CN1296913A - Process for preparing molecular sieve (MCM-22) with special crystal structure - Google Patents
Process for preparing molecular sieve (MCM-22) with special crystal structure Download PDFInfo
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Abstract
A process for preparing the molecular sieve (MCM-22) with special crystal structure includes proportional mixing OH(-), Al2O3, SiO2, organic template agent (R) and H2O in mole ratio of (0.1-0.6):(0.01-0.1):1:(0.1-0.6):(5-100) to obtain colloid, hydrothermal crystallizing at 160-200 deg.C for 1-16 hr, cooling to obtain guide colloid, adding Si, Al and alkali sources and water, mixing uniformly, and hydrothermal crystallizing at 130-155 deg.C for 8-180 hr. The product can be synthesized in static crystallizing condition with low consumption of organic template agent.
Description
Zeolite molecular sieve has been widely used in fields such as refining of petroleum, fine chemistry industry and fractionation by adsorption as effective solid acid catalyst.The outstanding advantage of zeolite molecular sieve is can modulation acidity, can provide the ducts of different sizes and hole to play simultaneously and select the shape effect.Thereby the molecular sieve of different pore sizes has the different shape effects of selecting.As in catalytic cracking just with the compound catalyzer of making of Y type (twelve-ring) and ZSM-5 (ten-ring) molecular sieve to satisfy the requirement of the distribution of transformation efficiency and product, quality simultaneously.Therefore, just reported some after the nineties and had the molecular sieve of ten-ring and twelve-ring simultaneously, as MCM-22, PSH-3, SSZ-25, SSZ-33 and CIT-1 etc.MCM-22 equimolecular sieve particular structure is indicating that it will be widely used at the petroleum chemistry catalytic field.
Bayer AG company has developed the molecular sieve (USP4 of a kind of PSH-3 of being referred to as, 439,409), this molecular sieve has the duct of not connected ten-ring and twelve-ring simultaneously, its synthetic method is to be the silicon source with water glass, with the hexamethylene imine is template, synthetic according to general hydrothermal synthesis method; People proved the stray crystal that contains other molecular sieve such as ZSM-5 or ZSM-12 with this method synthetic PSH-3 molecular sieve afterwards.The reason that stray crystal occurs may be because the Na ion concentration too high (is raw material with water glass) in the system.
Mobil company is in the MCM-22 molecular sieve (USP4 of nineteen ninety report, 954,325) also have not connected ten-ring and twelve-ring pore canal system, the difference of itself and PSH-3 just is not contain stray crystal, thereby there is not the peak (USP4 of stray crystal in its X-ray diffractogram (XRD), embodiment 21-23 in 954,325).At USP4, adopt conventional hydrothermal crystallization method in 954,325, be raw material with spray-dired precipitated silica, sodium metaaluminate and sodium hydroxide, with the hexamethylene imine the synthetic MCM-22 molecular sieve of template.Comprised static and dynamic crystallization method in the specification sheets of this patent, but all adopted dynamic crystallization in the example, and example synthesizes middle template agent big (N/Si=0.35～0.50); In fact, the applicant studies show that, the synthesis condition of MCM-22 molecular sieve needs strict control, at USP4,954, if adopt static crystallization under 325 conditions that adopted, then product is certain to produce stray crystal, and if under the lower situation of template agent (R/SiO
2Can not synthesize desirable product (product is amorphous) when＜0.3) adopting static crystallization.
The SSZ-25 molecular sieve (USP4,826,667) of Chevron company exploitation also is a kind of molecular sieve identical with the MCM-22 molecular sieve structure, and its difference is to adopt when it is synthetic the diamantane quaternary ammonium hydroxide as template.
Corma etc. also report if adopt static crystallization, change the brilliant ferrierite FER that generates easily.And the synthesis condition of MCM-22 molecular sieve needs strict control, if control is bad, can generate ZSM-5 or ZSM-12 stray crystal (Corma A, Zeolites, 15,1995, P2-8).
The method that the purpose of this invention is to provide a kind of synthetic MCM-22 makes the consumption of synthetic used template hexamethylene imine significantly reduce.
