CN108163872B - Preparation method of low-acid-density SAPO-34 molecular sieve - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002253 acid Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005057 refrigeration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 abstract 2
- 238000001228 spectrum Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 241000045365 Microporus <basidiomycete fungus> Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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Abstract
A preparation method of a low-acid-density SAPO-34 molecular sieve comprises the steps of firstly utilizing an alkaline organic amine template agent in reactants to neutralize phosphoric acid to release heat, raising the temperature of the whole reaction materials, then introducing liquid nitrogen to refrigerate the reactants to prepare initial gel, and finally crystallizing the gel at high temperature to prepare the low-acid-density SAPO-34 molecular sieve. The SAPO-34 molecular sieve prepared by the invention has the characteristic of low density of strong acid.
Description
Technical Field
The invention relates to the technical field of synthesis and preparation of molecular sieves, in particular to a preparation method of a low-acid-density SAPO-34 molecular sieve.
Background
SAPO-34 molecular sieve is a crystalline silicoaluminophosphate with a three-dimensional framework structure consisting of PO2 +、AlO2 +And SiO2Tetrahedron, main channel is composed of eight-membered ring, and the size of pore is 0.38nm × 0.38 nm. SAPO-34 molecular sieve is of great interest because of its unique pore structure and suitable acidity, and exhibits excellent catalytic performance in Methanol To Olefin (MTO) reactions.
However, the SAPO-34 molecular sieve is easy to deposit carbon and block the pore channels during the MTO reaction process, so that the SAPO-34 molecular sieve is quickly deactivated. Therefore, there have been constant attempts to modify the synthesis strategy to prepare SAPO-34 molecular sieves in an attempt to extend the catalyst life. The main methods include the following aspects: 1. the grain size of the molecular sieve is reduced, and the small-grain even nano SAPO-34 molecular sieve is prepared, for example, the 300nm SAPO-34 molecular sieve is prepared by Wangpeng and the like (CN101823728A) through gel aging, hydrogen peroxide treatment and ultrasonic dispersion methods, but the nano SAPO-34 molecular sieve has relatively poor hydrothermal stability; 2. a mesoporous or macroporous structure is introduced into the microporous SAPO-34 molecular sieve, but the preparation cost of the hierarchical pore is usually too high; 3. the SAPO-34 molecular sieve with low silicon content is synthesized, the formation of silicon islands is avoided, the strong acid sites and the acid concentration in the catalyst are reduced, the occurrence of hydrogen transfer in the reaction is reduced, the generation of carbon deposition is reduced, and the service life of the catalyst is prolonged. However, in the general hydrothermal synthesis, the low silicon content is not easy to control, and the product is easy to generate a heterocrystal phase.
Generally speaking, a low silicon SAPO-34 molecular sieve refers to a crystal with a Si/Al molar ratio of less than 0.17, otherwise referred to as a high silicon SAPO-34. Wilson et al showed that SAPO-34 molecular sieves with low silicon content are characterized by low density of strong acid and have excellent MTO reaction performance (microporus and mesoporus Materials,1999,29, 117-126). In the synthesis experiment, researchers (Microporous and mesorous Materials,2009,126,1-7) all find that the synthesis of low-silicon SAPO-34 is more difficult than that of high-silicon SAPO-34, the silicon content in the initial gel has a larger influence on the purity of the product, and the preparation of SAPO-34 molecular sieve by a low-silicon system is usually accompanied by SAPO-5 heterocrystal phase, and the strong acid density of the SAPO-34 molecular sieve is about 1.0 mmol/g.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a pure-phase low-acid-density SAPO-34 molecular sieve.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
(1) sequentially adding an organic amine template agent R and a silicon source into deionized water, stirring for 1-24 hours, and then quickly adding phosphoric acid to form a mixed solution A;
(2) after the temperature of the mixed solution A is raised to 60-80 ℃, adding an aluminum source after the mixed solution A is stabilized, and continuously stirring for 0.5-4 hours to form a mixed solution B;
(3) introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 0-20 ℃ within 0.5-2 hours;
(4) transferring the cooled mixed solution B to a high-pressure crystallization reaction kettle, crystallizing for 12-60 hours at 130-200 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the low-acid-density SAPO-34 molecular sieve;
wherein the aluminum source is Al2O3In terms of phosphorus source, P2O5The silicon source is SiO2The template agent is counted by R, and the molar ratio of the molecular sieve synthesis reaction materials is as follows: SiO 22:Al2O3:P2O5:R:H2O＝0.001～0.1:1.0:0.5～2:0.5～3:20～90。
The organic amine template agent is one or a mixture of more of tetraethyl ammonium hydroxide, triethylamine and diethylamine.
The silicon source is one or a mixture of silica sol, silica gel and white carbon black.
The aluminum source is one or a mixture of more of pseudo-boehmite, aluminum isopropoxide and active alumina.
