CN116371463A - Low-attrition rate SAPO-34 molecular sieve catalyst, and preparation method and application thereof - Google Patents
Low-attrition rate SAPO-34 molecular sieve catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 72
- 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 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 64
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 41
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003513 alkali Substances 0.000 claims abstract description 35
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 21
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 62
- 239000000084 colloidal system Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 239000004005 microsphere Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 12
- 238000009718 spray deposition Methods 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 7
- 239000011268 mixed slurry Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 carbon olefins Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The application discloses a low-abrasion rate SAPO-34 molecular sieve catalyst, a preparation method and application thereof, wherein the preparation method of the molecular sieve catalyst comprises the following steps: mixing kaolin, SAPO-34 molecular sieve powder, silica sol, quaternary ammonium alkali solution and water uniformly to prepare catalyst slurry, and then spray drying and roasting. The molecular sieve catalyst is applied to the reaction of preparing the low-carbon olefin from the methanol, can solve the problem of high catalyst abrasion rate, improves the conversion rate and the selectivity of the catalyst, and prolongs the service life of the catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of molecular sieve catalysts, and particularly relates to a low-attrition rate SAPO-34 molecular sieve catalyst, and a preparation method and application thereof.
Background
Among several basic chemical products that are most produced and consumed worldwide, ethylene and propylene rank first and second, respectively. In industrial production, ethylene and propylene are mainly prepared by cracking petroleum products such as light oil, heavy oil, light diesel oil and the like, and a non-petroleum route for preparing low-carbon olefin is one of the feasible methods for solving the problem of energy shortage, and a route for preparing low-carbon olefin (MTO) from methanol is considered as an ideal alternative process, so that the method has great development advantages.
Among numerous MTO molecular sieve catalysts, SAP0-34 molecular sieve with topological structure has proper acid strength, unique pore structure, good thermal stability and hydrothermal stability, and shows excellent catalytic activity and low-carbon olefin selectivity in methanol-to-olefin reaction; however, the MTO reaction catalyzed by the SAPO-34 molecular sieve has the advantages of high reaction speed, strong heat release, rapid carbon deposition deactivation, and the reaction mode of matching the circulating fluidized bed and the SAPO-34 molecular sieve catalyst, so that the reaction-regeneration of the catalyst, the rapid removal of reaction heat, the accurate control of bed temperature and the like can be realized.
The attrition index of a catalyst is a measure of the strength of the catalyst. Abrasion and breakage of the catalyst in the fluidized bed due to impact of air flow, collision between particles and walls, etc. are unavoidable, and therefore, compared with a fixed bed catalyst, the fluidized bed catalyst needs to ensure sufficient strength; the catalyst abrasion rate is high, and the catalyst running loss is increased, so that the reaction performance of the catalyst is reduced, the production cost is increased, the economy is reduced, and the fluidization state in the reactor can be possibly changed when serious; silica sol is one of the most commonly used colloids in spray forming methods, however, the abrasion rate of products obtained by spraying silica sol alone is generally high, and therefore, research on how to reduce the abrasion rate of catalysts spray formed with silica sol as a colloid is an important research direction in this field.
Disclosure of Invention
The invention aims to provide a low-attrition rate SAPO-34 molecular sieve catalyst, a preparation method and application thereof, and is applied to a reaction for preparing low-carbon olefin from methanol, so that the problem of high attrition rate of the catalyst is solved, and meanwhile, the conversion rate and selectivity of the catalyst are improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing a low attrition rate SAPO-34 molecular sieve catalyst, comprising: mixing kaolin, SAPO-34 molecular sieve powder, silica sol, quaternary ammonium alkali solution and water uniformly to prepare catalyst slurry, and then spray drying and roasting.
The method comprises the following steps:
1) Preparing slurry: adding SAPO-34 molecular sieve powder and kaolin into deionized water, pulping and uniformly mixing to prepare slurry I; adding silica sol into the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state to prepare slurry II;
2) Grinding the slurry II by a colloid mill to prepare colloid running-in slurry;
3) Spray forming: spraying and forming colloid running-in slurry to prepare catalyst microspheres;
4) Roasting: and roasting the catalyst microspheres to obtain the low-attrition rate SAPO-34 molecular sieve catalyst.