The synthetic method of MCM-22 molecular sieve provided by the present invention is made up of the following step basically:
(1). with silicon source, aluminium source, alkali source, organic formwork agent (R) and water according to OH
-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.01～0.1): 1: (0.1～0.6): (5～100) are preferably according to OH
-: Al
2O
3: SiO
2: R: H
2O=(0.2～0.5): (0.02～0.08): 1: (0.15～0.5): the mole proportioning of (8～50) mixes makes colloid, then with this colloid hydrothermal crystallizing 1～16 hour under 160～200 ℃ and autogenous pressure, preferably hydrothermal crystallizing 3～12 hours under 165～190 ℃ and autogenous pressure obtains a kind of guiding glue after the cooling;
(2). in (1) gained guiding glue, add and mix, make a kind of mole and consist of OH into silicon source, aluminium source, alkali source and water
-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.5): (0.01～0.1): 1: (0.02～0.5): (5～100) are preferably OH
-: Al
2O
3: SiO
2: R: H
2O=(0.15～0.35): (0.02～0.05): 1: (0.05～0.35): the reaction mixture of (8～50), wherein the silicon in the said guiding glue accounts in the reaction mixture 10～60%, preferred 20～50% of total silicon amount in this reaction mixture; Then with this reaction mixture hydrothermal crystallizing 8～180 hours under 130～155 ℃ and autogenous pressure, hydrothermal crystallizing 20～130 hours under 135～150 ℃ and autogenous pressure preferably;
(3). hydrothermal crystallizing products therefrom filtration in (2), washing and roasting are obtained desirable zeolite product.
The silicon source that adopt step in the synthetic method of MCM-22 molecular sieve provided by the present invention (1) and/or (2), aluminium source, alkali source, organic formwork agent (R) etc. determine that according to prior art the present invention has no particular limits it; But the preferred raw material of the present invention is to be the silicon source with the solid silicone, or is silicon source and part aluminium source with the solid silicon aluminium glue; With sodium metaaluminate is all or part of aluminium source; Alkali source can be a sodium hydroxide; Organic formwork agent can be hexamethylene imine or diamantane quaternary ammonium hydroxide, wherein hexamethylene imine preferably.
The characteristics of method provided by the present invention are earlier to synthesize a kind of guiding glue under the condition of higher basicity and bigger template consumption and higher temperature, this guiding glue is fine particle, diffraction peak does not appear in X-ray diffractogram, the silicon source of glue and the appropriate amount of will leading then, the aluminium source, alkali sources etc. are mixed and made into the crystallization reaction mixture, utilize the guide effect of guiding glue to make reaction mixture crystallization at a lower temperature, adopt this method that synthetic required template consumption is reduced greatly, thereby reduce synthetic cost, and stray crystal does not appear in products obtained therefrom under so low template consumption condition.Under condition of the present invention, at R/SiO
2＜0.2, even R/SiO
2Also can synthesize qualified product under＜0.1 the situation and not produce stray crystal, this be the prior art work less than.
Said hydrothermal crystallizing can not carry out under the stirring condition in dynamic agitation or static state in the synthetic method of MCM-22 molecular sieve provided by the present invention.The dynamic agitation condition can make the constant product quality that synthesizes, but higher to equipment requirements, and can increase synthetic cost.The present invention can not synthesize qualified product under the stirring condition in static state, and this also is that prior art is difficult to reach.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of Comparative Examples 1 products obtained therefrom, and wherein a is unfired product, and b is the product after the roasting.
Fig. 2 is the X-ray diffraction crystalline phase figure of synthetic guiding glue and last products obtained therefrom among the embodiment 3, and wherein c is the crystalline phase figure of guiding glue, and d is the crystalline phase figure after the final product roasting.
The following examples will the present invention is described further.In following embodiment and Comparative Examples, characterize the degree of crystallinity of the molecular sieve that synthesizes with the strongest diffraction peak height of the X-ray diffraction of MCM-22 molecular sieve, wherein relative crystallinity is 100% benchmark with the unfired MCM-22 molecular sieve of Comparative Examples 1 gained.
Embodiment 1
The present embodiment explanation is with the solid silicon aluminium glue microballoon of NaY mother liquor preparation as the raw material of synthetic MCM-22 molecular sieve.
The NaY mother liquor (is taken from Chang Ling oil-refining chemical factory molecular sieve workshop of Catalyst Factory, SiO
2Content is 47 grams per liters, Na
2O content is 25 grams per liters), with concentration is dilute sulphuric acid adjusting pH to 5～6 of 40 weight %, silicon in the mother liquor and aluminium are precipitated out with the form of alumino silica gel, after the filtration, filter cake is added the water making beating make the slurries that solid content is 10 weight %, to obtain the alumino silica gel microballoon after this slurries spraying drying, wherein the particle diameter more than 60% is 40～80 microns, again with the microballoon after this spraying drying with the ammoniumsulphate soln pulping and washing of 3 weight % to Na
2O content＜0.1 weight %, after the drying, the MCM-22 molecular sieve that the alumino silica gel microspheres product that obtains is used for the back synthesizes.Its SiO of x ray fluorescence spectrometry analysis revealed
2Content is 92.0 weight %, Al
2O
3Content is 3.16 weight %; Recording its calcination contents on dry basis is 85.2 weight %, and the BET surface-area is 501m
2/ g.
