CN116371454A - Preparation method and application of light hydrocarbon cracking catalyst - Google Patents
Preparation method and application of light hydrocarbon cracking catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000005336 cracking Methods 0.000 title claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 107
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000004005 microsphere Substances 0.000 claims abstract description 18
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 12
- 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 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012688 phosphorus precursor Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000006012 monoammonium phosphate Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000004537 pulping Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000002352 steam pyrolysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation method and application of a light hydrocarbon cracking catalyst, comprising the following steps: evenly mixing deoxidized ionized water, a ZSM-5 molecular sieve with a low silica-alumina ratio and a ZSM-5 molecular sieve with a high silica-alumina ratio to obtain slurry A; mixing deoxidized ionized water, kaolin and alumina sol, and then adding the mixture into the slurry A to obtain slurry B; uniformly mixing the slurry B and pseudo-boehmite to obtain slurry C; acidifying the slurry C to obtain slurry D; mixing the slurry D with a phosphorus precursor to obtain slurry E; ball milling the slurry E and granulating to obtain microsphere particles; and drying and burning the microsphere particles to obtain the light hydrocarbon cracking catalyst. The invention adopts the complex of the ZSM-5 molecular sieve with low silica-alumina ratio and the ZSM-5 molecular sieve with high silica-alumina ratio, so that the prepared catalyst has high yield of low-carbon olefin, good selectivity and good stability when being used for naphtha cracking, and is easy for industrialized application.
Description
Technical Field
The invention belongs to the technical field of petroleum catalytic cracking, and particularly relates to a preparation method and application of a light hydrocarbon cracking catalyst.
Background
Ethylene and propylene are important basic raw materials in petrochemical industry, and the traditional production mode is mainly prepared by a tube furnace steam cracking method. The cracking raw materials comprise naphtha, light diesel oil, ethane, liquefied petroleum gas and the like. However, with the rapid increase of the demand of diene derivatives, the propylene yield obtained by co-production by thermal cracking cannot meet the increasing demand of propylene in domestic and foreign markets. At the same time, steam pyrolysis itself suffers from a number of disadvantages. Therefore, on the basis of optimizing the allocation of pyrolysis raw material resources, the technology for preparing the low-carbon olefin by adopting a new process and a new technology to replace the traditional steam pyrolysis technology has become the necessary trend of development in the field. Light hydrocarbon catalytic cracking and other processes are gradually rising and developing in recent years, and the demand of the market for propylene is relieved to a certain extent.
For oil refining enterprises, the oil refining productivity is greatly excessive due to the rising of large-scale refining integrated enterprises, so that the oil market is larger than the demand. Therefore, the conversion of low-value-added oil products into high-value-added chemicals or chemical intermediates becomes a necessary trend. The light hydrocarbon catalytic cracking process is one technological process with great market foreground, and may be used in cracking alkane, alkene and cycloalkane below 10 into ethylene, propylene and BTX in the presence of catalyst to reduce gasoline yield to some extent, convert the hydrocarbon into low carbon olefin resource with high added value and increase the profitability of enterprise.
The hot spot and the difficulty in the technical field of catalytic cracking are the research and the preparation of the catalyst, however, the process for preparing the catalyst in the prior art is complicated, and the industrialization application is difficult to realize.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and application of a light hydrocarbon cracking catalyst, wherein the method is simple, and the light hydrocarbon catalytic cracking catalyst has the advantages of high yield of light olefins, good selectivity, easy industrial application and the like.
The invention provides a preparation method of a light hydrocarbon cracking catalyst, which comprises the following steps:
evenly mixing deoxidized ionized water, a ZSM-5 molecular sieve with a low silica-alumina ratio and a ZSM-5 molecular sieve with a high silica-alumina ratio to obtain slurry A;
mixing deoxidized ionized water, kaolin and alumina sol, and then adding the mixture into the slurry A to obtain slurry B;
uniformly mixing the slurry B and pseudo-boehmite to obtain slurry C;
acidifying the slurry C to obtain slurry D;
mixing the slurry D with a phosphorus precursor to obtain slurry E;
ball milling the slurry E and granulating to obtain microsphere particles;
and drying and burning the microsphere particles to obtain the light hydrocarbon cracking catalyst.
