CN107715908B - Hierarchical pore hydrocracking catalyst and preparation method thereof - Google Patents
Hierarchical pore hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN107715908B CN107715908B CN201610665199.9A CN201610665199A CN107715908B CN 107715908 B CN107715908 B CN 107715908B CN 201610665199 A CN201610665199 A CN 201610665199A CN 107715908 B CN107715908 B CN 107715908B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
- 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 66
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 239000011259 mixed solution Substances 0.000 claims abstract description 49
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 150000003657 tungsten Chemical class 0.000 claims abstract description 43
- 150000002815 nickel Chemical class 0.000 claims abstract description 38
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 23
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000012266 salt solution Substances 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 28
- 239000010457 zeolite Substances 0.000 description 28
- 229910021536 Zeolite Inorganic materials 0.000 description 26
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- -1 nickel salt Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- C10G2300/1033—Oil well production fluids
-
- 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
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a hierarchical pore hydrocracking catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing a modified Y/ASA composite molecular sieve for waterCarrying out steam treatment on the thermally synthesized Y/ASA composite molecular sieve, then carrying out mixed solution treatment on ammonium chloride and benzenesulfonic acid, and drying to obtain a modified Y/ASA composite molecular sieve; and secondly, mixing the modified Y/ASA composite molecular sieve with the prepared mixed solution of the metal tungsten salt solution and the nickel salt, adding concentrated nitric acid and pseudo-boehmite, mixing, extruding strips, molding, drying and roasting to obtain the hierarchical pore hydrocracking catalyst. The specific surface area of the multi-stage pore hydrocracking catalyst obtained by the method is 300-450m2The pore volume is 0.29-0.50 ml/g, and the pore size distribution is 5-30 nm.
Description
Technical Field
The invention relates to a hierarchical pore hydrocracking catalyst and a preparation method thereof, belonging to the technical field of catalysts.
Background
At present, the hydrocracking catalyst mainly uses Y-type zeolite and the like as main acidic components, and is obtained by mechanically mixing the main acidic components with carrier materials such as alumina, silicon-aluminum and the like and then extruding and molding the mixture.
The Y-type zeolite is widely applied to the petrochemical fields of hydrocracking and the like due to the unique pore structure, and is a main active component of a hydrocracking catalyst. The silicon-aluminum ratio of the unit cell framework of the Y-type zeolite directly affects the hydrothermal stability and acidity of the zeolite molecular sieve. However, with the heavy and inferior petroleum oils, the conventional zeolites have failed to meet the demanding reaction-regeneration conditions of catalytic cracking; the method has the advantages of improving the ratio of silicon to aluminum of the framework of the Y-type zeolite, reasonably reducing the density of acid centers, improving the relative strength of the acid centers, increasing the mesoporous structure of the zeolite, improving the ratio of cracking/hydrogen transfer activity, reducing the generation of catalytic coking and improving the distribution of products. At present, cheap water glass is generally adopted in the industrial production of NaY molecular sieves as a silicon source, the silicon-aluminum ratio of NaY obtained by direct synthesis is generally not more than 5.6, and the Y-type molecular sieves are limited in catalytic conversion of macromolecules due to small aperture and large particles, so that the application of the Y-type molecular sieves is greatly limited.
The conventional Y molecular sieve is subjected to post-treatment modification to remove part of aluminum atoms in a zeolite framework structure, or silicon supplement is performed on the basis, so that the silicon-aluminum ratio can be well improved, and meanwhile, relatively high crystallinity can be kept. Particularly, the high-silicon-aluminum ratio zeolite obtained by high-temperature steam treatment not only improves the silicon-aluminum ratio of the Y molecular sieve in the treatment process, but also greatly improves other properties, such as stronger acid strength, reduced acid center density, more acid types, secondary mesoporous generation, correspondingly improved catalytic activity, capability of meeting various performance indexes in the field of petrochemical industry and high application value.
Modification of Y-type zeolites, to reduce the sodium content of the zeolite and increase the acidity of the zeolite, and to increase the stability of the zeolite by calcination or high temperature steam dealumination to bring the zeolite unit cell size to between 24.2 and 24.5 angstrom, has been reported in various patents, such as USP3293192, 3449070, 3513108 and 3506400.
CN1060976A and CN1060977A introduce alumina gel and silica-alumina gel into NaY or NaHY zeolite, respectively, and then ammonium exchange, filtration and hydrothermal roasting are carried out to obtain USY zeolite containing amorphous alumina and amorphous silica-alumina, respectively, so that high activity and hydrothermal stability can be obtained, and high crystallinity is kept.