In the step 1), the solid content of the slurry I is 20-40% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 20-40% by weight of the dry basis, and the kaolin accounts for 60-80% by weight of the dry basis.
In the step 1), the silica sol is addedThe weight of the silica sol is 18-30% of the weight of the slurry, and SiO in the silica sol 2 The weight content is 28-32%.
In the step 1), the addition amount of the quaternary ammonium base solution is that according to the quaternary ammonium base and SiO in the silica sol 2 The molar ratio of the quaternary ammonium alkali solution is 0.5-5, and the weight concentration of the quaternary ammonium alkali solution is 5-30%.
In the step 1), the quaternary ammonium alkali solution is preferably at least one of tetrabutylammonium hydroxide solution, tetrapropylammonium hydroxide solution, tetraethylammonium hydroxide solution and tetramethylammonium hydroxide solution.
In the above step 2), the slurry II is preferably subjected to colloid mill grinding treatment for 3 to 5 times.
In the step 3), during the spray forming, the spray parameters are as follows: the inlet temperature of the spray tank is 340-360 ℃, the outlet temperature of the spray tank is 230-250 ℃, the rotating speed of the atomizing disk is 25-30rpm/min, and the sample injection amount of the atomizing disk is 20-30ml/min.
In the step 4), the roasting temperature is 550-650 ℃ and the roasting time is 4-8h.
In a second aspect, the invention provides a low attrition rate SAPO-34 molecular sieve catalyst, obtained by the method of preparation described above.
In a third aspect, the invention provides an application of the low attrition rate SAP0-34 molecular sieve catalyst in a reaction for preparing low carbon olefins from methanol.
In a fourth aspect, the present invention provides a method for preparing low-carbon olefin from methanol, which adopts the low attrition rate SAP0-34 molecular sieve catalyst, the method comprising: loading molecular sieve catalyst into fluidized bed reactor, heating the fluidized bed reactor to 400-550 deg.C, controlling pressure to 0.1-0.4MPa, and controlling mass space velocity to 1-3h -1 And introducing methanol-deionized water solution for reaction.
Preferably, the mass percentage of the methanol in the methanol-deionized water solution is 90%.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. silica sol and quaternary ammonium base are added into mixed slurry of SAPO-34 molecular sieve powder and kaolin, catalyst microspheres are obtained through a spray forming process, and after roasting, the abrasion rate of the obtained molecular sieve catalyst is obviously reduced and can be reduced to 0.1%;
2. the low-abrasion-rate SAPO-34 molecular sieve provided by the invention has excellent catalytic performance in a reaction for preparing low-carbon olefin from methanol, and can obviously improve the selectivity of the low-carbon olefin, wherein the total yield of ethylene and propylene can reach more than 89%, and the service life of the catalyst is obviously prolonged.
Detailed Description
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following description of the embodiments of the present invention will clearly illustrate the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which are obtained by a person skilled in the art based on the embodiments of the present invention, fall within the scope of protection of the present invention.
In the embodiment of the invention, the dry basis of the raw material SAPO-34 molecular sieve powder is 84 percent by weight.
In the embodiment of the invention, the dry basis of the raw material kaolin is 86% by weight.
In the embodiment of the invention, siO of the raw material silica sol 2 The weight content is 30%.
In the embodiment of the invention, the weight concentration of the tetrabutylammonium hydroxide solution, the tetrapropylammonium hydroxide solution, the tetraethylammonium hydroxide solution and the tetramethylammonium hydroxide solution is 25%.
In the embodiment of the invention, the diameter of the prepared catalyst microsphere is 20-120 mu m after spray molding.
In the embodiment of the invention, the service life of the catalyst is counted by starting the methanol charging, and the counting is stopped when the catalyst yield is reduced by more than 10%.