In the invention, the mole ratio of Si to Al in the low silica alumina ratio ZSM-5 molecular sieve is 20-50; the mole ratio of Si to Al in the ZSM-5 molecular sieve with high silicon-aluminum ratio is 60-150. In a specific embodiment, the mole ratio of Si to Al in the low silica alumina ratio ZSM-5 molecular sieve is 25; the mole ratio of Si to Al in the ZSM-5 molecular sieve with high silica alumina ratio is 110.
The ZSM-5 molecular sieve adopted by the invention has special MFI pore canal structure, adjustable acid property and good thermal stability. The invention compounds the ZSM-5 molecular sieve with low silicon-aluminum ratio and the ZSM-5 molecular sieve with high silicon-aluminum ratio, so that the prepared catalyst has the advantages of high yield, high selectivity and good stability of light hydrocarbon cracking reaction.
In the invention, the mass ratio of the total amount of deoxidized ion water to the total amount of molecular sieve to the mass ratio of kaolin, alumina sol, pseudo-boehmite to hydrochloric acid is (30-70): 5-40): 3-20): 3-30): 1-10): 0.5-8.
The invention preferably adopts hydrochloric acid for acidification; the mass concentration of the hydrochloric acid is 35-37%. The acidification time is 50-80 min.
In the invention, the phosphorus precursor is selected from one or more of phosphoric acid, monoammonium phosphate and diammonium phosphate; the mass ratio of the phosphorus precursor to the slurry D is 0.5-8%.
The invention adopts high-temperature spray centrifugal equipment to mold the slurry D after ball milling, and microsphere particles are prepared. The particle size of the microsphere particles is 20-150 mu m.
In the invention, the drying temperature is 100-130 ℃, and the drying time is 5-8 hours; the roasting temperature is 450-550 ℃, and the roasting time is 3-6 h.
The invention provides an application of the light hydrocarbon cracking catalyst prepared by the preparation method in naphtha cracking.
The invention provides a preparation method of a light hydrocarbon cracking catalyst, which comprises the following steps: evenly mixing deoxidized ionized water, a ZSM-5 molecular sieve with a low silica-alumina ratio and a ZSM-5 molecular sieve with a high silica-alumina ratio to obtain slurry A; mixing deoxidized ionized water, kaolin and alumina sol, and then adding the mixture into the slurry A to obtain slurry B; uniformly mixing the slurry B and pseudo-boehmite to obtain slurry C; acidifying the slurry C to obtain slurry D; mixing the slurry D with a phosphorus precursor to obtain slurry E; ball milling the slurry E and granulating to obtain microsphere particles; and drying and burning the microsphere particles to obtain the light hydrocarbon cracking catalyst. The invention adopts the complex of the ZSM-5 molecular sieve with low silica-alumina ratio and the ZSM-5 molecular sieve with high silica-alumina ratio, so that the prepared catalyst has high yield of low-carbon olefin, good selectivity and good stability when being used for naphtha cracking, and is easy for industrialized application.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe in detail a preparation method and application of a light hydrocarbon cracking catalyst according to the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 150g of ZSM-5 (SiO) having a low silica-alumina ratio was added to 1000g of deionized water 2 /Al 2 O 3 =25) molecular sieves and 150g high silica to alumina ratio ZSM-5 (SiO) 2 /Al 2 O 3 =110) molecular sieve, ball milling and mixing uniformly in a ball mill to obtain slurry a;
(2) 220g of kaolin and 320g of aluminum sol are added into deoxidized ionized water, slurry A is added after uniform stirring, and slurry B is obtained by mixing and pulping;
(3) Adding 100g of pseudo-boehmite into the slurry B, and uniformly stirring to obtain slurry C;
(4) Adding 30g of hydrochloric acid into the slurry C for acidification, and uniformly stirring to obtain slurry D;
(5) Adding 30g of monoammonium phosphate into the slurry D, and uniformly stirring to obtain slurry E;
(6) Ball milling is carried out on the slurry E by adopting a ball mill, and the slurry after ball milling is molded by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the granularity of 20-150 mu m;
(7) The microspherical catalyst was dried at 120℃for 3 hours and calcined at 540℃for 4 hours, and the calcined catalyst was evaluated using a riser.