Embodiment 2
The present embodiment explanation is with the solid silicone microballoon of water glass preparation as the raw material of synthetic MCM-22 molecular sieve.
(Qilu Petrochemical company Zhou village catalyst plant is produced, d with water glass
4 20=1.26 grams per milliliters, SiO
2Content is 265 grams per liters, Na
2O content is 86.4 grams per liters) dilute 1.5 times, with concentration is dilute sulphuric acid adjusting pH to 3～8 of 40 weight %, silicon in the water glass is precipitated out with the form of silica gel, after the filtration, filter cake is added the water making beating make the slurries that solid content is 10 weight %, to obtain silica gel microball after this slurries spraying drying, wherein the particle diameter more than 60% is 40～80 microns, again with the microballoon after this spraying drying with the ammoniumsulphate soln pulping and washing of 3 weight % to Na
2O content＜0.1 weight %, after the drying, the MCM-22 molecular sieve that the silica gel microball product that obtains is used for the back synthesizes.Its SiO of analysis revealed
2Content is 97 weight %, Al
2O
3Content is 1.65 weight %, and the calcination butt is 83.5 weight %, and the BET surface-area is 610m
2/ g.
Comparative Examples 1
This Comparative Examples explanation is according to USP4, the synthetic MCM-22 molecular sieve of method of report in 954,325.
With 2.4 gram sodium metaaluminate (Jiangpu, Shanghai chemical preparations factories, analytical pure) is dissolved in the 205.8 gram water with 0.44 gram sodium hydroxide (Beijing chemical reagents corporation, chemical pure), adds the commercially available silica gel microball of 20 grams (Qingdao silica gel manufacturer product while stirring, 120～200 orders, SiO
2Content is 96 weight %), add 12.78 gram hexamethylene imines (being called for short HMI) again, after stirring, the mole proportioning of gained mixture colloid is: 0.18NaOH: SiO
2: 0.033Al
2O
3: 0.50HMI: 40H
2O.Then the gained mixture is transferred in 600 milliliters the sealing autoclave, the speed of changeing with per minute 60 under 150 ℃ and autogenous pressure stirred crystallization 120 hours, product is taken out in the cooling back, after filtration, washing and dry, the XRD crystalline phase figure of products obtained therefrom as shown in Figure 1a, the product crystalline phase figure after the roasting is shown in Fig. 1 b, be indicated as the MCM-22 molecular sieve, the BET surface-area is 493m
2/ g.Its degree of crystallinity is set at 100%.
Embodiment 3
0.84 gram sodium metaaluminate and 2.46 gram sodium hydroxide are dissolved in the 60 gram water, add the silicon aluminium microsphere that makes among the 19.64 gram embodiment 1 while stirring, add 3.5 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.30NaOH: SiO
2: 0.033Al
2O
3: 0.14HMI: 12H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, in 175 ℃ of following static crystallizations 6 hours, product was taken out in the cooling back, obtains a kind of guiding glue.Figure is shown in Fig. 2 c for its XRD crystalline phase.
In addition 0.84 gram sodium metaaluminate and 1.28 gram sodium hydroxide are dissolved in the 70 gram water, add the silicon aluminium microsphere that makes among the 19.64 gram embodiment 1 while stirring, and then add above-mentioned guiding glue, after stirring, the mole proportioning of last gained reaction mixture is: 0.24NaOH: SiO
2: 0.033Al
2O
3: 0.07HMI: 13H
2O, the silicon in the glue that wherein leads account for the total reaction material total silicon amount 50%.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 96 hours under 143 ℃ and autogenous pressure, and product is taken out in the cooling back, after filtration, washing and dry, the XRD crystalline phase figure of products obtained therefrom is shown in Fig. 2 d after the roasting, be indicated as the MCM-22 molecular sieve, the BET surface-area is 467m
2/ g.Its relative crystallinity is 120%.
Comparative Examples 2
1.68 gram sodium metaaluminates and 3.74 gram sodium hydroxide are dissolved in the 130 gram water, add the silicon aluminium microsphere that makes among the 39.28 gram embodiment 1 while stirring, add 3.5 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.24NaOH: SiO
2: 0.033Al
2O
3: 0.07HMI: 13H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 144 hours under 180 ℃ and autogenous pressure, cooled product after filtration and washing, figure is similar to Fig. 2 c for its XRD crystalline phase, for amorphous.
