CN113912081A - Preparation method and application of modified SAPO-34 molecular sieve - Google Patents
Preparation method and application of modified SAPO-34 molecular sieve Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 85
- 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 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000010306 acid treatment Methods 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 44
- 239000000243 solution Substances 0.000 description 15
- 238000012216 screening Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- -1 Succinic acid Oxalic acid Nitric acid Nitric acid Chemical compound 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a modified SAPO-34 molecular sieve, which comprises the following steps: s1, the SAPO-34 molecular sieve is put at the temperature of 400 ℃ and 800 ℃, and the water-liquid phase mass space velocity is 0.06-3 h‑1Carrying out hydrothermal treatment on water vapor for 1-80h under the condition that the partial pressure of the water vapor is 0.01-0.1Mpa in an inert atmosphere to obtain a precursor I; s2, carrying out acid treatment on the precursor I at the temperature of 40-90 ℃ for 0.5-10h to obtain a precursor II; s3, mixing the precursor II with an adhesive, and roasting for 5-24h at the temperature of 450-650 ℃ after molding to obtain the modified SAPO-34 molecular sieve. The invention also relates toDiscloses an application of the modified SAPO-34 molecular sieve. The modified SAPO-34 molecular sieve of the invention can be used as a catalyst to solve the problem of overtemperature of the feed of an MTO reactor.
Description
Technical Field
The invention belongs to the technical field of SAPO-34 molecular sieves, and particularly relates to a preparation method and application of a modified SAPO-34 molecular sieve.
Background
Ethylene and propylene are used as industrial basic raw materials, so that the ethylene and propylene play a strong supporting role in the development of national economy, and once the development of the ethylene industry can be used as a measure of the national economic strength. The Chinese economic development is changed from high speed to medium-high speed, but the demand gap on ethylene and propylene markets is still larger, at present, the olefin production seriously depends on petroleum, the petroleum resources are increasingly in short supply, and the resources in China have the characteristics of rich coal, poor oil and less gas, so that the way of producing high-end chemical products by replacing the petroleum with the coal and maintaining clean and efficient utilization of the coal is determined, and the method is of great importance for optimizing the energy consumption structure in China, reducing import dependence and ensuring national energy safety. The MTO (methanol to olefin) technology is an important technical route for replacing petrochemical engineering by using a novel coal chemical technology in China, and has profound significance for economic development and national energy strategic requirements in China.
In US4499327 patent, a series of silicoaluminophosphate molecular sieves were developed by the carbon compounds of the united states company (UCC). Among them, the SAPO-34 molecular sieve shows excellent catalytic performance in the MTO reaction, and the MTO process using the SAPO-34 molecular sieve as the catalyst becomes a hot spot of research of people.
The MTO reaction is a fast reaction with strong exothermicity, and the reaction heat is-196 Kcal/Kg methanol. The reactor overtemperature condition often appears in the MTO device feeding process, and the overtemperature condition can also appear when serious, so that the temperature of a catalyst bed layer in the reactor is rapidly increased and deviates from a design value seriously, and great harm can be caused to reaction and equipment. The over-temperature of the reactor can cause the following hazards: (1) the great thermal stress generated by the over-temperature of the reactor causes irreversible damage to the lining of the reactor; (2) the generation of carbon deposition is aggravated by the excessively high reaction temperature, so that the catalyst is more easily deactivated; (3) the reaction temperature rises rapidly, and the generated thermal stress causes the catalyst to be thermally collapsed, so that the catalyst is crushed and blocks downstream pipelines and equipment.
CN110215886A discloses a reaction temperature control method for a reactor for preparing low-carbon alcohol from synthesis gas, wherein when a catalyst bed layer of the reactor has a temperature runaway trend, a cold shock gas bypass adjusting system is used for adding 60-90 ℃ cold shock gas into the reactor to reduce the temperature of gas entering the reactor, so that the problem of the over-temperature of the reactor is solved. However, the introduction of cold shock gas in this method can cause the temperature of the reactor bed to drop suddenly, and the resulting quenching condition can damage the strength of the catalyst. In addition, the bypass regulating system invisibly increases the equipment investment and the operation management cost.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method and application of a modified SAPO-34 molecular sieve, and the modified SAPO-34 molecular sieve has proper structure
And the acid density is used as a catalyst of the MTO reaction, so that the generation of aromatic hydrocarbon and carbon deposition species can be reduced, the heat effect of a reaction system is further weakened, and the purpose of preventing the feeding overtemperature of the MTO reactor is achieved.