Example 2
(1) 100g of ZSM-5 (SiO) with low silica-alumina ratio was added to 1000g of deionized water 2 /Al 2 O 3 Molecular sieves and 200g high silica to alumina ratio ZSM-5 (SiO) 2 /Al 2 O 3 =110) molecular sieve, ball milling and mixing uniformly in a ball mill to obtain slurry a;
(2) 220g of kaolin and 320g of aluminum sol are added into deoxidized ionized water, slurry A is added after uniform stirring, and slurry B is obtained by mixing and pulping;
(3) Adding 100g of pseudo-boehmite into the slurry B, and uniformly stirring to obtain slurry C;
(4) Adding 30g of hydrochloric acid into the slurry C for acidification, and uniformly stirring to obtain slurry D;
(5) 28g of monoammonium phosphate is added into the slurry D and stirred uniformly to obtain slurry E;
(6) Ball milling is carried out on the slurry E by adopting a ball mill, and the slurry after ball milling is molded by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the granularity of 20-150 mu m;
(7) The microspherical catalyst was dried at 120℃for 3 hours and calcined at 540℃for 4 hours, and the calcined catalyst was evaluated using a riser.
Example 3
(1) 200g of ZSM-5 (SiO) having a low silica/alumina ratio was added to 1000g of deionized water 2 /Al 2 O 3 =25) molecular sieves and 100g high silica to alumina ratio ZSM-5 (SiO) 2 /Al 2 O 3 =110) molecular sieve, ball milling and mixing uniformly in a ball mill to obtain slurry a;
(2) 220g of kaolin and 320g of aluminum sol are added into deoxidized ionized water, slurry A is added after uniform stirring, and slurry B is obtained by mixing and pulping;
(3) Adding 100g of pseudo-boehmite into the slurry B, and uniformly stirring to obtain slurry C;
(4) Adding 30g of hydrochloric acid into the slurry C for acidification, and uniformly stirring to obtain slurry D;
(5) Adding 35g of monoammonium phosphate into the slurry D, and uniformly stirring to obtain slurry E;
(6) Ball milling is carried out on the slurry E by adopting a ball mill, and the slurry after ball milling is molded by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the granularity of 20-150 mu m;
(7) The microspherical catalyst was dried at 120℃for 3 hours and calcined at 540℃for 4 hours, and the calcined catalyst was evaluated using a riser.
Comparative example 1
(1) 300g of ZSM-5 (SiO) with high silica-alumina ratio is added into 1000g of deoxidized ion water 2 /Al 2 O 3 =110) molecular sieve, ball milling and mixing uniformly in a ball mill to obtainSlurry A;
(2) 220g of kaolin and 320g of aluminum sol are added into deoxidized ionized water, slurry A is added after uniform stirring, and slurry B is obtained by mixing and pulping;
(3) Adding 100g of pseudo-boehmite into the slurry B, and uniformly stirring to obtain slurry C;
(4) Adding 30g of hydrochloric acid into the slurry C for acidification, and uniformly stirring to obtain slurry D;
(5) Adding 25g of monoammonium phosphate into the slurry D, and uniformly stirring to obtain slurry E;
(6) Ball milling is carried out on the slurry E by adopting a ball mill, and the slurry after ball milling is molded by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the granularity of 20-150 mu m;
(7) The microspherical catalyst was dried at 120℃for 3 hours and calcined at 540℃for 4 hours, and the calcined catalyst was evaluated using a riser.
Comparative example 2
(1) 300g of ZSM-5 (SiO) with low silica-alumina ratio was added to 500g of deionized water 2 /Al 2 O 3 =25) molecular sieve, ball milling and mixing uniformly in a ball mill to obtain slurry a;
(2) 220g of kaolin and 320g of aluminum sol are added into deoxidized ionized water, slurry A is added after uniform stirring, and slurry B is obtained by mixing and pulping;
(3) Adding 100g of pseudo-boehmite into the slurry B, and uniformly stirring to obtain slurry C;
(4) Adding 30g of hydrochloric acid into the slurry C for acidification, and uniformly stirring to obtain slurry D;
(5) Adding 35g of monoammonium phosphate into the slurry D, and uniformly stirring to obtain slurry E;
(6) Ball milling is carried out on the slurry E by adopting a ball mill, and the slurry after ball milling is molded by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the granularity of 20-150 mu m;
(7) The microspherical catalyst was dried at 120℃for 3 hours and calcined at 540℃for 4 hours, and the calcined catalyst was evaluated using a riser.