Comparative Examples 3
1.68 gram sodium metaaluminates and 3.74 gram sodium hydroxide are dissolved in the 130 gram water, add the silicon aluminium microsphere that makes among the 39.28 gram embodiment 1 while stirring, add 3.5 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.24NaOH: SiO
2: 0.033Al
2O
3: 0.07HMI: 13H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 144 hours under 143 ℃ and autogenous pressure, cooled product after filtration and washing, figure is similar to Fig. 2 c for its XRD crystalline phase, for amorphous.
The result of Comparative Examples 2 and Comparative Examples 3 shows, when under the situation of identical charge ratio, adopting the method for prior art, under the condition of so low template consumption and static crystallization, under higher crystallization temperature and lower crystallization temperature, all can not obtain the MCM-22 zeolite product.
Embodiment 4
1.82 gram sodium metaaluminates and 0.71 gram sodium hydroxide are dissolved in the 60 gram water, add the silica gel microball that makes among the 19.0 gram embodiment 2 while stirring, add 5.1 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.20NaOH: SiO
2: 0.04Al
2O
3: 0.20HMI: 12H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 12 hours under 170 ℃ and autogenous pressure, and product is taken out in the cooling back, obtains a kind of guiding glue, and figure is similar to Fig. 2 c for its XRD crystalline phase.
In addition 0.44 gram sodium metaaluminate and 1.66 gram sodium hydroxide are dissolved in the 70 gram water, add the silica gel microball that makes among the 19.0 gram embodiment 2 while stirring, and then add above-mentioned guiding glue, after stirring, the mole proportioning of last gained mixture colloid is: 0.20NaOH: SiO
2: 0.028Al
2O
3: 0.10HMI: 13H
2O, the silicon in the glue that wherein leads account for the total reaction material total silicon amount 50%.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 144 hours under 150 ℃ and autogenous pressure, and product is taken out in the cooling back, after filtration, washing and dry, the XRD crystalline phase figure of products obtained therefrom is similar to Fig. 2 d after the roasting, be indicated as the MCM-22 molecular sieve, the BET surface-area is 395m
2/ g.Its relative crystallinity is 85%.
Embodiment 5
0.29 gram sodium metaaluminate and 2.23 gram sodium hydroxide are dissolved in the 75 gram water, add the alumino silica gel microballoon that makes among the 20.21 gram embodiment 1 while stirring, add 9.0 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.24NaOH: SiO
2: 0.025Al
2O
3: 0.35HMI: 15H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 4 hours under 180 ℃ and autogenous pressure, and product is taken out in the cooling back, obtains a kind of guiding glue, and figure is similar to Fig. 2 c for its XRD crystalline phase.
In addition 1.72 gram sodium metaaluminates and 5.52 gram sodium hydroxide are dissolved in the 300 gram water, add the alumino silica gel microballoon that makes among the 80.84 gram embodiment 1 while stirring, and then add above-mentioned guiding glue, after stirring, the mole proportioning of last gained mixture colloid is: 0.18NaOH: SiO
2: 0.027Al
2O
3: 0.07HMI: 15H
2O, the silicon in the glue that wherein leads account for the total reaction material total silicon amount 20%.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 120 hours under 145 ℃ and autogenous pressure, and product is taken out in the cooling back, after filtration, washing and dry, the XRD crystalline phase figure of products obtained therefrom is similar to Fig. 2 d after the roasting, be indicated as the MCM-22 molecular sieve, the BET surface-area is 454m
2/ g.Its relative crystallinity is 93%.
Claims (10)
1, a kind of synthetic method of MCM-22 molecular sieve is characterized in that this method is made up of the following step basically:
(1). with silicon source, aluminium source, alkali source, organic formwork agent (R) and water according to OH
-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.01～0.1): 1: (0.1～0.6): the mole proportioning of (5～100) mixes makes colloid, with this colloid hydrothermal crystallizing 1～16 hour under 160～200 ℃ and autogenous pressure, obtains a kind of guiding glue after the cooling then;
(2). in (1) gained guiding glue, add and mix, make a kind of mole and consist of OH into silicon source, aluminium source, alkali source and water
-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.5): (0.01～0.1): 1: (0.02～0.5): the reaction mixture of (5～100), wherein the silicon in the said guiding glue accounts in the reaction mixture 10～60% of total silicon amount in this reaction mixture; Then with this reaction mixture hydrothermal crystallizing 8～180 hours under 130～155 ℃ and autogenous pressure;
(3). hydrothermal crystallizing products therefrom filtration in (2), washing and roasting are obtained desirable zeolite product.