The invention provides a preparation method of a modified SAPO-34 molecular sieve, which comprises the following steps:
s1, the SAPO-34 molecular sieve is put at the temperature of 400 ℃ and 800 ℃, and the water-liquid phase mass space velocity is 0.06-3 h-1Carrying out hydrothermal treatment on water vapor for 1-80h under the condition that the partial pressure of the water vapor is 0.01-0.1Mpa in inert atmosphere to obtain a precursor I;
s2, carrying out acid treatment on the precursor I at the temperature of 40-90 ℃ for 0.5-10h to obtain a precursor II;
s3, mixing the precursor II with an adhesive, and roasting for 5-24h at the temperature of 450-650 ℃ after molding to obtain the modified SAPO-34 molecular sieve.
Preference is given toIn S1, the SAPO-34 molecular sieve has chabazite structure, average particle size of 300nm-5 μm, and total pore volume of 0.1-1cm measured by physical adsorption method3(g) BET specific surface area of 200-2/g。
Preferably, in S1, the temperature of the hydrothermal treatment is 600-800 ℃, and the water-liquid phase mass space velocity is 0.1-2.5h-1The partial pressure of water vapor in inert atmosphere is 0.04-0.1Mpa, and the time of hydrothermal treatment is 1-50 h.
Preferably, in S2, the acid treatment temperature is 60-90 ℃ and the time is 0.5-6 h.
Preferably, in S2, the acid-treated acid solution is at least one of nitric acid, oxalic acid, citric acid and succinic acid, and the concentration of the acid solution is 0.01-0.2 mol/L.
Preferably, the concentration of the acid solution is 0.02 to 0.1 mol/L.
Preferably, in S3, the binder is at least one of silica sol, aluminum sol, pseudo-boehmite, and clay.
Preferably, in S3, the molding is tablet, extrusion or ball-blasting molding.
Preferably, the amount of the binder is 10-60% of the weight of the modified SAPO-34 molecular sieve.
The invention also discloses application of the modified SAPO-34 molecular sieve obtained by the preparation method as a catalyst in an MTO reaction.
The evaluation of the modified SAPO-34 molecular sieve catalyst is carried out in a fixed bed reactor, and the reaction conditions are as follows: takes methanol or a mixed solution of methanol and water as a raw material, and has the reaction temperature of 350-650 ℃, the reaction pressure of 0.01-1.0MPa and the methanol weight space velocity of 0.1-6h-1Under the condition (1), the raw materials generate catalytic reaction through a catalyst bed layer to generate low-carbon olefin and the like; wherein the weight percentage of the methanol in the mixed solution of the methanol and the water is at least 30 percent.
By applying the technical scheme of the invention, the SAPO-34 molecular sieve is subjected to hydrothermal treatment and acid treatment modification, and the molecular sieve can be effectively reduced under the optimal condition
The acid density further inhibits the side reaction of olefin polymerization and macromolecular aromatic hydrocarbon generation and reduces the generation rate of aromatic hydrocarbon and carbon deposition species, and finally the aim of reducing the heat effect of a reaction system is fulfilled.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention modifies SAPO-34 molecular sieve catalyst before MTO reaction, does not need to modify a reaction device, and has universality.
2. The preparation method has the advantages of simple operation steps, low equipment requirement and low raw material cost, is a preparation method with wide application prospect, and has good industrial application prospect and economic value.
3. The modified SAPO-34 molecular sieve of the invention is used as a catalyst, which not only can solve the problem of overtemperature of the feed of an MTO reactor, but also can effectively improve the product yield of ethylene and propylene under the optimal reaction condition.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the scope of the present invention, and any products similar or equivalent to the present invention, which can be obtained by combining the features of the present invention with other prior art according to the teaching of the present invention, are within the scope of the present invention.