The invention adopts low-temperature liquid nitrogen for quick refrigeration, and the introduction of the low-temperature liquid nitrogen leads the mixed solution to quickly form even and tiny ice crystals, thereby being beneficial to quickly removing neutralization heat, leading silicon species to be fully dispersed after depolymerization, avoiding the generation of silicon islands in the later crystallization process and reducing the density of strong acid of the molecular sieve.
The strong acid density of the low-acid-density SAPO-34 molecular sieve is 0.02-0.5 mmol/g.
The strong acid density of the low-acid-density SAPO-34 molecular sieve is preferably 0.05-0.2 mmol/g.
Compared with the prior art, the invention has the following beneficial effects.
1. The method for preparing the low-silicon SAPO-34 is simple, has good repeatability, is easy to control the silicon content, and is beneficial to industrial amplification.
2. The strong acid density of the low-acid-density SAPO-34 molecular sieve prepared by the invention is less than 0.5mmol/g, and the low-acid-density SAPO-34 molecular sieve is a pure-phase SAPO-34 molecular sieve.
Drawings
Fig. 1 is an XRD spectrum of samples prepared in each example and comparative example.
Detailed Description
Example 1
In the first step, 230g of deionized water, 330g of tetraethylammonium hydroxide (TEAOH mass fraction of 35%) and 15g of silica Sol (SiO) were successively mixed225% by mass) were mixed and stirred for 2 hours, and then 180g of phosphoric acid (H) was rapidly added3PO485% by mass) to form a mixed solution A;
second, the temperature of the mixture A was monitored to rise to 70 ℃ and 138g of pseudoboehmite (Al) was added2O365 percent of mass percent) and continuously stirring for 1 hour to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 10 ℃ within 0.5 hour;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 60 hours at 150 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S1. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Example 2
In the first step, 468g of deionized water, 170g of triethylamine (TEA with a mass fraction of 99%) and 1.5g of white carbon black (SiO) are sequentially mixed292% by mass), and then 250g of phosphoric acid (H) was rapidly added thereto3PO485% by mass) to form a mixed solution A;
second, the temperature of the mixed solution A is monitored to rise to 80 ℃, and 129g of pseudo-boehmite (Al) is added2O365 percent of mass percent) and stirring for 4 hours to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 5 ℃ within 2 hours;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 50 hours at 200 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S2. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Example 3
In the first step, 230g of deionized water, 30g of tetraethylammonium hydroxide (TEAOH mass fraction of 35%), 68g of diethylamine (DEA mass fraction of 99%) and 3.2g of silica gel (SiO) were sequentially mixed298% by mass) for 3 hours, and then rapidly added 243g phosphoric acid (H)3PO485% by mass) to form a mixed solution A;
second, monitoring the temperature of the mixed solution A to 70 ℃, and adding 150g of pseudo-boehmite (Al)2O365 percent of mass percent) and stirring for 2 hours to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 5 ℃ within 1 hour;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 24 hours at 180 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S3. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Example 4
In the first step, 350g of deionized water, 100g of triethylamine (TEA mass fraction of 99%), 50g of diethylamine (DEA mass fraction of 99%) and 2.5g of white carbon black (SiO) are sequentially mixed292% by mass), stirring for 14 hours, and then rapidly adding 290g of phosphoric acid (H)3PO485% by mass) to form a mixed solution A;
second, the temperature of the mixture A was monitored to rise to 80 ℃ and 159g of pseudoboehmite (Al) was added2O365 percent of mass percent) and continuously stirring for 5 hours to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 8 ℃ within 2 hours;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 48 hours at 190 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S4. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Example 5
In the first step, 290g of deionized water, 460g of tetraethylammonium hydroxide (TEAOH mass fraction of 35%) and 8g of silica Sol (SiO) were successively mixed225 percent of mass fraction), 1.2g of silica gel (SiO)2Quality of98% by weight, stirring for 2 hours, then adding rapidly 180g of phosphoric acid (H)3PO485% by mass) to form a mixed solution A;
second, the temperature of the mixture A was monitored to rise to 75 ℃ and 129g of pseudoboehmite (Al) was added2O365 percent of mass percent) and continuously stirring for 1 hour to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 12 ℃ within 1.5 hours;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 60 hours at 160 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S5. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Example 6
In the first step, 430g of deionized water, 130g of triethylamine (TEA mass fraction of 99%), 20g of diethylamine (DEA mass fraction of 99%) and 3.6g of white carbon black (SiO)292% by mass), and then 310g of phosphoric acid (H) was rapidly added thereto3PO485% by mass) to form a mixed solution A;
second, after monitoring the temperature of the mixed solution A rising to 60 ℃, 136g of pseudo-boehmite (Al) is added2O365 percent of mass fraction), 22g of active alumina (Al)2O398 percent of mass percent) and continuously stirring for 6 hours to form a mixed solution B;
thirdly, introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 8 ℃ within 2 hours;
and fourthly, transferring the cooled mixed liquid B to a high-pressure crystallization reaction kettle, crystallizing for 48 hours at 190 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S6. The XRD spectrum of the molecular sieve is consistent with that of a pure phase SAPO-34 molecular sieve sample S0.