CN1205915A discloses a method for preparing an ultra-stable Y-type molecular sieve, which comprises the steps of treating with high-temperature water vapor and then with an ammonium fluosilicate solution and an inorganic mixed acid.
CN1276267A discloses a method for modifying Y-type zeolite, which mixes Y-type zeolite with low sodium content, oxide of acid-forming metal element and oxide of alkali-forming metal, the modified zeolite has good effect on normal paraffin isomerization under the condition of high-temperature water vapor.
CN1284402A discloses a Y-type zeolite with a secondary pore structure and a preparation method thereof, wherein Y-type zeolite and a silicon-containing solution are impregnated, dried and then treated by steam to obtain the Y-type zeolite with high hydrothermal stability, but the silicon-aluminum ratio is not greatly improved.
CN102264643A discloses that a mesopore-containing zeolite is prepared, and the mesopore-containing zeolite can be obtained by alkali treatment and then ammonium exchange and calcination.
The modification method is only aimed at the investigation of special properties of the treated sample, such as the investigation of preparing zeolite containing secondary mesopores, or the investigation of improving the silicon-aluminum ratio to increase the stability of the zeolite or reducing the sodium content of the zeolite. It is hoped that a treatment method can improve the silicon-aluminum ratio of zeolite, increase the stability of zeolite, reduce sodium content, simultaneously generate secondary mesopores, improve the specific surface and pore volume, highly disperse hydrogenation metal and improve the activity of a hydrocracking catalyst.
Disclosure of Invention
The invention provides a hierarchical pore hydrocracking catalyst and a preparation method thereof, wherein the hierarchical pore hydrocracking catalyst is prepared by mainly adopting a modified Y/ASA composite molecular sieve, a tungsten salt and nickel salt mixed solution, pseudo-boehmite and the like as raw materials through extrusion, molding, drying and roasting. The Y/ASA composite molecular sieve is modified to improve the specific surface area and the pore volume, simultaneously improve the pore size distribution of mesopores and remove amorphous aluminum species of zeolite. The multi-stage pore hydrocracking catalyst obtained by the method has the characteristics of large specific surface area, large pore volume and wide pore size distribution.
The invention provides a preparation method of a hierarchical pore hydrocracking catalyst, which comprises the following steps:
(1) preparation of modified Y/ASA composite molecular sieve
①, carrying out steam treatment on the hydrothermally synthesized Y/ASA composite molecular sieve;
②, performing ion exchange on the Y/ASA composite molecular sieve by using a mixed solution of ammonium chloride and benzenesulfonic acid, filtering, and drying at 50-120 ℃ for 1-4 h to obtain a modified Y/ASA composite molecular sieve;
(2) preparation of mixed solution of tungsten salt and nickel salt
Adding the carbon nano tube and polyacrylic acid into the mixed solution of tungsten salt and nickel salt, and uniformly stirring to obtain a mixed solution of tungsten salt and nickel salt;
(3) preparation of hydrocracking catalyst
①, mixing the modified Y/ASA composite molecular sieve prepared in the step (1) with the mixed solution of tungsten salt and nickel salt prepared in the step (2), wherein the ratio of the modified Y/ASA composite molecular sieve to the mixed solution of tungsten salt and nickel salt is that 1g of the modified Y/ASA composite molecular sieve corresponds to 0.5-1.5 ml of the mixed solution of tungsten salt and nickel salt;
②, adding concentrated nitric acid accounting for 1-8% of the mass of the modified Y/ASA composite molecular sieve, adding pseudo-boehmite accounting for 10-20% of the mass of the modified Y/ASA composite molecular sieve, uniformly mixing, extruding into strips, forming, drying at 50-120 ℃ for 1-4 h, and roasting at 300-550 ℃ for 1-6h to obtain the hierarchical pore hydrocracking catalyst.
According to the preparation method of the hierarchical pore hydrocracking catalyst, ASA in the Y/ASA composite molecular sieve is preferably amorphous silica-alumina.
The preparation method of the multi-stage pore hydrocracking catalyst provided by the invention is characterized in that the temperature for treating the water vapor in the step (1) is preferably between 500 ℃ and 600 ℃, the flow rate of the water vapor is preferably kept between 10ml/min and 25ml/min, and the treatment time is preferably kept between 1h and 6 h.
According to the preparation method of the hierarchical pore hydrocracking catalyst, the ion exchange process in the step (1) is preferably carried out at 80-100 ℃, the concentration of ammonium chloride is preferably 0.01-0.1mol/L, the concentration of benzenesulfonic acid is preferably 0.01-0.1mol/L, and the mass ratio of the Y/ASA composite molecular sieve to the mixed solution of ammonium chloride and benzenesulfonic acid is preferably 1: 2-10.