X-ray diffraction (XRD) characterization of SAPO-34 molecular sieve samples in the following examples was performed on a rotary target X-ray polycrystalline diffractometer model Japanese physical D-MAX-2550, with a radiation source Cu-Ka, a tube voltage of 45kV, a tube current of 200mA, and a scanning 2 theta angle ranging from 3 deg. to 50 deg.. Six main characteristic diffraction peak 2 theta values of the SAPO-34 molecular sieve are respectively as follows: 9.5 °, 12.8 °, 16.0 °, 20.5 °, 25.8 °, 30.5 °. The calculation of the relative crystallinity of the SAPO-34 molecular sieve of each example was performed using the sum of the individual characteristic diffraction peak heights in comparison to the comparative example SAPO-34 molecular sieve.
Example 1
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (with physical property: average particle diameter of 4 μm, total pore volume of 0.23cm measured by physical adsorption method)3Per g, BET specific surface area 462m2/g) at 700 deg.C, water liquid phase mass space velocity of 0.2h-1Carrying out hydrothermal treatment on water vapor for 10 hours under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a citric acid solution with the concentration of 0.1mol/L for 1h at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 500 ℃ muffle furnace for 12 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 2
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 750 deg.C, and water liquid phase mass space velocity of 0.2h-1Carrying out hydrothermal treatment on water vapor for 10 hours under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a citric acid solution with the concentration of 0.1mol/L for 2h at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 500 ℃ muffle furnace for 12 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 3
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, commercial SAPO-34 molecular sieves (as in example 1)The products are the same batch) at the temperature of 800 ℃ and the water-liquid phase mass space velocity of 0.2h-1Carrying out hydrothermal treatment on water vapor for 10 hours under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a citric acid solution with the concentration of 0.1mol/L for 4 hours at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 550 ℃ muffle furnace for 12 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 4
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 0.2h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a nitric acid solution with the concentration of 0.05mol/L for 2h at the temperature of 80 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 500 ℃ muffle furnace for 8 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 5
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 750 deg.C, and water liquid phase mass space velocity of 0.8h-1Carrying out hydrothermal treatment on water vapor for 10 hours under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a citric acid solution with the concentration of 0.1mol/L for 4 hours at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with silica sol, extruding the mixture into strips, forming, drying the dried strip mixture in a 120 ℃ oven for 12h, crushing, screening out particles with the diameter of 0.6-0.9mm, and roasting in a 600 ℃ muffle furnace for 10h to obtain the modified SAPO-34 molecular sieve, wherein the silica sol accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 6
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 750 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with oxalic acid solution with the concentration of 0.05mol/L for 6 hours at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 550 ℃ muffle furnace for 24 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 7
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a nitric acid solution with the concentration of 0.05mol/L for 4 hours at the temperature of 80 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 600 ℃ muffle furnace for 8 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 8
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a succinic acid solution with the concentration of 0.1mol/L for 5h at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite and clay, extruding into strips, forming, drying the dried strip mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and roasting in a 600 ℃ muffle furnace for 6 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 28% of the total weight of the modified SAPO-34 molecular sieve, and the clay accounts for 2% of the total weight of the modified SAPO-34 molecular sieve.
Example 9
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 60 hours under the condition that the partial pressure of the water vapor is 0.1Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with oxalic acid solution with the concentration of 0.05mol/L for 3 hours at the temperature of 60 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite, extruding into strips, forming, drying the dried strip-shaped mixture in a 120 ℃ oven for 6 hours, crushing, screening out particles with the diameter of 0.6-0.9mm, and baking in a 600 ℃ muffle furnace for 10 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 30% of the total weight of the modified SAPO-34 molecular sieve.
Example 10
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a nitric acid solution with the concentration of 0.05mol/L for 4 hours at the temperature of 80 ℃ to obtain a precursor II;
s3, tabletting, molding and crushing the precursor II, screening out particles with the diameter of 0.6-0.9mm, and roasting in a muffle furnace at 600 ℃ for 6h to obtain the modified SAPO-34 molecular sieve.
