CN106064823A - A kind of method of modified SAPO 34 molecular sieve - Google Patents
A kind of method of modified SAPO 34 molecular sieve Download PDFInfo
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- CN106064823A CN106064823A CN201610373710.8A CN201610373710A CN106064823A CN 106064823 A CN106064823 A CN 106064823A CN 201610373710 A CN201610373710 A CN 201610373710A CN 106064823 A CN106064823 A CN 106064823A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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Abstract
The invention provides a kind of method of modified SAPO 34 molecular sieve, including: SAPO 34 molecular screen primary powder is carried out in a modifying agent once modified, in twice-modified dose, then carry out twice-modified step；Wherein, a described modifying agent is for can ionize out phosphate radical (PO4 3‑) compound or its mixture, described twice-modified dose is organic base or its mixture.The invention can improve SAPO 34 molecular sieve catalyst anti-carbon performance in methanol to olefins reaction and catalytic performance, has higher yield and longer service life, beneficially industrial amplification production, has obvious economic serviceability.
Description
Technical field
The invention belongs to molecular sieve modified technical field, and being suitable in methanol to olefins reaction particularly to one should
The method of modifying of SAPO-34 molecular sieve.
Background technology
Low-carbon alkene particularly ethylene, propylene are synthetic plastic, fiber and the important source material of all kinds of chemical materials, in the modern times
Chemical industry has very important status.Under existing technique, these alkene mostly come from the cracking of Petroleum, due to stone
Oil be non-renewable resources and reserves limited, find new synthetic route with replace original technique become a very important class
Topic.It it is the new work being hopeful most petroleum replacing route by preparing light olefins from methanol (Methanol to Olefins, be called for short MTO)
Skill.Methanol is one of the maximum amount of chemical products, can be from coal, natural gas and solid waste via synthesis gas (CO+H2) obtain, and
The most ripe by synthesising gas systeming carbinol technique.
SAPO-34 molecular sieve has heat stability and the hydrothermal stability of excellence, has stable as MTO catalysts
Property good, methanol conversion and the high advantage of ethylene, propylene selectivity, become the molecular sieve that exploitation MTO catalyst is first-selected.It is applied to
The SAPO-34 molecular sieve of MTO reaction, easily occurs carbon distribution seriously to reduce its service life in catalytic reaction process, and not
Easily regeneration.In order to improve the effect of MTO reaction, obtaining more purpose product, existing technique is frequently with in framework of molecular sieve
The method such as metal ion or modulation molecular sieve surface acidity that introduces is modified.By introducing in SAPO-34 framework of molecular sieve
Metal ion is possible not only to change its acid intensity, and can modify pore passage structure, obtains suitable aperture and appropriate acid is strong
The molecular sieve of degree, but the metal ion content of method introducing at present is less and distribution is concentrated, it is impossible to well it is scattered in SAPO-34
In molecular sieve, anti-carbon performance and the catalytic performance test experimental repeatability of modified molecular sieve are poor；Some techniques also use
Molecular sieve is modified by organic base, the micropore sieved by Molecular regulator and mesopore orbit structure and acid intensity, modified
The anti-carbon performance of SAPO-34 molecular sieve and catalytic performance are increased, but modified molecular sieve yield is relatively low, is unfavorable for
Industrial amplification production.
Summary of the invention
The invention is for solving the problems of the prior art, it is provided that a kind of method of modified SAPO-34 molecular sieve, especially
The SAPO-34 molecular sieve of its applicable classical formalism synthesis, can improve SAPO-34 molecular sieve catalyst in methanol to olefins reaction
Anti-carbon performance and catalytic performance, there is higher yield and longer service life, beneficially industrial amplification production, tool
There is obvious economic serviceability.
The method that the invention provides includes, is once changed by SAPO-34 molecular screen primary powder in a modifying agent
Property, in twice-modified dose, then carry out twice-modified step；Wherein, a described modifying agent is for can ionize out phosphate radical
(PO4 3-) compound or its mixture, described twice-modified dose is organic base or its mixture.
Wherein, a described modifying agent is preferably capable ionizing out the acid of phosphate radical or salt or its mixture (can ionize
Go out the acid of phosphate radical or the mixture of salt), more preferably phosphoric acid, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, sodium phosphate, phosphorus
The mixture of one or more in acid disodium hydrogen, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate.
Wherein, described twice-modified dose of one or more being preferably in organic primary amine, organic secondary, organic ammonium salt is mixed
Compound, more preferably diethylamine, triethylamine, diethanolamine, diisopropanolamine (DIPA), di-n-propylamine, Tri-n-Propylamine, tri-n-butylamine, four
The mixture of one or more in ethyl ammonium hydroxide, TPAOH, TBAH.