The preparation method of the hierarchical pore hydrocracking catalyst provided by the invention is characterized in that the specific surface area of the modified Y/ASA composite molecular sieve is preferably 500-700m2Per g, pore volume is preferably 0.45-0.75 ml/g, and the pore size distribution is preferably 5-30 nm.
In the step (2), in the mixed solution of tungsten salt and nickel salt, the concentration of tungsten salt is preferably 10-30 g/ml, the concentration of nickel salt is preferably 5-30 g/ml, the amount of carbon nano tubes is preferably 1-10 wt% of the modified Y/ASA composite molecular sieve, and the amount of polyacrylic acid is preferably 1-10 wt% of the modified Y/ASA composite molecular sieve.
The preparation method of the hierarchical pore hydrocracking catalyst provided by the invention is characterized in that the specific surface area of the hierarchical pore hydrocracking catalyst obtained in the step (3) is preferably 300-450m2The pore volume is preferably 0.29-0.50 ml/g, and the pore size distribution is preferably 5-30 nm.
According to the invention, the Y/ASA composite molecular sieve is mixed with tungsten salt and nickel salt solution, and then added with alumina and concentrated nitric acid to be directly extruded into strips to obtain the multi-stage pore hydrocracking catalyst, so that the step of preparing a catalyst carrier is omitted, the roasting frequency is reduced, the specific surface area and pore volume of the catalyst are improved, and the pore size distribution is improved. The specific surface area of the catalyst is 400-500m2The pore volume is 0.35-0.45 ml/g, and the pore diameter distribution is 5-30 nm.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
(1) Preparation of modified Y/ASA composite molecular sieve
① steam treatment is carried out on 100g of the Y/ASA composite molecular sieve synthesized by the hydrothermal method, the temperature of the steam treatment is 550 ℃, the flow rate of the steam is kept at 17ml/min, and the treatment time is 3 h.
② ion exchange of ammonium chloride and benzene sulfonic acid solution
And carrying out ion exchange on the Y/ASA composite molecular sieve by adopting a mixed solution of ammonium chloride and benzenesulfonic acid. Taking 80g of the Y/ASA composite molecular sieve after the hydrothermal treatment,adding into 240g of mixed solution of ammonium chloride and benzenesulfonic acid, exchanging at 80 deg.C, ammonium chloride concentration of 0.1mol/L, benzenesulfonic acid concentration of 0.1mol/L, filtering, and drying at 110 deg.C for 3 hr. The specific surface area of the obtained treated Y/ASA composite molecular sieve is 530m2The pore volume is 0.54ml/g, and the pore size distribution is 5-30 nm.
(2) Preparation of mixed solution of tungsten salt and nickel salt
100ml of a mixed solution of a tungsten salt and a nickel salt was prepared, the concentration of the tungsten salt being 30g/ml and the concentration of the nickel salt being 5 g/ml. Adding 2g of carbon nano tube and 2g of polyacrylic acid into the tungsten salt and nickel salt mixed solution, and uniformly stirring to obtain the tungsten salt and nickel salt mixed solution.
(3) Preparation of hydrocracking catalyst
Uniformly mixing 60g of Y/ASA composite molecular sieve, 50ml of mixed solution of tungsten salt and nickel salt and 4.5g of concentrated nitric acid, adding 8g of pseudo-boehmite, uniformly mixing, extruding into strips, forming, drying at 110 ℃ for 2h, and roasting at 450 ℃ for 3h to obtain the multi-stage pore hydrocracking catalyst. The specific surface area of the catalyst is 305m2The pore volume is 0.29ml/g, and the pore size distribution is 5-30 nm.
Example 2
(1) Preparation of modified Y/ASA composite molecular sieve
① steam treatment is carried out on 100g of the Y/ASA composite molecular sieve synthesized by the hydrothermal method, the temperature of the steam treatment is 500 ℃, the flow rate of the steam is kept at 25ml/min, and the treatment time is 6 h.
② ion exchange of ammonium chloride and benzene sulfonic acid solution
And carrying out ion exchange on the Y/ASA composite molecular sieve by adopting a mixed solution of ammonium chloride and benzenesulfonic acid. Adding 80g of the Y/ASA composite molecular sieve subjected to the hydrothermal treatment into 400g of a mixed solution of ammonium chloride and benzenesulfonic acid, wherein the exchange temperature is 90 ℃, the ammonium chloride concentration is 0.1mol/L, the benzenesulfonic acid concentration is 0.01mol/L, and after the exchange is finished, filtering the product, and drying at 110 ℃ for 2 h. The specific surface area of the obtained treated Y/ASA composite molecular sieve is 675m2The pore volume is 0.72ml/g, and the pore size distribution is 5-30 nm.