Example 1
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 40% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 20% by weight of the dry basis, and the kaolin accounts for 80% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 10 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is as follows the adding amount of the quaternary ammonium alkali solution and SiO in the silica sol 2 The molar ratio of (2) is 5, and a mixed slurry is prepared; the quaternary ammonium alkali solution is tetramethyl ammonium hydroxide solution;
(3) Carrying out colloid running-in treatment on the mixed slurry for 5 times to prepare colloid running-in slurry, wherein the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Example 2
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 35% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 25% by weight of the dry basis, and the kaolin accounts for 75% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 15 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is based on the weight of the quaternary ammonium alkali and SiO in the silica sol 2 The molar ratio of (2) is 2, and mixed slurry is prepared; season for seasonThe ammonium alkali solution is tetraethylammonium hydroxide solution;
(3) Carrying out colloid running-in treatment on the mixed slurry for 5 times to prepare colloid running-in slurry, wherein the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Example 3
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 30% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 30% by weight of the dry basis, and the kaolin accounts for 70% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 20 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is as follows the adding amount of the quaternary ammonium alkali solution and SiO in the silica sol 2 The molar ratio of (2) is 1, and a mixed slurry is prepared; the quaternary ammonium alkali solution is tetrapropylammonium hydroxide solution;
(3) Carrying out colloid running-in treatment on the mixed slurry for 5 times to prepare colloid running-in slurry, wherein the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Example 4
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 25% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 35% by weight of the dry basis, and the kaolin accounts for 65% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 25 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is based on the weight of the quaternary ammonium alkali and SiO in the silica sol 2 The molar ratio of (2) is 0.5, and a mixed slurry is prepared; the quaternary ammonium alkali solution is tetrabutylammonium hydroxide solution;
(3) Colloid grinding treatment is carried out on the mixed slurry for 4 times to prepare colloid grinding slurry, and the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Example 5
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 20% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 40% by weight of the dry basis, and the kaolin accounts for 60% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 20 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is according to seasonsSiO in ammonium base and silica sol 2 The molar ratio of (3) is 3, and mixed slurry is prepared; the quaternary ammonium alkali solution is tetramethyl ammonium hydroxide solution;
(3) Carrying out colloid running-in treatment on the mixed slurry for 5 times to prepare colloid running-in slurry, wherein the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at 550 ℃ for 6 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Example 6
The embodiment provides a preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst, which comprises the following steps:
(1) Adding SAPO-34 molecular sieve powder (200 g) and kaolin into deionized water, pulping and uniformly mixing to prepare slurry; the solid content of the slurry is 20% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 40% by weight of the dry basis, and the kaolin accounts for 60% by weight of the dry basis;
(2) Adding silica sol into the slurry, wherein the adding amount of the silica sol is 15 percent of the weight of the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state, wherein the adding amount of the quaternary ammonium alkali solution is based on the weight of the quaternary ammonium alkali and SiO in the silica sol 2 The molar ratio of (2) is 4, and a mixed slurry is prepared; the quaternary ammonium alkali solution is tetramethyl ammonium hydroxide solution;
(3) Carrying out colloid running-in treatment on the mixed slurry for 5 times to prepare colloid running-in slurry, wherein the D50 of the slurry is less than 2 mu m;
(4) Carrying out spray forming on colloid running-in slurry, wherein the spray parameters are as follows: the inlet temperature of the atomizing disc is 350 ℃, the outlet temperature of the atomizing disc is 240 ℃, the rotating speed of the atomizing disc is 28rpm/min, and the sample injection amount of the atomizing disc is 25ml/min; preparing catalyst microspheres;
(5) And (3) placing the catalyst microspheres in a muffle furnace for roasting at the temperature of 650 ℃ for 4 hours to obtain the low-abrasion-rate SAPO-34 molecular sieve catalyst.
Comparative example 1
The process for preparing a SAPO-34 molecular sieve catalyst of this comparative example is the same as in example 1, except that: after adding the silica sol, no quaternary ammonium base solution is added; directly grinding, spraying and roasting the mixture to prepare the molecular sieve catalyst product.
Comparative example 2
The process for preparing a SAPO-34 molecular sieve catalyst of this comparative example is the same as in example 1, except that: after the silica sol is added, the addition amount of the tetramethylammonium hydroxide solution is as follows 2 The molar ratio of (2) was 0.2.
Comparative example 3
The process for preparing a SAPO-34 molecular sieve catalyst of this comparative example is the same as in example 1, except that: after the silica sol is added, the addition amount of the tetramethylammonium hydroxide solution is as follows 2 The molar ratio of (2) was 8.
Comparative example 4
The process for preparing a SAPO-34 molecular sieve catalyst of this comparative example is the same as in example 1, except that: adding 25% trimethylamine solution under stirring after adding silica sol, wherein the addition amount of the trimethylamine solution is that SiO in the trimethylamine and the silica sol is 2 The molar ratio of (2) was 5.
