CN107715908A - Hierarchical pore hydrocracking catalyst and preparation method thereof - Google Patents
Hierarchical pore hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN107715908A CN107715908A CN201610665199.9A CN201610665199A CN107715908A CN 107715908 A CN107715908 A CN 107715908A CN 201610665199 A CN201610665199 A CN 201610665199A CN 107715908 A CN107715908 A CN 107715908A
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- composite molecular
- hydrocracking catalyst
- asa composite
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- mixed solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002149 hierarchical pore Substances 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000011259 mixed solution Substances 0.000 claims abstract description 47
- 150000003657 tungsten Chemical class 0.000 claims abstract description 43
- 150000002815 nickel Chemical class 0.000 claims abstract description 37
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 239000002808 molecular sieve Substances 0.000 claims abstract description 11
- 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 11
- 238000000465 moulding 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
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 claims 1
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 239000012266 salt solution Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 26
- 239000010457 zeolite Substances 0.000 description 26
- 229910021536 Zeolite Inorganic materials 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- -1 nickel salt Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000001914 filtration Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910000632 Alusil Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J29/04—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
Landscapes
- 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, carrying out steam treatment on the hydrothermally synthesized Y/ASA composite molecular sieve, then carrying out mixed solution treatment of ammonium chloride and benzenesulfonic acid, and drying to obtain the 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 present invention relates to a kind of multi-stage porous hydrocracking catalyst and preparation method, belong to catalyst technical field.
Background technology
At present, hydrocracking catalyst is mainly using zeolites such as Y types as main acidic components, by with aluminum oxide, sial etc.
After carrier material mechanical mixture, extruded moulding obtains hydrocracking catalyst.
Y-type zeolite is hydrocracking catalyst because its unique pore structure such as is widely used in being hydrocracked at the petrochemical field
The main active component of agent.The silica alumina ratio of y-type zeolite structure cell skeleton directly affects the hydrothermal stability and acid of zeolite molecular sieve
Property.However as the heaviness and in poor quality of oil, Conventional zeolites can not meet harsh reaction-regeneration of catalytic cracking
The demand of condition；Improve y-type zeolite framework si-al ratio, rationally reduce acid site density, improve acid site relative intensity and
Increase the meso-hole structure of zeolite, the ratio between cracking/hydrogen transfer activity can be improved, reduce the generation of catalytic coking, improve product point
Cloth.Industrial NaY molecular sieve production generally uses cheap waterglass as silicon source at present, and directly synthesis obtains NaY silica alumina ratios one
As be not more than 5.6, because Y type molecular sieve aperture is small, particle is big, limits the catalyzed conversion to macromolecular, greatly limit it
Using.
Conventional Y molecular sieve is post-processed and is modified, removes part aluminium atom in skeleton structure of zeolite, or enter on this basis
Row mends silicon, can improve silica alumina ratio well, while can also keep of a relatively high crystallinity.Particularly high-temperature vapor is handled
The zeolite of high silica alumina ratio is obtained, due to not exclusively improving the silica alumina ratio of Y molecular sieve, other performances in processing procedure
It is greatly improved, such as acid strength change by force, acid site density reduces, and sour species becomes more, while is also accompanied by secondary Jie
The generation in hole, catalytic activity are also accordingly greatly improved, and disclosure satisfy that each performance indications of petrochemical industry, have very high
Application value.
The modification of y-type zeolite, first, reducing the sodium content of zeolite, increase the acidity of zeolite, second, improving the stabilization of zeolite
Property i.e. by roasting or high-temperature vapor dealuminzation so that between 24.2-24.5 angstroms, many patents have zeolite unit cell size
Report, such as USP3293192,3449070,3513108 and 3506400 etc..
Aluminium glue and Alusil are incorporated into NaY or NaHY zeolites by CN1060976A and CN1060977A respectively, then
Exchanged again by ammonium, filtering and hydrothermal calcine, respectively obtain the USY zeolite containing amorphous alundum (Al2O3) and amorphous silica-alumina,
High activity and hydrothermal stability can be obtained and keep higher crystallinity.
CN1205915A discloses the method for preparing super-stable Y molecular sieves, and first high-temperature water vapor handles and then used fluosilicic acid
Ammonium salt solution and inorganic mixing acid treatment.
The method that CN1276267A discloses modified zeolite of Y-type, by the y-type zeolite of low sodium content and into sour metallic element
Oxide and the oxide mixing into alkali metal, modified zeolite has very to normal alkane isomerization under the conditions of high-temperature water vapor
Good effect.
CN1284402A discloses a kind of y-type zeolite and preparation method for preparing two level pore structure, by by y-type zeolite and
Dried after siliceous solution dipping, then through steam treatment, obtain the Y zeolites of high hydrothermal stability, but silica alumina ratio does not have
Too big raising.
CN102264643A, which is disclosed, prepares a kind of zeolite containing mesopore, is exchanged by alkali process and then by ammonium, roasting
The zeolite containing mesopore can be obtained.
Above-mentioned method of modifying, just for the investigation of the sample special nature after processing, as prepared containing secondary mesopore
Zeolite either improves silica alumina ratio to increase zeolite stability or reduce the investigation in terms of some such as zeolite sodium content.We are uncommon
Hope by a kind of processing method, Zeolite can either be improved, increase the stability of zeolite, produced while reducing sodium content
Secondary mesopore, high-ratio surface and pore volume are carried, make hydrogenation metal high degree of dispersion, improve hydrocracking catalyst activity.