Wherein, described once modification is carried out in the solution (preferably aqueous solution) of a modifying agent, described once modified
In the solution of agent, the concentration of a modifying agent by ionizable go out phosphate radical in terms of, for 0.05-0.3mol/L；Described twice-modified
The solution of twice-modified dose (preferably aqueous solution) is carried out, in the solution of described twice-modified dose, twice-modified dose dense
Degree is in terms of the nitrogen (N) in primary amine, secondary amine or ammonium ion, for 0.1-0.5mol/L.
Wherein, in described once modification, the mass ratio of the solution of SAPO-34 molecular screen primary powder and a modifying agent is 1:
(3-10)；Described twice-modified in, be 1 through the mass ratio of once modified SAPO-34 molecular sieve with the solution of twice-modified dose:
(3-10)。
Wherein, in described once modification, at reaction condition is 15-60 DEG C, 0.5-3h is reacted in stirring；Described twice-modified in,
At reaction condition is 70-130 DEG C, 0.5-3h is reacted in stirring.
Wherein, between described the most modified and twice-modified step, and after twice-modified step, wrap the most respectively
Include filtration, the process step washed, be dried；The condition of described drying steps is dried 5-20h at being 80-150 DEG C.Further, institute
State twice-modified after also include the calcination steps after drying steps, the condition of described calcination steps be 450-650 DEG C at roasting 5-
20h。
The advantage of the invention is: operating condition is simple and easy to control, reaction condition is gentle；By once modified and secondary
Modified operation, the twice-modified SAPO-34 molecular sieve yield of preparation reaches more than 85%, is applied in methanol to olefins reaction catalysis
Performance is greatly improved, and the selectivity of ethylene and propylene reaches more than 80%, conversion ratio reaches more than 99%, and catalyst reaches service life
More than 80min.These advantages are conducive to the enlarged experiment of this preparation method, have obvious economic benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of modified SAPO-34 molecular sieve method of the present invention；
Fig. 2 is the stereoscan photograph of the SAPO-34 molecular screen primary powder of preparation in comparative example 1；
Fig. 3 is the stereoscan photograph of the twice-modified SAPO-34 molecular sieve of preparation in embodiment 1.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, logical below
Cross specific embodiment technical solution of the present invention is described further, but do not limit protection scope of the present invention.For sake of convenience,
Omit in embodiment necessity or conventional technique condition or step, such as feed way, wash temperature, time, standard, materials
Consumptions etc., these conditions or step are considered as that this area is conventional or technical staff is easily known.
Comparative example 1:
Use classical hydrothermal synthesis method to prepare SAPO-34 molecular screen primary powder, with water as solvent, phosphoric acid as phosphorus source, silicon molten
Glue be silicon source, boehmite be aluminum source, triethylamine be template.Then crystallization 48h in autoclave, crystallization temperature is
220℃.Obtaining SAPO-34 molecular screen primary powder through filtering, wash, being dried, after roasting, its macro morphology is as shown in Figure 2.Use solid
Fixed bed micro anti-evaluation device is evaluated catalytic performance and the life-span of SAPO-34 molecular screen primary powder, and evaluation result is shown in Table 1.
Embodiment 1:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the phosphoric acid solution of 0.05mol/L, controls
SAPO-34 molecular screen primary powder is 1:10 with the mass ratio of phosphoric acid solution.Constant temperature stirring 0.5h at 60 DEG C, through filtering, washing, in
It is dried 20h at 80 DEG C, obtains a modified SAPO-34 molecular sieve；Modified SAPO-34 molecular sieve is added to 0.2mol/L's
In Tri-n-Propylamine aqueous solution, the mass ratio controlling a modified SAPO-34 molecular sieve and Tri-n-Propylamine aqueous solution is 1:7.130
Stir 0.5h at DEG C, through filtering, washing, at 150 DEG C, be dried 5h, roasting 20h at 450 DEG C, obtain twice-modified SAPO-34 molecule
Sieve, its macro morphology is as shown in Figure 2.The yield of twice-modified SAPO-34 molecular sieve is 86.1%.Use fixed bed micro anti-evaluation
Device is evaluated catalytic performance and the life-span of twice-modified SAPO-34 molecular screen primary powder, and evaluation result is shown in Table 1.
Embodiment 2:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the potassium dihydrogen phosphate of 0.3mol/L, control
SAPO-34 molecular screen primary powder processed is 1:3 with the mass ratio of potassium dihydrogen phosphate.Constant temperature stirring 3h at 15 DEG C, through filtering, washing
Wash, at 100 DEG C, be dried 10h, obtain a modified SAPO-34 molecular sieve；Modified SAPO-34 molecular sieve is added to
In the tri-n-butylamine aqueous solution of 0.3mol/L, control the mass ratio of a modified SAPO-34 molecular sieve and tri-n-butylamine aqueous solution
For 1:5.At 70 DEG C, stir 3h, through filtering, washing, at 80 DEG C, be dried 20h, roasting 10h at 550 DEG C, obtain twice-modified
SAPO-34 molecular sieve.The yield of twice-modified SAPO-34 molecular sieve is 87.2%.Fixed bed micro anti-evaluation device is used to carry out
Evaluating catalytic performance and the life-span of twice-modified SAPO-34 molecular screen primary powder, evaluation result is shown in Table 1.
