CN105036153A - Modification method of SAPO-34 molecular sieve - Google Patents
Modification method of SAPO-34 molecular sieve Download PDFInfo
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- CN105036153A CN105036153A CN201510422457.6A CN201510422457A CN105036153A CN 105036153 A CN105036153 A CN 105036153A CN 201510422457 A CN201510422457 A CN 201510422457A CN 105036153 A CN105036153 A CN 105036153A
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Abstract
The invention provides a modification method of a SAPO-34 molecular sieve. The method comprises a process for modification on molecular sieve by using a mixed liquor containing SAPO-34 molecular sieve, organic base and water. The organic base is a mixture of one or more selected from organic primary amine and organic secondary amine. The invention can improve the anti-coking properties and catalytic properties of a SAPO-34 molecular sieve catalyst in a methanol-to-olefins reaction, and also has economic applicability.
Description
Technical field
The invention belongs to molecular sieve modified technical field, particularly a kind of method of modifying of the SAPO-34 molecular sieve being adapted at applying in methanol to olefins reaction.
Background technology
1984, U.S. combinating carbide company (UCC) developed series of new silicoaluminophosphamolecular molecular sieves (SAPO-n) (USP4,440,871).Sial phosphorus SAPO-34 molecular sieve is a kind of molecular sieve with chabazite analog structure be made up of silicon, aluminium, phosphorus and oxygen.Its structural unit is by SiO
2, AlO
2 -and PO
2 +tetrahedron is formed, and anhydrous chemical composition can be expressed as: mR (Si
xal
yp
z) O
2, in above formula, R is present in the template in molecular sieve crystal micropore, and m is the mole number of R, and x, y, z is respectively the molar fraction of Si, Al, P, and meets x+y+z=1.
SAPO-34 molecular sieve has suitable acidity and pore passage structure, has the high advantage of good stability, methanol conversion and ethylene, propylene selectivity as MTO catalysts, becomes the molecular sieve of exploitation MTO catalyzer first-selection.Freshly prepd SAPO-34 molecular sieve through modification can improve its MTO reaction in application performance, therefore people have done many research in the modification of SAPO-34 molecular sieve.
Be applied to the SAPO-34 molecular sieve of MTO reaction, very easily in catalytic reaction process, carbon distribution occur and seriously reduce its work-ing life, and not easily regenerating, its anti-carbon performance can be improved by improving its mesoporous content; Meanwhile, for ensureing that it realizes the high conversion of methyl alcohol and the highly selective of ethylene, propylene, need while improving the mesoporous content of SAPO-34 molecular sieve, keep the microvoid structure of SAPO-34 molecular sieve not to be destroyed.In prior art, conventional mineral alkali carries out modification to molecular sieve, because hydroxide ion radius is less, is easy to enter in the micropore of SAPO-34 molecular sieve, thus affect its micropore canals structure, the transformation efficiency of methanol to olefins reaction and selectivity are had a negative impact; Also adopt the organic bases in reaction mother liquor to carry out modification to molecular sieve in some technology, although make mother liquor obtain effective utilization like this, often little to the mesoporous content influence of SAPO-34 molecular sieve, anti-carbon performance cannot effectively improve.
Summary of the invention
The invention is for solving the problems of the prior art, provide a kind of method that SAPO-34 is molecular sieve modified, especially the SAPO-34 molecular sieve of classical formalism synthesis is applicable to, the anti-carbon performance of SAPO-34 molecular sieve catalyst in methanol to olefins reaction and catalytic performance can be improved, and there is economic serviceability.
The method that the invention provides comprises, and use the mixed solution containing SAPO-34 molecular sieve, organic bases and water molecular sieve to be carried out to the process of modification, wherein, described organic bases is one or more the mixture in organic primary amine, organic secondary.
Preferably, described organic bases is one or more the mixture in diethylamine, triethylamine, n-Butyl Amine 99, Di-n-Butyl Amine, monoisopropanolamine, diisopropanolamine (DIPA), amylamine, diamylamine, morpholine.
Wherein, the mol ratio of described SAPO-34 molecular sieve, organic bases and water is 0.01:(0.001-0.5): (0.01-5), is preferably 0.01:(0.01-0.1): (1-5).
Wherein, in described mixed solution, the source of described organic bases reclaim after can comprising the mixture of organic bases or the organic bases added separately and/or SAPO-34 molecular sieving containing one or more in the mother liquor of the specific organic bases kind of the present invention.
Further, described method comprises the steps: the SAPO-34 molecular screen primary powder of separation, organic bases and/or the mother liquor containing organic bases and water to be mixed to get mixed solution, the mol ratio of SAPO-34 molecular sieve, organic bases and water in mixed solution is made to be 0.01:(0.001-0.5): (0.01-5), be preferably 0.01:(0.01-0.1): (1-5), at 15-90 DEG C, stir 20-240min, obtain modified SAPO-34 molecular sieve through washing, drying, roasting.
Wherein, the temperature of described drying process is 80-150 DEG C, and the time is 1-15h.
