CN1107645C - Process for synthesizing molecular sieve (MCM-22) with special crystal structure - Google Patents
Process for synthesizing molecular sieve (MCM-22) with special crystal structure Download PDFInfo
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- CN1107645C CN1107645C CN99123719A CN99123719A CN1107645C CN 1107645 C CN1107645 C CN 1107645C CN 99123719 A CN99123719 A CN 99123719A CN 99123719 A CN99123719 A CN 99123719A CN 1107645 C CN1107645 C CN 1107645C
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Abstract
The present invention relates to a process for synthesizing MCM-22 molecular sieves. A silicon resource, an aluminum source, an alkali source, an organic template agent and water are prepared into a synthetic colloid according to the method of the prior art; then, hydrothermal crystallization is carried out on the synthetic colloid; a product is recovered. The present invention is characterized in that the hydrothermal crystallization is carried out under the temperature of 160 to 200 DEG C for 1 to 20 hours; then, the temperature is dropped to 130 to 155 DEG C for the hydrothermal crystallization for 8 to 100 hours. The process of the present invention can be used for synthesizing a qualified product under the condition of static crystallization. Moreover, the process can reduce the dosage of the 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 modification method that the purpose of this invention is to provide a kind of synthetic MCM-22 makes just to synthesize desirable pure zeolite product under the condition of static crystallization; And the inventive method can be produced under the condition of dynamic crystallization than the better product of ordinary method performance; The inventive method can make the consumption of synthetic used template hexamethylene imine reduce simultaneously.
In general, the crystallization temperature when synthesizing the MCM-22 molecular sieve can not be too high, otherwise be easy to generate stray crystal or can not synthesize desirable product.The inventor finds, after adopting first high temperature during cryogenic two sections crystallization methods, can not only under the condition of static crystallization, just can synthesize desirable pure zeolite product, and the consumption of synthetic used template hexamethylene imine is reduced, thereby reach purpose of the present invention.
The synthetic method of MCM-22 molecular sieve provided by the present invention is with the silicon source, the aluminium source, alkali source, organic formwork agent and water are mixed with synthetic colloid according to the method for prior art, should synthesize the colloid hydrothermal crystallizing then and reclaim product, it is characterized in that said hydrothermal crystallizing is first hydrothermal crystallizing 1～20 hour under 160～200 ℃ and autogenous pressure, and then be cooled to 130～155 ℃ of hydrothermal crystallizings 8～100 hours under autogenous pressure, first hydrothermal crystallizing 3～12 hours under 165～190 ℃ and autogenous pressure preferably, and then be cooled to 135～150 ℃ of hydrothermal crystallizings 16～80 hours under autogenous pressure.
The silicon source of being adopted in the synthetic method of MCM-22 molecular sieve provided by the present invention, 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.
Said synthetic colloidal mole consists of OH in the synthetic method of MCM-22 molecular sieve provided by the present invention
-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.01～0.1): 1: (0.05～0.5): (5～100) are preferably OH
-: Al
2O
3: SiO
2: R: H
2O=(0.15～0.5): (0.015～0.05): 1: (0.1～0.35): (8～50).About the consumption of organic formwork agent (R), synthesis condition was controlled well when this consumption was high, and was difficult for stray crystal, good product quality, but synthetic cost improves greatly; Under condition of the present invention, at R/SiO
2＜0.3, even R/SiO
2Also can synthesize qualified product under＜0.2 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 X-ray diffraction (XRD) the crystalline phase figure after the embodiment 3 products obtained therefrom roastings.
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 analysis revealed
2Content is 92.0 weight %, Al
2O
3Content is 3.16 weight %, and the 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 1.28 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, after adding 5.1 grams again hexamethylene imines stirring, the mole proportioning of gained mixture colloid is: 0.18NaOH: SiO
2: 0.033Al
2O
3: 0.20HMI: 12H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 6 hours under 180 ℃ and autogenous pressure, and then be cooled to 145 ℃ of static crystallizations 46 hours, product is taken out in the cooling back, after filtration, washing and dry, the product crystalline phase figure after the roasting is as shown in Figure 2, be indicated as the MCM-22 molecular sieve, the BET surface-area is 480m
2/ g.Its relative crystallinity is 110%.
Comparative Examples 2
0.84 gram sodium metaaluminate and 1.28 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 5.1 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.18NaOH: SiO
2: 0.033Al
2O
3: 0.20HMI: 12H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 72 hours under 180 ℃ and autogenous pressure, and product is taken out in the cooling back, after filtration, washing and dry, it is amorphous that the product after the roasting detects its crystalline phase through XRD.
Comparative Examples 3
0.84 gram sodium metaaluminate and 1.28 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 5.1 gram hexamethylene imines again, after stirring, the mole proportioning of gained mixture colloid is: 0.18NaOH: SiO
2: 0.033Al
2O
3: 0.20HMI: 12H
2O.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, it is amorphous that the product after the roasting detects its crystalline phase through XRD.