2, according to the process of claim 1 wherein that said silicon source is solid silicone or solid silicon aluminium glue; Said aluminium source is the aluminium in sodium metaaluminate or sodium metaaluminate and the solid silicon aluminium glue; Said alkali source is a sodium hydroxide; Said organic formwork agent is hexamethylene imine or diamantane quaternary ammonium hydroxide.
3, according to the method for claim 2, wherein said organic formwork agent is a hexamethylene imine.
4, according to the process of claim 1 wherein that said colloidal mole consists of OH in the step (1)
-: Al
2O
3: SiO
2: R: H
2O=(0.2～0.5): (0.02～0.08): 1: (0.15～0.5): (8～50).
5, according to the process of claim 1 wherein that the mole of said reaction mixture consists of OH in the step (2)
-: Al
2O
3: SiO
2: R: H
2O=(0.15～0.35): (0.02～0.05): 1: (0.05～0.35): (8～50).
6, according to the process of claim 1 wherein that the silicon in the guiding glue in the said reaction mixture of step (2) accounts for 20～50% of total silicon amount in the reaction mixture.
7, according to the process of claim 1 wherein that said hydrothermal crystallizing is not carry out under the stirring condition in dynamic agitation or static state.
8, according to the method for claim 7, wherein said hydrothermal crystallizing is not carry out under the stirring condition in static state.
9, according to the process of claim 1 wherein that the said hydrothermal crystallizing of step (1) is a hydrothermal crystallizing 3～12 hours under 165～190 ℃ and autogenous pressure.
10, according to the process of claim 1 wherein that the said hydrothermal crystallizing of step (2) is a hydrothermal crystallizing 20～130 hours under 135～150 ℃ and autogenous pressure.
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| US4826667A (en) * | 1986-01-29 | 1989-05-02 | Chevron Research Company | Zeolite SSZ-25 |
| US4954325A (en) * | 1986-07-29 | 1990-09-04 | Mobil Oil Corp. | Composition of synthetic porous crystalline material, its synthesis and use |
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| US9795949B2 (en) | 2006-05-08 | 2017-10-24 | Exxonmobil Chemical Patents Inc. | Catalyst composition |
| CN102311127B (en) * | 2010-07-07 | 2013-06-19 | 中国石油化工股份有限公司 | Method for preparing small-grain MCM-22 molecular sieve |
| CN102311127A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing small-grain MCM-22 molecular sieve |
| CN102452659B (en) * | 2010-10-15 | 2013-04-10 | 中国石油化工股份有限公司 | Preparation method of MCM-22 zeolite |
| CN102452659A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of MCM-22 zeolite |
| US9359216B2 (en) | 2010-11-23 | 2016-06-07 | Reliance Industries Limited | Method for the preparation of MWW type zeolite |
| CN103384644A (en) * | 2010-11-23 | 2013-11-06 | 信实工业公司 | A method for the preparation of MWW type zeolite |
| WO2012070067A3 (en) * | 2010-11-23 | 2012-07-19 | Reliance Industries Ltd. | Preparation method of mww type zeolite |
| WO2012070067A2 (en) * | 2010-11-23 | 2012-05-31 | Reliance Industries Ltd. | A method for the preparation of mww type zeolite |
| CN103384644B (en) * | 2010-11-23 | 2016-10-26 | 信实工业公司 | A kind of preparation method of MWW type zeolite |
| CN102757069A (en) * | 2011-04-29 | 2012-10-31 | 山东齐鲁华信高科有限公司 | Method for reusing mother liquor generated in ZSM (zeolite socony mobil)-5 molecular sieve preparation |
| CN103508466B (en) * | 2012-06-27 | 2015-07-01 | 中国石油化工股份有限公司 | Synthesis method of MCM (Mobil Composition of Matter)-22 molecular sieve |
| CN103508466A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Synthesis method of MCM (Mobil Composition of Matter)-22 molecular sieve |
| CN104803397A (en) * | 2014-01-28 | 2015-07-29 | 中国石油化工股份有限公司 | MCM-49 molecular sieve with low silica-alumina ratio, and preparation method thereof |
| CN105384181A (en) * | 2015-11-06 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for synthesizing aluminum-containing MCM-48 mesoporous molecular sieve with co-template agent |
| CN110862098A (en) * | 2019-11-28 | 2020-03-06 | 上海华谊（集团）公司 | Method for synthesizing MCM-22 molecular sieve |
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