(2) Preparation of mixed solution of tungsten salt and nickel salt
100ml of a mixed solution of a tungsten salt and a nickel salt was prepared, the concentration of the tungsten salt being 10g/ml and the concentration of the nickel salt being 30 g/ml. Adding 2g of carbon nano tube and 4g of polyacrylic acid into the tungsten salt and nickel salt mixed solution, and uniformly stirring to obtain the tungsten salt and nickel salt mixed solution.
(3) Preparation of hydrocracking catalyst
Uniformly mixing 60g of Y/ASA composite molecular sieve, 70ml of mixed solution of tungsten salt and nickel salt and 3.0g of concentrated nitric acid, adding 10g of pseudo-boehmite, uniformly mixing, extruding into strips, forming, drying at 110 ℃ for 2h, and roasting at 550 ℃ for 1h to obtain the multi-stage pore hydrocracking catalyst. The specific surface area of the catalyst is 440m2The pore volume is 0.48ml/g, and the pore size distribution is 5-30 nm.
Example 3
(1) Preparation of modified Y/ASA composite molecular sieve
① steam treatment is carried out on 100g of the Y/ASA composite molecular sieve synthesized by the hydrothermal method, the temperature of the steam treatment is 600 ℃, the flow rate of the steam is kept at 10ml/min, and the treatment time is 1 h.
② ion exchange of ammonium chloride and benzene sulfonic acid solution
And carrying out ion exchange on the Y/ASA composite molecular sieve by adopting a mixed solution of ammonium chloride and benzenesulfonic acid. Adding 80g of the Y/ASA composite molecular sieve subjected to the hydrothermal treatment into 400g of a mixed solution of ammonium chloride and benzenesulfonic acid, wherein the exchange temperature is 90 ℃, the ammonium chloride concentration is 0.1mol/L, the benzenesulfonic acid concentration is 0.1mol/L, filtering the product after the exchange is finished, and drying the product at 110 ℃ for 2 hours. The specific surface area of the obtained treated Y/ASA composite molecular sieve is 675m2The pore volume is 0.72ml/g, and the pore size distribution is 5-30 nm.
(2) Preparation of mixed solution of tungsten salt and nickel salt
100ml of a mixed solution of a tungsten salt and a nickel salt was prepared, the concentration of the tungsten salt being 20g/ml and the concentration of the nickel salt being 20 g/ml. Adding 4g of carbon nano tube and 2g of polyacrylic acid into the tungsten salt and nickel salt mixed solution, and uniformly stirring to obtain the tungsten salt and nickel salt mixed solution.
(3) Preparation of hydrocracking catalyst
Mixing Y/ASA composite molecular sieve 60g, tungsten salt and nickel salt 70ml mixed solution and concentrated nitric acid 3.0g, adding pseudo-boehmite 10g, mixing, extruding to form strips, and adding into the obtained mixtureDrying at 110 ℃ for 2h, and roasting at 300 ℃ for 6h to obtain the hierarchical pore hydrocracking catalyst. The specific surface area of the catalyst is 445m2The pore volume is 0.49ml/g, and the pore size distribution is 5-30 nm.
Example 4
(1) Preparation of modified Y/ASA composite molecular sieve
① steam treatment is carried out on 100g of the Y/ASA composite molecular sieve synthesized by the hydrothermal method, the temperature of the steam treatment is 550 ℃, the flow rate of the steam is kept at 17ml/min, and the treatment time is 3 h.
② ion exchange of ammonium chloride and benzene sulfonic acid solution
And carrying out ion exchange on the Y/ASA composite molecular sieve by adopting a mixed solution of ammonium chloride and benzenesulfonic acid. And adding 80g of the Y/ASA composite molecular sieve subjected to the hydrothermal treatment into 240g of a mixed solution of ammonium chloride and benzenesulfonic acid, wherein the exchange temperature is 90 ℃, the ammonium chloride concentration is 0.05mol/L, the benzenesulfonic acid concentration is 0.05mol/L, and after the exchange is finished, filtering the product, and drying at 110 ℃ for 7 hours. The specific surface area of the obtained treated Y/ASA composite molecular sieve is 632m2The pore volume is 0.65ml/g, and the pore size distribution is 5-30 nm.