Example 7
The 10 samples obtained in examples 1 to 6 and comparative examples 1 to 4 were subjected to methanol-to-olefin performance evaluation; weighing 100g of molecular sieve catalyst product, loading the molecular sieve catalyst product into a fluidized bed reactor, heating and controlling the pressure of the reactor, and then introducing 90wt% methanol-deionized water solution for reaction; the reaction temperature is 440 ℃, and the mass space velocity of the methanol solution is 2.0h -1 The reaction pressure is 0.25MPa; the obtained product was analyzed by online gas chromatography (Agilcnt 7890) and the results are shown in table 1;
table 1 MTO reaction test results of catalysts prepared in examples
As can be seen from Table 1, inventive examples 1-6 significantly reduced catalyst attrition rates and prolonged catalyst life with overall yields of ethylene and propylene exceeding 89%, with catalyst attrition rates of example 1 as low as 0.10%. In addition, too high or too low a quantity of quaternary ammonium base can adversely affect the life and attrition rate of the catalyst, which would not be acceptable if the quaternary ammonium base were replaced with trimethylamine.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a low-attrition rate SAPO-34 molecular sieve catalyst is characterized in that: comprising the following steps: mixing kaolin, SAPO-34 molecular sieve powder, silica sol, quaternary ammonium alkali solution and water uniformly to prepare catalyst slurry, and then spray drying and roasting.
2. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: the method comprises the following steps:
1) Preparing slurry: adding SAPO-34 molecular sieve powder and kaolin into deionized water, pulping and uniformly mixing to prepare slurry I; adding silica sol into the slurry, stirring uniformly again, and then adding quaternary ammonium alkali solution in a stirring state to prepare slurry II;
2) Grinding the second slurry by a colloid mill, preferably 3-5 times; preparing colloid running-in slurry;
3) Spray forming: spraying and forming colloid running-in slurry to prepare catalyst microspheres;
4) Roasting: and roasting the catalyst microspheres to obtain the low-attrition rate SAPO-34 molecular sieve catalyst.
3. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: the solid content of the slurry I is 20-40% by weight of the dry basis, wherein the SAPO-34 molecular sieve powder accounts for 20-40% by weight of the dry basis, and the kaolin accounts for 60-80% by weight of the dry basis.
4. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: the addition amount of the silica sol is 18-30% of the weight of the slurry, and SiO in the silica sol 2 The weight content is 28-32%.
5. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: the addition amount of the quaternary ammonium alkali solution is based on the quaternary ammonium alkali and Sio in silica sol 2 The molar ratio of the quaternary ammonium alkali solution is 0.5-5, and the weight concentration of the quaternary ammonium alkali solution is 5-30%; preferably, the quaternary ammonium hydroxide solution is at least one of tetrabutylammonium hydroxide solution, tetrapropylammonium hydroxide solution, tetraethylammonium hydroxide solution, and tetramethylammonium hydroxide solution.
6. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: during spray forming, the spray parameters are as follows: the inlet temperature of the atomizing disc is 340-360 ℃, the outlet temperature of the atomizing disc is 230-250 ℃, the rotating speed of the atomizing disc is 25-30rpm/min, and the sample injection amount of the atomizing disc is 20-30ml/min.
7. The method for preparing the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 1, wherein: the roasting temperature is 550-650 ℃ and the roasting time is 4-8h.
8. A low attrition rate SAPO-34 molecular sieve catalyst, characterized by: is obtained by the preparation method according to any one of claims 1 to 7.
9. The use of the low attrition rate SAPO-34 molecular sieve catalyst of claim 8 in a reaction for the production of low olefins from methanol.
10. A method for preparing low-carbon olefin from methanol is characterized by comprising the following steps: the use of the low attrition rate SAPO-34 molecular sieve catalyst as claimed in claim 8, which method comprises: loading molecular sieve catalyst into fluidized bed reactor, heating the fluidized bed reactor to 400-550 deg.C, controlling pressure to 0.1-0.4MPa, and controlling mass space velocity to 1-3h -1 Introducing methanol-deionized water solution for reaction;
preferably, the mass percentage of the methanol in the methanol-deionized water solution is 90%.
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