Comparative example
In the first step, 230g of deionized water and 330g of deionized water are sequentially mixedEthylammonium hydroxide (TEAOH mass fraction 35%) and 15g of silica Sol (SiO)225% by mass) were mixed and stirred for 2 hours, and then 180g of phosphoric acid (H) was rapidly added3PO485% by mass) to form a mixed solution A;
secondly, 138g of pseudo-boehmite (Al) is added after the temperature of the mixed solution A is monitored to rise to 70 ℃ and is stable and not increased any more2O365 percent of mass percent) and continuously stirring for 1 hour to form a mixed solution B;
and thirdly, transferring the mixed solution B to a high-pressure crystallization reaction kettle, crystallizing for 60 hours at 170 ℃ under a stirring state, separating, washing, drying and roasting after crystallization is finished to obtain the SAPO-34 molecular sieve, wherein the sample is marked as S0, and an XRD spectrogram shows that the sample is a pure-phase SAPO-34 molecular sieve.
TABLE 1 amount of acid in samples prepared in examples and comparative examples
The above-described embodiments of the present invention are intended to be illustrative of the present invention and not to limit the present invention, and therefore, any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (6)
1. A preparation method of a low acid density SAPO-34 molecular sieve is characterized by comprising the following steps:
(1) sequentially adding an organic amine template agent R and a silicon source into deionized water, stirring for 1-24 hours, and then quickly adding phosphoric acid to form a mixed solution A;
(2) after the temperature of the mixed solution A is raised to 60-80 ℃, adding an aluminum source after the mixed solution A is stabilized, and continuously stirring for 0.5-4 hours to form a mixed solution B;
(3) introducing low-temperature liquid nitrogen into the mixed liquid B for refrigeration, and stopping introducing the liquid nitrogen when the temperature of the mixed liquid B is reduced to 0-20 ℃ within 0.5-2 hours;
(4) transferring the cooled mixed solution B to a high-pressure crystallization reaction kettle, crystallizing for 12-60 hours at 130-200 ℃ under a stirring state, and separating, washing, drying and roasting after crystallization to obtain the low-acid-density SAPO-34 molecular sieve;
wherein the aluminum source is Al2O3In terms of phosphorus source, P2O5The silicon source is SiO2The template agent is counted by R, and the molar ratio of the molecular sieve synthesis reaction materials is as follows: SiO 22 : Al2O3 : P2O5 : R : H2O = 0.001～0.1 : 1.0 : 0.5～2 : 0.5～3 : 20～90。
2. The method for preparing the low acid density SAPO-34 molecular sieve according to claim 1, wherein the organic amine template is one or a mixture of tetraethyl ammonium hydroxide, triethylamine and diethylamine.
3. The method for preparing the low acid density SAPO-34 molecular sieve according to claim 1, wherein the silicon source is one or a mixture of silica sol, silica gel and silica white.
4. The method for preparing the low acid density SAPO-34 molecular sieve according to claim 1, wherein the aluminum source is one or more of pseudo-boehmite, aluminum isopropoxide and activated alumina.
5. The low acid density SAPO-34 molecular sieve prepared according to any one of claims 1 to 4, wherein the low acid density SAPO-34 molecular sieve has a strong acid density of 0.02 to 0.5 mmol/g.
6. The low acid density SAPO-34 molecular sieve prepared according to any one of claims 1 to 4, wherein the low acid density SAPO-34 molecular sieve has a strong acid density of 0.05 to 0.2 mmol/g.
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| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
| CN107434252A (en) * | 2016-05-27 | 2017-12-05 | 中国科学院大连化学物理研究所 | The preparation method of the low molecular sieves of silicon nanometer SAPO 34 |
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| CN102336412A (en) * | 2011-06-24 | 2012-02-01 | 神华集团有限责任公司 | SAPO-34 molecular sieve preparation method |
| CN102557073A (en) * | 2011-12-15 | 2012-07-11 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve, SAPO-34 molecular sieve and application of SAPO-34 molecular sieve |
| CN103011192A (en) * | 2012-12-17 | 2013-04-03 | 中国海洋石油总公司 | Silicon-aluminium carrier comprising molecular sieve and preparation method thereof |
| CN107434252A (en) * | 2016-05-27 | 2017-12-05 | 中国科学院大连化学物理研究所 | The preparation method of the low molecular sieves of silicon nanometer SAPO 34 |
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| "The eVect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction";De Chen et al.，;《Microporous and Mesoporous Materials》;19991231;第191–203页 * |
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