Example 11
A preparation method of a modified SAPO-34 molecular sieve comprises the following steps:
s1, mixing commercial SAPO-34 molecular sieve (same batch as the sample in example 1) at 800 deg.C, and water liquid phase mass space velocity of 1.6h-1Carrying out hydrothermal treatment on water vapor for 40h under the condition that the partial pressure of the water vapor is 0.05Mpa in an inert atmosphere to obtain a precursor I;
s2, treating the precursor I with a nitric acid solution with the concentration of 0.05mol/L for 4 hours at the temperature of 80 ℃ to obtain a precursor II;
s3, uniformly mixing the precursor II with pseudo-boehmite and clay, performing ball-spraying molding, screening particles with the diameter of 0.6-0.9mm, and roasting in a muffle furnace at 600 ℃ for 6 hours to obtain the modified SAPO-34 molecular sieve, wherein the pseudo-boehmite accounts for 28% of the total weight of the modified SAPO-34 molecular sieve, and the clay accounts for 2% of the total weight of the modified SAPO-34 molecular sieve.
Comparative example
Uniformly mixing a commercial SAPO-34 molecular sieve (which is the same batch as the sample in example 1) and pseudo-boehmite, extruding and molding, wherein the pseudo-boehmite accounts for 30% of the total weight of the unmodified SAPO-34 molecular sieve, drying the dried strip mixture in an oven at 120 ℃ for 6h, crushing and screening out particles with the diameter of 0.6-0.9mm, and roasting in a muffle furnace at 600 ℃ for 6h to obtain the unmodified SAPO-34 molecular sieve.
Examples of the experiments
The modified SAPO-34 molecular sieves prepared in examples 1 to 11 and the unmodified SAPO-34 molecular sieves prepared in comparative examples were evaluated as catalysts in a fixed bed reactor under the following reaction conditions: methanol aqueous solution (40 wt% methanol, 60 wt% water) is used as raw material, the reaction temperature is 475 ℃, the reaction pressure is 0.01-1.0MPa, and the methanol weight space velocity is 2.0h-1Under the condition of (3), the raw materials are subjected to catalytic reaction through a catalyst bed layer to generate low-carbon olefin and the like. The results are shown in Table 1.
Wherein the conversion rate X of methanolmSelectivity of ethylene and propylene SE+PThe calculation methods are respectively as follows:
note: methanoinRepresents the molar flow rate of methanol entering the reactor per unit time; methane alcoholoutRepresents the molar flow rate of methanol out of the reactor per unit time; DMEoutExpressing the molar flow of dimethyl ether out of the reactor per unit time; ethylene (E)outRepresents the molar flow of ethylene out of the reactor per unit time; propyleneoutRepresents the molar flow of propylene out of the reactor per unit time.
TABLE 1 Experimental results for the conversion of methanol to olefins
TABLE 1 reaction results for methanol conversion to olefins
| Examples | 8 | 9 | 10 | 11 | Comparative example |
| Temperature (. degree.C.) for Water treatment | 800 | 800 | 800 | 800 | Is free of |
| Water liquid phase mass space velocity (h)-1) | 1.6 | 1.6 | 1.6 | 1.6 | Is free of |
| Time of Water treatment (h) | 40 | 60 | 40 | 40 | Is free of |
| Kind of acid treatment | Succinic acid | Oxalic acid | Nitric acid | Nitric acid | Is free of |
| Acid treatment concentration (mol/L) | 0.1 | 0.05 | 0.05 | 0.05 | Is free of |
| Temperature (. degree.C.) for acid treatment | 60 | 60 | 80 | 80 | Is free of |
| Acid treatment time (h) | 5 | 3 | 4 | 4 | Is free of |
| Form of molding | Extrusion strip | Extrusion strip | Tabletting | Spray ball | Extrusion strip |
| Relative crystallinity (%) | 87 | 82 | 85 | 85 | 100 |
| Xm(％) | 100 | 100 | 100 | 100 | 100 |
| SE+P(％) | 76.9 | 72.9 | 74.0 | 76.2 | 72.5 |
| Maximum temperature rise (. degree.C.) of the reactor bed at 3min of feed | +7 | +5 | +10 | +5 | +49 |
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent technical solutions made by using the contents of the present invention in the specification can be directly or indirectly applied to other related technical fields, and are within the scope of the present invention.
