CN103420388A - Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method - Google Patents
Metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method Download PDFInfo
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- CN103420388A CN103420388A CN2012101502631A CN201210150263A CN103420388A CN 103420388 A CN103420388 A CN 103420388A CN 2012101502631 A CN2012101502631 A CN 2012101502631A CN 201210150263 A CN201210150263 A CN 201210150263A CN 103420388 A CN103420388 A CN 103420388A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a metal ion-containing silicon-phosphorus-aluminum molecular sieve preparation method, wherein problems of poor activity and rapid coking during application of the silicon-phosphorus-aluminum molecular sieve prepared by using the previous method in methanol-to-low carbon olefin reactions are mainly solved with the present invention. The technical scheme comprises that: a dry glue prepared from precursor compounds of aluminum, silicon and phosphorus, metal ions and an organic template agent is placed on the upper portion of a reaction kettle, a water and organic amine mixed solution is placed on the lower portion of the reaction kettle, and the silicon-phosphorus-aluminum molecular sieve is prepared under a certain reaction condition. With the technical scheme, the problems are well solved, and the preparation method can be used for industrial production of methanol-to-low carbon olefin catalysts.
Description
Technical field
The present invention relates to a kind of preparation method of metal ion containing Si-P, specifically, the invention relates to the method for preparing metal ion silicon phosphorus aluminium SAPO-34 molecular sieve by vapor phase process.
Background technology
Within 1984, U.S. Union Carbide Corp has developed a series of silicoaluminophosphamolecular molecular sieves, and wherein the SAPO-34 molecular sieve has similar phosphorus zeolite type structure, belongs to pore zeolite, can be used as sorbent material, catalyzer and support of the catalyst.Shown good catalytic activity in methane producing light olefins (MTO) reaction, selectivity of light olefin is up to more than 90%, and the therein ethylene selectivity can reach more than 50%, C
5Above product amount is considerably less.The classical method for preparing SAPO-34 is Hydrothermal Synthesis (USP 4440871, CN 1037334C, CN 1038125C, CN 1048428C), i.e. crystallization and obtaining in the high-temperature water hot system.Hydrothermal method prepares molecular sieve process more complicated, needs to use a large amount of organic formwork agents, and finally need to from mother liquor, isolate zeolite product.
Vapor phase process is as a kind of method for preparing molecular sieve, and at zeolite molecular sieve, particularly there has been deep research the ZSM-5 molecular sieve aspect, but, aspect phosphate aluminium molecular sieve synthetic, reports at present less.So-called vapor phase process refers in building-up process, at first the Zeolite synthesis presoma is prepared into to dry glue under certain condition, then dry glue is placed in to reactor top, the mixing solutions that simultaneously in the reactor bottom, adds a certain amount of organic amine and water is as template, and dry glue does not contact with liquid phase part.With traditional Hydrothermal Synthesis, compare, vapor phase process can reduce the usage quantity of organic formwork agent greatly, saved numerous and diverse step that product separates with mother liquor, organic formwork agent easily reclaims and reuses, and is a kind of method for preparing the easy economic environment close friend of molecular sieve.
Aspect the synthetic SAPO-34 molecular sieve of vapor phase process, also just like CN1363519A, use vapor phase process to prepare the SAPO-34 molecular sieve at present, but it only use organic formwork agent at liquid phase part, degree of crystallinity is poor.CN1693202 drops into template in dry glue preparation process, but through experimental verification, and SAPO-34 molecular sieve crystallinity prepared by this kind of method improves not obvious, and while using it for methanol to olefins reaction, activity is poor, and coking rate is very fast.
Utilize vapor phase process to synthesize SAPO-34, by the process prepared at dry glue, dropping into metal-salt, under certain synthesis condition, metal ion can be introduced to the SAPO-34 molecular sieve, can improve its catalytic performance.