Wherein, the temperature of described roasting process is 400-600 DEG C, and the time is 2-15h.
Advantage of the present invention and active effect are:
(1) mixed solution of specific organic bases and water is adopted to carry out modification to SAPO-34 molecular sieve, operation steps is simple, mild condition, while effectively enriching SAPO-34 molecular sieve mesopore orbit structure, maintain micropore canals structure not to be destroyed, specific surface area and total pore volume increase, and improve diene selective and catalyzer work-ing life of methanol-to-olefins process;
(2) source of organic bases reclaim after comprising SAPO-34 molecular sieving containing the mother liquor of the specific organic bases kind of the present invention, when the raw materials such as the template contained in described mother liquor are consistent with organic bases kind specific in technical solution of the present invention, the recycling of mother liquor can be realized, cost-saving;
(3) the present invention has general applicability, be particularly useful for the SAPO-34 molecular sieve of classical way synthesis, the modified SAPO-34 molecular sieve obtained by the present invention is for methanol-to-olefins catalyzed reaction, reactivity worth increases substantially, and reduced price is cheap, has economic serviceability.
Accompanying drawing explanation
Fig. 1 is the SAPO-34 molecular sieve electromicroscopic photograph in the comparative example 1 of non-modified process.
Fig. 2 is the SAPO-34 molecular sieve electromicroscopic photograph in the embodiment 1 of modification.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below by specific embodiment, technical solution of the present invention being described further, but not limiting protection scope of the present invention.For sake of convenience, omit technical qualification that are necessary or routine or step in embodiment, as feed way, wash temperature, time, standard, materials consumption etc., these conditioned disjunction steps are considered to that the conventional or technician in this area easily knows.
Comparative example 1
The preparation of SAPO-34 molecular sieve is carried out according to classical hydrothermal synthesis method, and be that template prepares SAPO-34 molecular sieve with triethylamine, the silicon source of employing is silicon sol, and the phosphorus source of employing is phosphoric acid, and the aluminium source of employing is diaspore, mR (SixAlyPz) O
2middle m, x, y, z is respectively 1.2,0.3,0.3,0.4, adopts water as solution.Then crystallization 48h at 220 DEG C in autoclave, filters, washing, obtains SAPO-34 molecular screen primary powder after dry, roasting.
Embodiment 1
Molecular screen primary powder comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water mol ratio=0.01:0.1:5 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 2
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water mol ratio=0.01:0.1:1 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 3
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: n-Butyl Amine 99: water mol ratio=0.01:0.1:1 prepares mixing solutions, processes 4h at 50 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 4
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: amylamine: water mol ratio=0.01:0.1:1 prepares mixing solutions, processes 2h at 90 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 5
Molecular sieve comparative example 1 obtained carries out modification, utilizes in comparative example 1 mother liquor after isolating molecular sieve to carry out modification.The mol ratio of triethylamine in mother liquor and water is adjusted to 0.1:5, adds the SAPO-34 molecular sieve that molar fraction is 0.01.2h is processed at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 6
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water mol ratio=0.01:0.001:5 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Embodiment 7
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water mol ratio=0.01:0.5:0.01 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Comparative example 2
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: NaOH: water=0.01:0.1:1 prepares mixing solutions, processes 4h at 50 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Comparative example 3
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: tri-n-butylamine: water=0.01:0.1:1 prepares mixing solutions, processes 4h at 50 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Comparative example 4
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: tetraethyl ammonium hydroxide: water=0.01:0.1:1 prepares mixing solutions, processes 4h at 90 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Comparative example 5
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water=0.01:1:1 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
Comparative example 6
Molecular sieve comparative example 1 obtained carries out modification, according to SAPO-34 molecular sieve: triethylamine: water=0.01:0.1:10 prepares mixing solutions, processes 2h at 80 DEG C.Washing after filtering, 80 DEG C of dry 15h, 500 DEG C of roasting 15h, obtain modified molecular sieve.
SAPO-34 molecular sieve the various embodiments described above and comparative example obtained is used for methanol to olefins reaction, compares catalyst performance, and micro anti-evaluation system carries out reaction evaluating, and concrete grammar is as follows:
Reactor is fixed-bed reactor, and adopt electrical heater heating, raw material is methyl alcohol, and by Micropump coutroi velocity, loaded catalyst is 1 ~ 3g, and reaction pressure is synthesis under normal pressure, and temperature of reaction is 400 ~ 470 DEG C, and the mass space velocity of methyl alcohol is 15 ~ 30h
-1, the reaction times is 10 ~ 20 minutes, and reaction product is analyzed through gas-chromatography.
Evaluation result as shown in Table 1 and Table 2, wherein, when catalyst life refers to and tests under these conditions, the time required when methanol conversion drops to below 90%.
Table 1 embodiment and comparative example SAPO-34 molecular sieve catalyst evaluation result
The specific surface area of table 2 embodiment and comparative example molecular sieve and pore volume data
Method of modifying of the present invention and effect thereof are described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize other object corresponding, its relevant change does not all depart from content of the present invention, all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included within scope of the present invention.