Claims (10)
1. The preparation method of the modified SAPO-34 molecular sieve is characterized by comprising the following steps of:
s1, the SAPO-34 molecular sieve is put at the temperature of 400 ℃ and 800 ℃, and the water-liquid phase mass space velocity is 0.06-3 h-1Carrying out hydrothermal treatment on water vapor for 1-80h under the condition that the partial pressure of the water vapor is 0.01-0.1Mpa in an inert atmosphere to obtain a precursor I;
s2, carrying out acid treatment on the precursor I at the temperature of 40-90 ℃ for 0.5-10h to obtain a precursor II;
s3, mixing the precursor II with an adhesive, and roasting for 5-24h at the temperature of 450-650 ℃ after molding to obtain the modified SAPO-34 molecular sieve.
2. The method of claim 1, wherein the SAPO-34 molecular sieve in S1 has a chabazite-type structure with an average particle size of 300nm to 5 μm and a total pore volume of 0.1 to 1cm as measured by physical adsorption3(g) BET specific surface area of 200-2/g。
3. The preparation method according to claim 1, wherein in S1, the temperature of the hydrothermal treatment is 600-800 ℃, and the mass space velocity of the water phase is 0.1-2.5h-1The partial pressure of water vapor in inert atmosphere is 0.04-0.1Mpa, and the time of hydrothermal treatment is 1-50 h.
4. The method according to claim 1, wherein the acid treatment in S2 is carried out at a temperature of 60 to 90 ℃ for a time of 0.5 to 6 hours.
5. The method according to claim 1 or 4, wherein in S2, the acid-treated acid solution is at least one of nitric acid, oxalic acid, citric acid and succinic acid, and the concentration of the acid solution is 0.01-0.2 mol/L.
6. The method according to claim 5, wherein the acid solution has a concentration of 0.02 to 0.1 mol/L.
7. The method according to claim 1, wherein the binder is at least one of silica sol, alumina sol, pseudo-boehmite, and clay at S3.
8. The method according to claim 1 or 7, wherein the molding is tablet, extrusion or spray ball molding in S3.
9. The method of claim 1 or 7, wherein the binder is present in an amount of 10 to 60 wt.% based on the weight of the modified SAPO-34 molecular sieve.
10. Use of a modified SAPO-34 molecular sieve obtained by the method of any one of claims 1 to 9 as a catalyst in an MTO reaction.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095163A (en) * | 1991-02-28 | 1992-03-10 | Uop | Methanol conversion process using SAPO catalysts |
| CN101172246A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Process for preparation of propylene catalysts with methanol conversion |
| CN102259883A (en) * | 2011-05-20 | 2011-11-30 | 大连理工大学 | Dealuminzation method of hydrogenous and ammonic Y,ZSM-5,beta and SAPO-34 molecular sieves |
| CN107285342A (en) * | 2016-03-31 | 2017-10-24 | 中国科学院上海高等研究院 | The method of solid acid post processing synthesis multi-stage porous SAPO-34 molecular sieves |
| CN111320186A (en) * | 2018-12-13 | 2020-06-23 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5095163A (en) * | 1991-02-28 | 1992-03-10 | Uop | Methanol conversion process using SAPO catalysts |
| CN101172246A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Process for preparation of propylene catalysts with methanol conversion |
| CN102259883A (en) * | 2011-05-20 | 2011-11-30 | 大连理工大学 | Dealuminzation method of hydrogenous and ammonic Y,ZSM-5,beta and SAPO-34 molecular sieves |
| CN107285342A (en) * | 2016-03-31 | 2017-10-24 | 中国科学院上海高等研究院 | The method of solid acid post processing synthesis multi-stage porous SAPO-34 molecular sieves |
| CN111320186A (en) * | 2018-12-13 | 2020-06-23 | 国家能源投资集团有限责任公司 | SAPO-34 molecular sieve, and preparation method and application thereof |
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