Embodiment 3:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the disodium phosphate soln of 0.2mol/L, control
SAPO-34 molecular screen primary powder processed is 1:8 with the mass ratio of disodium phosphate soln.Constant temperature stirring 2h at 30 DEG C, through filtering, washing
Wash, at 150 DEG C, be dried 5h, obtain a modified SAPO-34 molecular sieve；Modified SAPO-34 molecular sieve is added to
In the triethylamine aqueous solution of 0.1mol/L, the mass ratio controlling a modified SAPO-34 molecular sieve and triethylamine aqueous solution is 1:
10.At 90 DEG C, stir 1h, through filtering, washing, at 100 DEG C, be dried 10h, roasting 10h at 650 DEG C, obtain twice-modified SAPO-
34 molecular sieves.The yield of twice-modified SAPO-34 molecular sieve is 85.8%.Fixed bed micro anti-evaluation device is used to be evaluated two
The catalytic performance of the former powder of secondary modified SAPO-34 molecular sieve and life-span, evaluation result is shown in Table 1.
Embodiment 4:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the ammonium dihydrogen phosphate of 0.1mol/L, control
SAPO-34 molecular screen primary powder processed is 1:6 with the mass ratio of ammonium dihydrogen phosphate.Constant temperature stirring 1.5h at 45 DEG C, through filtering,
Washing, is dried 8h at 120 DEG C, obtains a modified SAPO-34 molecular sieve；Modified SAPO-34 molecular sieve is added to
In the tetraethyl ammonium hydroxide aqueous solution of 0.5mol/L, control a modified SAPO-34 molecular sieve and tetraethyl ammonium hydroxide water
The mass ratio of solution is 1:3.At 110 DEG C, stir 1.5h, through filtering, washing, at 120 DEG C, be dried 15h, roasting at 500 DEG C
12h, obtains twice-modified SAPO-34 molecular sieve.The yield of twice-modified SAPO-34 molecular sieve is 85.3%.Employing fixed bed is micro-
Anti-evaluating apparatus is evaluated catalytic performance and the life-span of twice-modified SAPO-34 molecular screen primary powder, and evaluation result is shown in Table 1.
Embodiment 5:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the potassium phosphate solution of 0.2mol/L, controls
SAPO-34 molecular screen primary powder is 1:7 with the mass ratio of potassium phosphate solution.Constant temperature stirring 2.5h at 40 DEG C, through filtering, washing,
At 90 DEG C, it is dried 12h, obtains a modified SAPO-34 molecular sieve；Modified SAPO-34 molecular sieve is added to 0.4mol/L
Diisopropanol amine aqueous solution in, the mass ratio controlling modified SAPO-34 molecular sieve and diisopropanol amine aqueous solution is 1:
6.At 100 DEG C, stir 2h, through filtering, washing, at 130 DEG C, be dried 8h, roasting 10h at 600 DEG C, obtain twice-modified SAPO-
34 molecular sieves.The yield of twice-modified SAPO-34 molecular sieve is 88.1%.Fixed bed micro anti-evaluation device is used to be evaluated two
The catalytic performance of the former powder of secondary modified SAPO-34 molecular sieve and life-span, evaluation result is shown in Table 1.
Comparative example 2:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the sodium dihydrogen phosphate of 0.1mol/L, control
SAPO-34 molecular screen primary powder processed is 1:7 with the mass ratio of potassium phosphate solution.Constant temperature stirring 2h at 35 DEG C, through filtering, washing,
Being dried 10h, roasting 12h at 600 DEG C at 100 DEG C, obtain a modified SAPO-34 molecular sieve, its yield is 95.4%.Use solid
Fixed bed micro anti-evaluation device is evaluated catalytic performance and the life-span of a former powder of modified SAPO-34 molecular sieve, and evaluation result is shown in
Table 1.