Current document adopts liquid phase method more aspect metal ion-modified, the patent of EXXON (US6040264) is introduced alkaline-earth metal Sr in the SAPO-34 molecular sieve, catalyst performance is improved, in the preparing olefin by conversion of methanol reaction, the total recovery of ethene and propylene can be up to 89.5%, but alkaline-earth metal Sr is expensive and be difficult to obtain.CN1167654A introduces alkaline-earth metal Ca by the method for ion-exchange in molecular sieve
2+Also make catalytic performance obtain certain improvement, but it is also more to generate by product.
Summary of the invention
Technical problem to be solved by this invention is that while overcoming SAPO-34 that in the past prepared by vapor phase process for methanol-to-olefins reaction, activity is low, and the problem that coking rate is fast provides a kind of preparation method of new metal ion containing Si-P.When the method has the metal ion SAPO-34 molecule that makes for methanol-to-olefins reaction, activity is high, the advantage that coking rate is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of metal ion containing Si-P in turn includes the following steps: (a) precursor compound of phosphorus, aluminium, silicon, organic amine and metal-salt are mixed and are made into mixture with water
, make mixture
In the mol ratio of each material consist of: Al
2O
3: 0.05～2SiO
2: 0.05～2P
2O
5: 10～200H
2O: 0～10R: 0.03～0.6M, wherein R is organic amine, M is metal ion; (b) by mixture
Be warming up to 70～90 ℃ and obtain colloid, then colloid is warming up to 100～160 ℃ and obtains dry glue; (c) dry glue is placed in to reactor upper gaseous phase position, the water that is 0.1～4:1 by mass ratio and the mixture of organic amine are placed in liquid phase position, reactor bottom, and under the condition that is 140～220 ℃ at crystallization temperature, organic amine steam reacts 12～72 hours to obtain the SAPO-34 molecular sieve with dry glue.
In technique scheme, the metal ion preferred version is selected from least one in Cu ﹑ Co ﹑ Fe ﹑ Ca ﹑ Bi and Zn; The presoma preferred version of phosphorus is at least one in ortho-phosphoric acid or phosphorous acid, the ortho-phosphoric acid that more preferably scheme is quality 85%; The presoma preferred version of aluminium is selected from least one in activated alumina, pseudo-boehmite or aluminum isopropylate; The presoma preferred version of silicon is at least one in silicon sol, active silica or tetraethoxy, the silicon sol that more preferably scheme is quality 30～40%; The organic amine preferred version is selected from least one in triethylamine, diethylamine, tetraethyl-oxyammonia or morpholine.In step (a), preferred version is first the precursor compound of phosphorus, aluminium, silicon to be mixed with water, at room temperature stirs after 1～3 hour and adds organic amine and metal-salt to obtain mixture again
.In step (b), preferred version is mixture
At room temperature stir after 12～24 hours and be warming up to 80～90 ℃, then continue to stir 3～5 hours to obtain colloid; Colloid is warming up to 120～140 ℃, after 12～24 hours, obtains dry glue.Template preferred version in step (c) is selected from least one in triethylamine, tetraethyl-oxyammonia or morpholine.The crystallization temperature preferable range is 160～200 ℃.
Utilize the synthetic means of gas phase, drop into metal-salt in the process prepared at dry glue, metal ion can be introduced to the SAPO-34 molecular sieve by certain synthesis condition, thereby realize the acidity of SAPO-34 molecular sieve is regulated, can improve its catalytic activity and anti-coking performance.
The present invention is by being incorporated into metal ion in the synthetic SAPO-34 molecular sieve of vapor phase process, while using it as catalyzer, being used for methanol-to-olefins reaction, the diene selective of ethene and propylene is increased to 80.8% from 79.2%, and coking rate also is reduced, and has obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[Comparative example 1
]
Under the state stirred, the silicon sol of the phosphoric acid of 23g 85% and 28.2g silicone content 30% is dropped in the 94g deionized water, after fully mixing, add again the 14.6g aluminum oxide.
At room temperature stir after 2 hours and add TEAOH, the mol ratio that now adds each component is Al
2O
3: P
2O
5: 1.25SiO
2: 75H
2O: TEAOH.