The pilot riser evaluation conditions were:
table 1 evaluation conditions
Table 2 naphtha feedstock properties
TABLE 3 Properties of the product
As can be seen from the above examples, the present invention provides a method for preparing a light hydrocarbon cracking catalyst, comprising the following steps: evenly mixing deoxidized ionized water, a ZSM-5 molecular sieve with a low silica-alumina ratio and a ZSM-5 molecular sieve with a high silica-alumina ratio to obtain slurry A; mixing deoxidized ionized water, kaolin and alumina sol, and then adding the mixture into the slurry A to obtain slurry B; uniformly mixing the slurry B and pseudo-boehmite to obtain slurry C; acidifying the slurry C to obtain slurry D; mixing the slurry D with a phosphorus precursor to obtain slurry E; ball milling the slurry E and granulating to obtain microsphere particles; and drying and burning the microsphere particles to obtain the light hydrocarbon cracking catalyst. The invention adopts the complex of the ZSM-5 molecular sieve with low silica-alumina ratio and the ZSM-5 molecular sieve with high silica-alumina ratio, so that the prepared catalyst has high yield of low-carbon olefin, good selectivity and good stability when being used for naphtha cracking, and is easy for industrialized application. The experimental results show that: the yield of ethylene is 19.65-21.03%, and the yield of propylene is 21.64-23.63%.
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 (9)
1. The preparation method of the light hydrocarbon cracking catalyst comprises the following steps:
evenly mixing deoxidized ionized water, a ZSM-5 molecular sieve with a low silica-alumina ratio and a ZSM-5 molecular sieve with a high silica-alumina ratio to obtain slurry A;
mixing deoxidized ionized water, kaolin and alumina sol, and then adding the mixture into the slurry A to obtain slurry B;
uniformly mixing the slurry B and pseudo-boehmite to obtain slurry C;
acidifying the slurry C to obtain slurry D;
mixing the slurry D with a phosphorus precursor to obtain slurry E;
ball milling the slurry E and granulating to obtain microsphere particles;
and drying and burning the microsphere particles to obtain the light hydrocarbon cracking catalyst.
2. The preparation method according to claim 1, wherein the mole ratio of Si to Al in the low silica alumina ratio ZSM-5 molecular sieve is 20 to 50;
the mole ratio of Si to Al in the ZSM-5 molecular sieve with high silicon-aluminum ratio is 60-150.
3. The preparation method according to claim 1, wherein the mass ratio of the low silica alumina ratio ZSM-5 molecular sieve to the high silica alumina ratio ZSM-5 molecular sieve is 0.1:1-10:1.
4. The preparation method according to claim 1, wherein the mass ratio of the total amount of the deoxidized ion water, the total amount of the molecular sieve, the kaolin, the alumina sol, the pseudo-boehmite and the hydrochloric acid is (30-70): 5-40): 3-20): 3-30): 1-10): 0.5-8.
5. The method of claim 1, wherein the phosphorus precursor is selected from one or more of phosphoric acid, monoammonium phosphate, and diammonium phosphate;
the mass ratio of the phosphorus precursor to the slurry D is 0.5-8%.
6. The method according to claim 1, wherein the granulation is by spray centrifugation.
7. The preparation method according to claim 1, wherein the drying temperature is 100-130 ℃ and the drying time is 5-8 hours;
the roasting temperature is 450-550 ℃, and the roasting time is 3-6 h.
8. The method according to claim 1, wherein the microsphere particles have a particle size of 20 to 150 μm.
9. Use of a light hydrocarbon cracking catalyst prepared by the preparation method of any one of claims 1 to 8 in naphtha cracking.
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