XRD analysis the results are shown in Figure 2 (b).
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams again and place muffle furnace in 800 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, and its relative crystallinity is 55%, I
c/ I=0.51, its XRD analysis the results are shown in Figure 2 (c).
Embodiment 4
With gained raw material colloidal 1/3rd among the embodiment 2, pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 11.2, the stainless steel sealed reactor of packing into after stirring, in 98 ℃ of following crystallization 2 hours, taking-up is cooled to 60 ℃, adds the linking agent 10 gram (SiO in the linking agent among the embodiment 1 under vigorous stirring
2Account for totally middle mutually SiO
27 heavy %), pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 11.2 again, stir the back and continued crystallization 18 hours down in 98 ℃, product is taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom and Fig. 2 (a) are similar, be indicated as the MCM-41 structure, its relative crystallinity is 101%.
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams and place muffle furnace in 550 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, and its relative crystallinity is 135%, I
c/ I=1.33.
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams again and place muffle furnace in 680 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, and its relative crystallinity is 77%, I
c/ I=0.76.
Embodiment 5
The present embodiment explanation is as the preparation of the faujusite directed agents of linking agent of the present invention.
(Chang Ling oil-refining chemical factory catalyst plant is produced, Na with the high sodium metaaluminate of 13ml with 20ml water glass (with embodiment 1)
2O content is 280.6g/L, Al
2O
3Content is 45g/L, d
4 20=1.375) thorough mixing is even, places promptly to get the y-type zeolite directed agents in 24 hours under room temperature, it is directly used as linking agent of the present invention, wherein SiO
2Content is 11.7 heavy %.
Embodiment 6
After being dissolved in 5 gram NaOH in the 10 gram water, under agitation condition, it being dropped to 80 gram alkaline silica sols and (produce SiO in Beijing 93
2Content 26 heavy %, Na
2O content 0.3 heavy %) in, after stirring 30 minutes, join in the above-mentioned reaction mixture after being dissolved in 16 gram palmityl trimethyl ammonium chlorides (code name is CTMACl, the commerical prod that the Tokyo changes into) in the 30 gram water, promptly get the raw material colloid of synthetizing ultramacropore molecular sieve after stirring.This raw material colloidal mole proportioning is: 0.19 Na
2O: 0.14CTMACl: SiO
2: 16H
2O
Comparative Examples 2
The explanation of this Comparative Examples does not add the effect of linking agent synthetizing ultramacropore molecular sieve of the present invention according to a conventional method.
To implement gained raw material colloidal 1/2nd in 6, pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 12.0, the stainless steel sealed reactor of packing into after stirring, in 98 ℃ of following crystallization 20 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom and Fig. 1 (a) are similar, are indicated as the MCM-41 structure, and its relative crystallinity is 120%.
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams and place muffle furnace, but the XRD analysis of sample shows the structure avalanche of molecular sieve, I after the roasting in 550 ℃ of direct roasting 4 hours
c/ I=0.
Get gained raw material colloidal 1/2nd among the embodiment 6, under agitation add linking agent 20 grams of gained among the embodiment 5, (SiO in the linking agent
2Account for totally middle mutually SiO
218 heavy %), pH with the sulfuric acid conditioned reaction mixture system of 25 heavy % is 12.0, the stainless steel sealed reactor of packing into after stirring, in 98 ℃ of following crystallization 20 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom and Fig. 2 (a) are similar, are indicated as the MCM-41 structure, and its relative crystallinity is 118%.
Getting the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams places muffle furnace in 550 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, its relative crystallinity is 165%, and the XRD crystalline phase figure of products obtained therefrom and Fig. 2 (b) are similar, its I
c/ I=1.39.
Embodiment 8
The present embodiment explanation prepares linking agent of the present invention with the ZSM-5 zeolite.
10 gram water are joined 10 gram HZSM-5, and (American I NTERCAT company produces, and burning residual solid content is 85.0 heavy %, SiO
2/ Al
2O
3Mol ratio=1000) in, fully be ground to particle diameter less than 10 microns, adding 10 gram concentration is the NaOH aqueous solution of 20 heavy %, stirred 30 minutes, the stainless steel sealed reactor of packing into was placed 16 hours down in 80 ℃, and taking-up is cooled to room temperature and promptly gets linking agent of the present invention, wherein SiO
2Content is 28 heavy %.
Embodiment 9
25 gram TPAOH (code name TPAOH will be joined under the 25 gram tetraethyl orthosilicates stirrings, the commerical prod that the Tokyo changes into) concentration is in the aqueous solution of 22.2 heavy %, fully hydrolysis under room temperature, get the settled solution of homogeneous, (Great Wall, Beijing chemical reagent factory produces with 1 gram tetrabutyl titanate, chemical pure) is dissolved in 5 grams and is added drop-wise in the above-mentioned settled solution behind the anhydrous isopropyl alcohols, in the process that drips the titanium source, should keep the reaction mixture clarification always.The gained mixture after 2 hours, restrains 1227Cls (with embodiment 3), the raw material colloid that stir promptly get synthetizing ultramacropore molecular sieve to wherein adding 13.2 in 70 ℃ of reactions.This raw material colloidal mole proportioning is: 0.35TPAOH: 0.15 1227Cl: SiO
2: 0.025TiO
2: 20H
2O
Comparative Examples 3
Get gained raw material colloidal 1/2nd among the embodiment 9, the pH that regulates this mixture system with the sulfuric acid of 25 heavy % is 10.5, the stainless steel sealed reactor of packing into after stirring, in 120 ℃ of following crystallization 48 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom and Fig. 1 (a) are similar, are indicated as the MCM-41 structure, and its relative crystallinity is 160%.