At room temperature continue to stir after 24 hours the temperature to 80 ℃ that raises gradually, continue to stir 3-5 hour, along with the evaporation of moisture in reaction process, the viscosity of system becomes greatly gradually, is colloidal.Colloid is dropped into to baking oven, and 120 ℃ of heating are more than 12 hours, and moisture evaporates fully, becomes dry glue.
By dry glue grind into powder, get the dry glue of 6.5g and be placed in reactor top, the mixing solutions that the reactor bottom is 7.5g triethylamine and 15g water.After reactor sealing, 180 ℃ of lower crystallization 48 hours, after cooling rear products therefrom fully washs, filters, 120 ℃ of dryings 5 hours, 550 ℃ of roastings obtained the SAPO-34 molecular sieve in 6 hours.
[Comparative example 2
]
According to each Step By Condition of comparative example 1, but the template triethylamine of reactor bottom is changed to morpholine.
[Comparative example 3
]
After making the SAPO-34 molecular sieve according to each Step By Condition of comparative example 1, by the Zn (NO) of itself and 10 wt%
3Solution carries out the exchange of 4 hours under 90 ℃, then centrifugation, washing solid product four times, by above-mentioned sample under 120 ℃ dry 12 hours, 550 ℃ of roastings 6 hours the ZnHSAPO-34 molecular sieve.
[Embodiment 1
]
Under the state stirred, the silicon sol of the phosphoric acid of 23g 85% and 28.2g silicone content 30% is dropped in the 94g deionized water, after fully mixing, add again the 14.6g aluminum oxide.
At room temperature stir after 2 hours and add TEAOH and Zn (NO
3)
2, the mol ratio that now adds each component is Al
2O
3: P
2O
5: 1.25SiO
2: 75H
2O: TEAOH: 0.06Zn (NO
3)
2.
At room temperature continue to stir after 24 hours the temperature to 80 ℃ that raises gradually, continue to stir 3 ~ 5 hours, along with the evaporation of moisture in reaction process, the viscosity of system becomes greatly gradually, is colloidal.Colloid is dropped into to baking oven, and 120 ℃ of heating are more than 12 hours, and moisture evaporates fully, becomes dry glue.
By dry glue grind into powder, get the dry glue of 6.5g and be placed in reactor top, the mixing solutions that the reactor bottom is 7.5g triethylamine and 15g water.After reactor sealing 180 ℃ of lower crystallization 48 hours, after cooling rear products therefrom fully washs, filters 120 ℃ of dryings 5 hours, 550 ℃ of roastings 6 hours.Through the XRD check, products obtained therefrom is the SAPO-34 molecular sieve, there is no impurity peaks, illustrates that metal ion enters framework of molecular sieve uniformly.
[Embodiment 2
]
According to each Step By Condition of embodiment 1, but the template triethylamine of reactor bottom is changed to the morphine woods, products obtained therefrom is the SAPO-34 molecular sieve, also the inclusion-free peak.
[Embodiment 3
]
According to each Step By Condition of embodiment 1, but by Zn (NO
3)
2Change to Cu (NO
3)
2, finally obtain the Cu-SAPO-34 molecular sieve.
[Embodiment 4
]
According to each Step By Condition of embodiment 1, but by 0.06Zn (NO
3)
2Change to 0.04Fe (NO
3)
3, finally obtain the Fe-SAPO-34 molecular sieve.
[Embodiment 5
]
According to each Step By Condition of embodiment 1, but by 0.06Zn (NO
3)
2Change to 0.12Bi (NO
3)
3, finally obtain the Bi-SAPO-34 molecular sieve.
[Embodiment 6
]
Adopt fixed-bed catalytic reactor, will adopt respectively comparative example 1, the comparative example 2 that triethylamine, morpholine are template, containing Zn
2+Embodiment 1, embodiment 2 gained molecular sieves carry out preparing light olefins from methanol catalysis examination experiment.Experiment condition is, the catalyst loading amount is 2.0 grams, 460 ℃ of temperature of reaction, and reaction pressure is normal pressure, and raw material adopts pure methyl alcohol, and air speed is 6 gram methanol/gram catalyst hour.The results are shown in Table 1.