Comparative example 3:
The SAPO-34 molecular screen primary powder obtained in comparative example 1 is added in the diethylamine aqueous solution of 0.3mol/L, controls
SAPO-34 molecular screen primary powder is 1:5 with the mass ratio of diethylamine aqueous solution.1h is stirred at 100 DEG C, through filtering, washing, in
Being dried 10h, roasting 18h at 550 DEG C at 120 DEG C, obtain modified SAPO-34 molecular sieve, its yield is 67.9%.Use fixing
Bed micro anti-evaluation device is evaluated catalytic performance and the life-span of modified SAPO-34 molecular screen primary powder, and evaluation result is shown in Table
1。
Fixed bed micro anti-evaluation:
Catalyst catalytic performance and life-span are carried out on fixed bed micro anti-evaluation device, apparatus with catalyst inside 1.0g, and raw material is
Analytical pure methanol, mass space velocity is 3.0h-1, and reaction temperature is 450 DEG C, normal pressure.Use gas chromatographic analysis (Agilent GC-
7890B, fid detector, HP-PLOT chromatographic column 50m 0.53mm 15 μm) response time is the product of 15min, and with this point
Analysis result carries out catalyst performance contrast；Catalyst life is defined as under these experimental conditions, and methanol conversion drops to
Time required when 90%, by measuring the conversion ratio of differential responses time, extrapolation is used to record.Changing of embodiment 1～5
Catalyst catalytic performance and life-span in property SAPO-34 molecular sieve and comparative example 1～3 are as shown in table 1.
The fixed bed micro anti-evaluation result of SAPO-34 molecular sieve in table 1 embodiment and comparative example
Method of modifying and the effect thereof of the present invention are described by specific embodiment.Those skilled in the art
Can use for reference the links such as the suitable feed change of present disclosure, process conditions and realize other purpose corresponding, it is correlated with and changes
Becoming all without departing from present disclosure, all similar replacements and change are apparent to those skilled in the art
, it is considered as being included within the scope of the present invention.
Claims (9)
1. a method for modified SAPO-34 molecular sieve, including: SAPO-34 molecular screen primary powder is carried out in a modifying agent
Once modified, in twice-modified dose, then carry out twice-modified step；Wherein, a described modifying agent is for ionizing out
Phosphate radical (PO4 3-) compound or its mixture, described twice-modified dose is organic base or its mixture.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 1, it is characterised in that described once modified
Agent is preferably capable ionizing out the acid of phosphate radical or salt or its mixture, more preferably phosphoric acid, ammonium phosphate, diammonium phosphate, phosphorus
One in acid dihydride ammonium, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate or
Several mixture.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 1, it is characterised in that described twice-modified
Agent is preferably the mixture of one or more in organic primary amine, organic secondary, organic ammonium salt, more preferably diethylamine, three second
Amine, diethanolamine, diisopropanolamine (DIPA), di-n-propylamine, Tri-n-Propylamine, tri-n-butylamine, tetraethyl ammonium hydroxide, tetrapropyl hydroxide
The mixture of one or more in ammonium, TBAH.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 1, it is characterised in that described once modified
The solution of a modifying agent is carried out, in the solution of a described modifying agent, the concentration of a modifying agent with ionizable go out
Phosphate radical meter, for 0.05-0.3mol/L；Described twice-modified carry out in the solution of twice-modified dose, described twice-modified dose
Solution in, the concentration of twice-modified dose is in terms of the nitrogen in primary amine, secondary amine or ammonium ion, for 0.1-0.5mol/L.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 4, it is characterised in that described once modified
In, the mass ratio of the solution of SAPO-34 molecular screen primary powder and a modifying agent is 1:(3-10)；Described twice-modified in, through one
The SAPO-34 molecular sieve of secondary modification is 1:(3-10 with the mass ratio of the solution of twice-modified dose).
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 1, it is characterised in that described once modified
In, at reaction condition is 15-60 DEG C, 0.5-3h is reacted in stirring；Described twice-modified in, reaction condition be 70-130 DEG C at stir
Reaction 0.5-3h.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 1, it is characterised in that described once modified
And after step between twice-modified step and twice-modified, respectively further comprise filtration, the process step washed, be dried
Suddenly.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 7, it is characterised in that described drying steps
Condition be 80-150 DEG C at be dried 5-20h.
The method of a kind of modified SAPO-34 molecular sieve the most according to claim 7, it is characterised in that described twice-modified
After also include the calcination steps after drying steps, the condition of described calcination steps be 450-650 DEG C at roasting 5-20h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626345A (en) * | 2016-07-18 | 2018-01-26 | 任丘市华北石油科林环保有限公司 | A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst |
| CN109179448A (en) * | 2018-08-15 | 2019-01-11 | 潍坊天晟新材料有限公司 | A kind of new method quickly preparing mesoporous small particle size SAPO-34 molecular sieve |
| CN110498425A (en) * | 2018-05-17 | 2019-11-26 | 中国科学院大连化学物理研究所 | A method for selectively modifying the acidity of the outer surface of zeolite molecular sieves |
| CN115178293A (en) * | 2022-06-30 | 2022-10-14 | 上海应用技术大学 | Organic base modified SAPO-34 molecular sieve and preparation and application thereof |
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| CN109179448A (en) * | 2018-08-15 | 2019-01-11 | 潍坊天晟新材料有限公司 | A kind of new method quickly preparing mesoporous small particle size SAPO-34 molecular sieve |
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