Get the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams and place muffle furnace, but the XRD analysis of sample shows the structure avalanche of molecular sieve, I after the roasting in 430 ℃ of direct roasting 4 hours
c/ I=0.
Embodiment 10
Get gained raw material colloidal 1/2nd among the embodiment 9, under agitation add the linking agent 8 gram (SiO in the linking agent of gained among the embodiment 8
2Account for totally middle mutually SiO
224 heavy %), the pH that regulates the gained mixture system with the sulfuric acid of 25 heavy % is 10.5, the stainless steel sealed reactor of packing into after stirring, in 120 ℃ of following crystallization 48 hours, product was taken out in the cooling back, after filtration, after washing and the drying, the XRD crystalline phase figure of products obtained therefrom and Fig. 2 (a) are similar, are indicated as the MCM-41 structure, and its relative crystallinity is 150%.
Getting the above-mentioned synthetic super macroporous molecular sieve sample of 2.0 grams places muffle furnace in 550 ℃ of direct roasting 4 hours, the XRD analysis of sample shows that molecular sieve keeps the MCM-41 structure after the roasting, its relative crystallinity is 178%, and the XRD crystalline phase figure of products obtained therefrom and Fig. 2 (b) are similar, its I
c/ I=1.18.
Claims (7)
1. one kind prepares the method that pore diameter range is the super macroporous molecular sieve of 1.5 to 10 nanometers, it is characterized in that this method comprises:
(1). prepare a kind of raw material colloid of synthetizing ultramacropore molecular sieve by the method for prior art, this raw material colloidal mole consists of:
RNaO
2: SiO
2: xM
2O
n: yQ: zH
2O is r=0.1-0.5 wherein; X=0-0.1; Y=0.1-0.2; Z=20-100; M is Al, B, Ti, Cr or V; Q is an organic formwork agent;
(2). a kind of alkaline mixt or a kind of faujusite directed agents that contains molecular sieve mixed as linking agent and the said raw material colloid of step (1); The said solid content that contains the alkaline mixt of molecular sieve is the heavy % of 5-50, OH
-/ Si mol ratio is 0.1-2.0; The mole of said faujusite directed agents consists of (11～18) Na
2OAl
2O
3(10～17) SiO
2(100～350) H
2O;
(3). with pH regulator to 9.5～12.0 of (2) gained mixture, hydrothermal crystallizing according to a conventional method then.
2. according to the process of claim 1 wherein that M is Al or Ti in the said raw material colloid of step (1); Said template Q contains a quaternary ammonium salt or the alkali with alkyl of 10～16 carbon atoms, or contains one and have the alkyl of 10～16 carbon atoms and the quaternary ammonium salt or the alkali of a benzyl.
3. according to the process of claim 1 wherein that the said alkaline mixt that contains molecular sieve of step (2) is made up of molecular sieve and a kind of alkaline matter that is selected from sodium hydroxide, water glass or alkaline silica sol; Said molecular sieve is faujusite or ZSM-5 zeolite.
4. according to the process of claim 1 wherein that said molecular sieve is a rare earth Y type molecular sieve.
5. according to the SiO that the process of claim 1 wherein in the linking agent that adds in the step (2)
2Content accounts for totally middle mutually SiO
2The heavy % of the 2-30 of content.
6. according to the SiO that the process of claim 1 wherein in the linking agent that adds in the step (2)
2Content accounts for totally middle mutually SiO
2The heavy % of the 5-20 of content.
7. according to the process of claim 1 wherein that the condition of the said crystallization of step (3) is 80～140 ℃ of crystallization 10～60 hours.
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| CN108238611B (en) * | 2016-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Method for manufacturing molecular sieve, product thereof and application of product |
| CN109160521B (en) * | 2018-09-10 | 2021-11-19 | 太原理工大学 | Molecular sieve and preparation method thereof, catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156829A (en) * | 1990-01-25 | 1992-10-20 | Mobil Oil Corporation | Method for stabilizing synthetic mesoporous crystalline material |
| CN1110252A (en) * | 1994-04-11 | 1995-10-18 | 中国科学院大连化学物理研究所 | Method for synthetizing ultramacropore molecular sieve |
| CN1137023A (en) * | 1995-05-30 | 1996-12-04 | 中国石油化工总公司 | Synthesis of Ti-Si ultra macroporous molecular sieve |
| CN1147800A (en) * | 1994-05-10 | 1997-04-16 | 国际壳牌研究有限公司 | Process for preparing a large pore molecular sieve |
-
1998
- 1998-04-24 CN CN98101644A patent/CN1074750C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156829A (en) * | 1990-01-25 | 1992-10-20 | Mobil Oil Corporation | Method for stabilizing synthetic mesoporous crystalline material |
| CN1110252A (en) * | 1994-04-11 | 1995-10-18 | 中国科学院大连化学物理研究所 | Method for synthetizing ultramacropore molecular sieve |
| CN1147800A (en) * | 1994-05-10 | 1997-04-16 | 国际壳牌研究有限公司 | Process for preparing a large pore molecular sieve |
| CN1137023A (en) * | 1995-05-30 | 1996-12-04 | 中国石油化工总公司 | Synthesis of Ti-Si ultra macroporous molecular sieve |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROCHEMIC Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; RESEARCH INST. OF PETROLEUM PROCESSING, SINOPEC |
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Granted publication date: 20011114 |