Table 1
As can be seen from Table 1, by Zn
2+Introducing the synthetic SAPO-34 molecular sieve of vapor phase process can make the coking rate of catalyzer be reduced, when the catalytic activity aspect adopts triethylamine to be template, diene selective brings up to 80.8% by 79.2%, and while adopting morpholine to be template, diene selective brings up to 81.0% by 79.6%.The simple mode of ion-exchange that adopts can not promote the reaction for preparing light olefins from methanol activity.
Claims (7)
1. the preparation method of a metal ion containing Si-P in turn includes the following steps:
(a) precursor compound of phosphorus, aluminium, silicon, organic amine and metal-salt are mixed and are made into mixture with water
, make mixture
In the mol ratio of each material consist of: Al
2O
3: 0.05～2SiO
2: 0.05～2P
2O
5: 10～200H
2O: 0～10R: 0.03～0.6M, wherein R is organic amine, M is metal ion;
(b) by mixture
Be warming up to 70～90 ℃ and obtain colloid, then colloid is warming up to 100～160 ℃ and obtains dry glue;
(c) dry glue is placed in to reactor upper gaseous phase position, the water that is 0.1～4:1 by mass ratio and the mixture of organic amine are placed in liquid phase position, reactor bottom, and under the condition that is 140～220 ℃ at crystallization temperature, organic amine steam reacts 12～72 hours to obtain the SAPO-34 molecular sieve with dry glue.
2. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that metal ion is selected from least one metal ion in Cu ﹑ Co ﹑ Fe ﹑ Ca ﹑ Bi or Zn.
3. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that the precursor compound of phosphorus is selected from least one in ortho-phosphoric acid or phosphorous acid; The precursor compound of aluminium is selected from least one in activated alumina, pseudo-boehmite or aluminum isopropylate; The precursor compound of silicon is selected from least one in silicon sol, active silica or tetraethoxy; Organic amine is selected from least one in triethylamine, diethylamine, tetraethyl ammonium hydroxide or morpholine.
4. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that first the precursor compound of phosphorus, aluminium, silicon being mixed with water in step (a), at room temperature stirs after 1～3 hour and add organic amine and metal-salt to obtain mixture again
.
5. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that mixture in step (b)
At room temperature stir after 12～24 hours and be warming up to 80～90 ℃, then continue to stir 3～5 hours to obtain colloid.
6. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that, in step (b), colloid is warming up to 120～140 ℃, after 12～24 hours, obtains dry glue.
7. the preparation method of metal ion containing Si-P according to claim 1, is characterized in that crystallization temperature is 160 ~ 200 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
| CN109928407A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of SAPO-34 molecular sieve |
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|---|---|---|---|---|
| CN1693202A (en) * | 2005-04-14 | 2005-11-09 | 南京工业大学 | Process for prepareing SAPO-34 molecular siever |
| CN101555022A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
| EP2269733A1 (en) * | 2009-06-08 | 2011-01-05 | Basf Se | Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34) |
| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
-
2012
- 2012-05-16 CN CN2012101502631A patent/CN103420388A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693202A (en) * | 2005-04-14 | 2005-11-09 | 南京工业大学 | Process for prepareing SAPO-34 molecular siever |
| CN101555022A (en) * | 2009-04-22 | 2009-10-14 | 神华集团有限责任公司 | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve |
| EP2269733A1 (en) * | 2009-06-08 | 2011-01-05 | Basf Se | Process for the direct synthesis of cu containing silicoaluminophosphate (cu-sapo-34) |
| CN102372288A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing SAPO-34 molecular sieve |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109928407A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of synthetic method of SAPO-34 molecular sieve |
| CN109928407B (en) * | 2017-12-15 | 2021-01-05 | 中国石油化工股份有限公司 | Synthesis method of SAPO-34 molecular sieve |
| CN109317193A (en) * | 2018-11-12 | 2019-02-12 | 上海第二工业大学 | A kind of application of Fe-SAPO-34 catalyst in methyl stearate synthesis |
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Application publication date: 20131204 |