Claims (7)
1. the method that SAPO-34 is molecular sieve modified, comprise the process using the mixed solution containing SAPO-34 molecular sieve, organic bases and water molecular sieve to be carried out to modification, wherein, described organic bases is one or more the mixture in organic primary amine, organic secondary.
2. the method that a kind of SAPO-34 according to claim 1 is molecular sieve modified, it is characterized in that, described organic bases is one or more the mixture in diethylamine, triethylamine, n-Butyl Amine 99, Di-n-Butyl Amine, monoisopropanolamine, diisopropanolamine (DIPA), amylamine, diamylamine, morpholine.
3. the method that a kind of SAPO-34 according to claim 1 is molecular sieve modified, it is characterized in that, the mol ratio of described SAPO-34 molecular sieve, organic bases and water is 0.01:(0.001-0.5): (0.01-5), is preferably 0.01:(0.01-0.1): (1-5).
4. the method that a kind of SAPO-34 according to claim 1 is molecular sieve modified, it is characterized in that, in described mixed solution, the source of described organic bases reclaim after can comprising the mixture of organic bases or the organic bases added separately and/or SAPO-34 molecular sieving containing one or more in the mother liquor of the specific organic bases kind of the present invention.
5. the method that a kind of SAPO-34 according to claim 1 is molecular sieve modified, it is characterized in that, the SAPO-34 molecular screen primary powder of separation, organic bases and/or the mother liquor containing organic bases and water is comprised the steps: to be mixed to get mixed solution, the mol ratio of SAPO-34 molecular sieve, organic bases and water in mixed solution is made to be 0.01:(0.001-0.5): (0.01-5), at 15-90 DEG C, stir 20-240min, obtain modified SAPO-34 molecular sieve through washing, drying, roasting.
6. the method that a kind of SAPO-34 according to claim 5 is molecular sieve modified, is characterized in that, the temperature of described drying process is 80-150 DEG C, and the time is 1-15h.
7. the method that a kind of SAPO-34 according to claim 5 is molecular sieve modified, is characterized in that, the temperature of described roasting process is 400-600 DEG C, and the time is 2-15h.
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Cited By (3)
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| CN106064823A (en) * | 2016-05-30 | 2016-11-02 | 中国天辰工程有限公司 | A kind of method of modified SAPO 34 molecular sieve |
| US20170239649A1 (en) * | 2014-08-22 | 2017-08-24 | W.R. Grace & Co.-Conn. | Method For Synthesizing Silicoaluminophosphate-34 Molecular Sieves Using Monoisopropanolamine |
| CN107176614A (en) * | 2017-05-16 | 2017-09-19 | 中国天辰工程有限公司 | A kind for the treatment of fluid for washing sial phosphorus molecular sieve and the method for detecting amine component and content in the treatment fluid |
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| US20040116761A1 (en) * | 2002-12-12 | 2004-06-17 | Kun Wang | Modified metalloaluminophosphate molecular sieves |
| CN1642645A (en) * | 2002-03-29 | 2005-07-20 | 埃克森美孚化学专利公司 | Treatment of acid catalysts with nitrogen compounds |
| CN1993167A (en) * | 2004-08-03 | 2007-07-04 | 科罗拉多州立大学董事会 | Membranes for highly selective separations |
| CN104556093A (en) * | 2014-12-26 | 2015-04-29 | 烟台万润精细化工股份有限公司 | Preparation method of small-grain SAPO-34 molecular sieve |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1642645A (en) * | 2002-03-29 | 2005-07-20 | 埃克森美孚化学专利公司 | Treatment of acid catalysts with nitrogen compounds |
| US20040116761A1 (en) * | 2002-12-12 | 2004-06-17 | Kun Wang | Modified metalloaluminophosphate molecular sieves |
| CN1993167A (en) * | 2004-08-03 | 2007-07-04 | 科罗拉多州立大学董事会 | Membranes for highly selective separations |
| CN104556093A (en) * | 2014-12-26 | 2015-04-29 | 烟台万润精细化工股份有限公司 | Preparation method of small-grain SAPO-34 molecular sieve |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170239649A1 (en) * | 2014-08-22 | 2017-08-24 | W.R. Grace & Co.-Conn. | Method For Synthesizing Silicoaluminophosphate-34 Molecular Sieves Using Monoisopropanolamine |
| US10532350B2 (en) * | 2014-08-22 | 2020-01-14 | W.R. Grace & Co.-Conn | Method for synthesizing silicoaluminophosphate-34 molecular sieves using monoisopropanolamine |
| CN106064823A (en) * | 2016-05-30 | 2016-11-02 | 中国天辰工程有限公司 | A kind of method of modified SAPO 34 molecular sieve |
| CN107176614A (en) * | 2017-05-16 | 2017-09-19 | 中国天辰工程有限公司 | A kind for the treatment of fluid for washing sial phosphorus molecular sieve and the method for detecting amine component and content in the treatment fluid |
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Application publication date: 20151111 |