(2) Preparation of mixed solution of tungsten salt and nickel salt
100ml of a mixed solution of tungsten salt and nickel salt was prepared, the concentration of tungsten salt was 17g/ml, and the concentration of nickel salt was 17 g/ml. Adding 4g of carbon nano tube and 4g of polyacrylic acid into the tungsten salt and nickel salt mixed solution, and uniformly stirring to obtain the tungsten salt and nickel salt mixed solution.
(3) Preparation of hydrocracking catalyst
Uniformly mixing 60g of Y/ASA composite molecular sieve, 50ml of mixed solution of tungsten salt and nickel salt and 4.5g of concentrated nitric acid, adding 8g of pseudo-boehmite, uniformly mixing, extruding into strips, drying at 110 ℃ for 6h, and roasting at 425 ℃ for 3h to obtain the multi-stage pore hydrocracking catalyst. The specific surface area of the catalyst is 430m2The pore volume is 0.42ml/g, and the pore size distribution is 5-30 nm.
Claims (6)
1. A preparation method of a hierarchical pore hydrocracking catalyst comprises the following steps:
(1) preparation of modified Y/ASA composite molecular sieve
①, carrying out steam treatment on the hydrothermally synthesized Y/ASA composite molecular sieve;
wherein the temperature of the water vapor treatment is between 500 ℃ and 600 ℃, the flow rate of the water vapor is kept between 10mL/min and 25mL/min, and the treatment time is kept between 1h and 6 h;
②, performing ion exchange on the Y/ASA composite molecular sieve by using a mixed solution of ammonium chloride and benzenesulfonic acid, filtering, and drying at 50-120 ℃ for 1-4 h to obtain a modified Y/ASA composite molecular sieve;
wherein in the ion exchange process, the concentration of ammonium chloride is 0.01-0.1mol/L, the concentration of benzenesulfonic acid is 0.01-0.1mol/L, and the mass ratio of the Y/ASA composite molecular sieve to the mixed solution of ammonium chloride and benzenesulfonic acid is 1:2-10 at the temperature of 80-100 ℃;
(2) preparation of mixed solution of tungsten salt and nickel salt
Adding the carbon nano tube and polyacrylic acid into the mixed solution of tungsten salt and nickel salt, and uniformly stirring to obtain a mixed solution of tungsten salt and nickel salt; the amount of the carbon nano tube accounts for 1-10 wt% of the modified Y/ASA composite molecular sieve, and the amount of the polyacrylic acid accounts for 1-10 wt% of the modified Y/ASA composite molecular sieve;
(3) preparation of hydrocracking catalyst
①, mixing the modified Y/ASA composite molecular sieve prepared in the step (1) with the mixed solution of tungsten salt and nickel salt prepared in the step (2), wherein the ratio of the modified Y/ASA composite molecular sieve to the mixed solution of tungsten salt and nickel salt is that 1g of the modified Y/ASA composite molecular sieve corresponds to 0.5-1.5 ml of the mixed solution of tungsten salt and nickel salt;
②, adding concentrated nitric acid accounting for 1-8% of the mass of the modified Y/ASA composite molecular sieve, adding pseudo-boehmite accounting for 10-20% of the mass of the modified Y/ASA composite molecular sieve, uniformly mixing, extruding into strips, forming, drying at 50-120 ℃ for 1-4 h, and roasting at 300-550 ℃ for 1-6h to obtain the hierarchical pore hydrocracking catalyst.
2. The method for preparing a hierarchical pore hydrocracking catalyst according to claim 1, wherein ASA in the Y/ASA composite molecular sieve is amorphous silica-alumina.
3. The hierarchical pore hydrocracking catalyst according to claim 1 or 2The preparation method is characterized in that the specific surface area of the modified Y/ASA composite molecular sieve is 500-700m2The pore volume is 0.45-0.75 ml/g, and the pore diameter is distributed at 5-30 nm.
4. The preparation method of the hierarchical pore hydrocracking catalyst according to claim 1 or 2, wherein in the step (2), the concentration of the tungsten salt is 10-30 g/ml and the concentration of the nickel salt is 5-30 g/ml in the mixed solution of the tungsten salt and the nickel salt.
5. The process for preparing a multiwell hydrocracking catalyst as claimed in claim 1 or 2, wherein the multiwell hydrocracking catalyst obtained in the step (3) has a specific surface area of 300-450m2The pore volume is 0.29-0.50 ml/g, and the pore diameter is distributed at 5-30 nm.
6. A hierarchical pore hydrocracking catalyst prepared by the preparation method of the hierarchical pore hydrocracking catalyst according to any one of claims 1 to 5.
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