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
1.46 gram sodium metaaluminates and 1.49 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, after adding 4.8 grams again hexamethylene imines stirring, the mole proportioning of gained mixture colloid is: 0.25NaOH: SiO
2: 0.033Al
2O
3: 0.18HMI: 14H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 4 hours under 175 ℃ and autogenous pressure, and then be cooled to 150 ℃ of static crystallizations 54 hours under autogenous pressure, product is taken out in the cooling back, after filtration, washing and dry, the product crystalline phase figure after the roasting is similar to Fig. 2, be indicated as the MCM-22 molecular sieve, the BET surface-area is 449m
2/ g.Its relative crystallinity is 81%.
0.29 gram sodium metaaluminate and 1.30 gram sodium hydroxide are dissolved in the 75 gram water, add the silica gel microball that makes among the 19.64 gram embodiment 2 while stirring, after adding 4.0 grams again hexamethylene imines stirring, the mole proportioning of gained mixture colloid is: 0.15NaOH: SiO
2: 0.025Al
2O
3: 0.15HMI: 15H
2O.Then the gained mixture is transferred in the stainless steel sealed reactor, static crystallization is 12 hours under 170 ℃ and autogenous pressure, and then be cooled to 143 ℃ of static crystallizations 40 hours under autogenous pressure, product is taken out in the cooling back, after filtration, washing and dry, the product crystalline phase figure after the roasting is similar to Fig. 2, be indicated as the MCM-22 molecular sieve, the BET surface-area is 467m
2/ g.Its relative crystallinity is 97%.
Claims (8)
1, a kind of synthetic method of MCM-22 molecular sieve, this method is that silicon source, aluminium source, alkali source, organic formwork agent and water are mixed with synthetic colloid, should synthesize the colloid hydrothermal crystallizing then and reclaim product, it is characterized in that said hydrothermal crystallizing is first hydrothermal crystallizing 1～20 hour under 160～200 ℃ and autogenous pressure, and then be cooled to 130～155 ℃ of hydrothermal crystallizings 8～100 hours under autogenous pressure.
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 synthetic colloidal mole consists of OH-: Al
2O
3: SiO
2: R: H
2O=(0.1～0.6): (0.01～0.1): 1: (0.05～0.5): (5～100).
5, according to the method for claim 4, wherein said synthetic colloidal mole consists of OH-: Al
2O
3: SiO
2: R: H
2O=(0.15～0.5): (0.015～0.05): 1: (0.1～0.35): (8～50).
6, 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.
7, according to the method for claim 6, wherein said hydrothermal crystallizing is not carry out under the stirring condition in static state.
8,, and then be cooled to 135～150 ℃ of hydrothermal crystallizings 16～80 hours under autogenous pressure according to the process of claim 1 wherein that said hydrothermal crystallizing is first hydrothermal crystallizing 3～12 hours under 165～190 ℃ and autogenous pressure.
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|---|---|---|---|
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| CN99123719A CN1107645C (en) | 1999-11-17 | 1999-11-17 | Process for synthesizing molecular sieve (MCM-22) with special crystal structure |
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| CN1107645C true CN1107645C (en) | 2003-05-07 |
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Cited By (1)
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|---|---|---|---|---|
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
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| CN100341784C (en) * | 2004-12-17 | 2007-10-10 | 中国科学院大连化学物理研究所 | Synthetic method for MCM-22 molecular sieve |
| CN100345756C (en) * | 2006-03-03 | 2007-10-31 | 南开大学 | Synthetic method for MCM-22 molecular sieve |
| CN101489676B (en) * | 2006-07-28 | 2012-04-04 | 埃克森美孚化学专利公司 | Molecular sieve composition (emm-10-p), its method of making, and use for hydrocarbon conversions |
| CN102049294B (en) * | 2009-10-27 | 2012-06-27 | 中国石油化工股份有限公司 | Molecular sieve with composite structure, and preparation method and use thereof |
| CN102351211B (en) * | 2011-08-01 | 2012-11-21 | 大连理工大学 | Synthesis method of MCM-22 family molecular sieve |
| 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 |
| CN103663489B (en) * | 2012-09-26 | 2015-11-18 | 中国科学院大连化学物理研究所 | A kind of SAPO-44 molecular sieve and synthetic method thereof |
| CN102989506B (en) * | 2012-12-18 | 2015-07-01 | 常州大学 | Preparation method of novel immobilized ionic liquid catalyst |
| CN105271291B (en) * | 2014-07-21 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of synthetic method of the molecular sieves of MCM 49 |
| CN106395848B (en) * | 2016-08-31 | 2018-11-06 | 武汉工程大学 | A kind of methods and applications synthesizing MWW structure molecular screens using fluosilicic acid |
| CN109019751B (en) * | 2018-10-17 | 2021-02-19 | 齐鲁工业大学 | Organic waste liquid adsorption treatment method |
| CN110862098B (en) * | 2019-11-28 | 2023-01-20 | 上海华谊（集团）公司 | Method for synthesizing MCM-22 molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1999
- 1999-11-17 CN CN99123719A patent/CN1107645C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
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