The content of the invention
The present invention provides a kind of multi-stage porous hydrocracking catalyst and preparation method, main using modified compound point of Y/ASA
Son sieve, tungsten salt and nickel salt mixed solution and boehmite etc. are raw material, through extrusion, shaping, drying and roasting, prepare multi-stage porous and add
Hydrogen Cracking catalyst.Y/ASA composite molecular screens improve specific surface area and pore volume after modified, while improve mesoporous pore size point
Cloth, remove the amorphous aluminium species of zeolite.The multi-stage porous hydrocracking catalyst that this method obtains has bigger serface, macropore
Hold, the characteristics of pore-size distribution is wide.
The present invention provides a kind of preparation method of multi-stage porous hydrocracking catalyst, comprises the following steps：
(1) prepared by modified Y/ASA composite molecular screens
1. steam treatment is carried out to the Y/ASA composite molecular screens of Hydrothermal Synthesiss；
2. ion exchange is carried out to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid, filter after
50~120 DEG C of dry 1~4h, obtain being modified Y/ASA composite molecular screens；
(2) prepared by the mixed solution of tungsten salt and nickel salt
Carbon nanotube and polyacrylic acid are added in the mixed solution of tungsten salt and nickel salt and stirred, obtains tungsten salt and nickel salt
Mixed solution；
(3) preparation of hydrocracking catalyst
1. the tungsten salt that the modification Y/ASA composite molecular screens prepared in step (1) are prepared with step (2) and the mixing of nickel salt
Solution mixes, and modified Y/ASA composite molecular screens and tungsten salt and the mixed solution ratio of nickel salt are:1g is modified Y/ASA compound molecules
Sieve is corresponding to 0.5~1.5ml tungsten salts and the mixed solution of nickel salt；
2. adding the concentrated nitric acid for accounting for modified Y/ASA composite molecular screens quality 1~8%, add and account for compound point of modified Y/ASA
The boehmite of son sieve quality 10~20%, extruded moulding after being well mixed, in 50~120 DEG C of dry 1~4h, in 300~
550 DEG C of 1~6h of roasting, obtain multi-stage porous hydrocracking catalyst.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, in the Y/ASA composite molecular screens
ASA be preferably amorphous silica-alumina.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, steam treatment in step (1)
Temperature is preferably between 500-600 DEG C, and keeping the flow velocity of vapor, processing time is preferably in 1-6h preferably in 10-25ml/min.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, step (1) intermediate ion exchange process
It is preferably under the conditions of 80~100 DEG C, ammonium chloride concentration is preferably 0.01-0.1mol/L, and benzene sulfonic acid concentration is preferably 0.01-
The mass ratio of 0.1mol/L, Y/ASA composite molecular screen and ammonium chloride and the mixed solution of benzene sulfonic acid is preferably 1:2-10.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, the modified Y/ASA compound molecules
The specific surface area of sieve is preferably 500-700m2/ g, pore volume are preferably 0.45~0.75ml/g, and pore-size distribution is preferably in 5-30nm.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, in step (2), tungsten salt and nickel salt
Mixed solution in, tungsten salt concentration preferably 10~30g/ml, nickel salt concentration preferably 5~30g/ml, carbon nanotube dosage preferably account for
1~10wt% of modified Y/ASA composite molecular screens, polyacrylic acid dosage preferably account for modified Y/ASA composite molecular screens 1~
10wt%.
The preparation method of multi-stage porous hydrocracking catalyst of the present invention, wherein, the multi-stage porous obtained in step (3)
Hydrocracking catalyst specific surface area is preferably 300-450m2/ g, pore volume are preferably 0.29~0.50ml/g, and pore-size distribution is preferred
In 5-30nm.
After the present invention mixes Y/ASA composite molecular screens with tungsten salt and nickel salt solution, add aluminum oxide and concentrated nitric acid is direct
Extruded moulding obtains multi-stage porous hydrocracking catalyst, eliminates the step of preparing catalyst carrier, reduces roasting number, carry
High specific surface area of catalyst and pore volume, improve pore-size distribution.Specific surface area of catalyst is in 400-500m2/ g, pore volume exist
0.35~0.45ml/g, pore-size distribution 5-30nm.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
Embodiment 1
(1) prepared by modified Y/ASA composite molecular screens
1. carrying out steam treatment to the Y/ASA composite molecular screens of 100g Hydrothermal Synthesiss, the temperature of steam treatment is 550
DEG C, keeping the flow velocity of vapor, processing time is in 3h in 17ml/min.
2. ammonium chloride and benzene sulfonic acid solution ion exchange
Ion exchange is carried out to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid.Take at 80g hydro-thermals
Y/ASA composite molecular screens after reason, are added in the mixed solution of 240g ammonium chlorides and benzene sulfonic acid, 80 DEG C of exchange temperature, chlorination
Ammonium concentration is in 0.1mol/L, and benzene sulfonic acid concentration is in 0.1mol/L, and exchange terminates rear product after filtering, in 110 DEG C of dry 3h.Institute
Y/ASA composite molecular screen specific surface areas after must handling are in 530m2/ g, pore volume is in 0.54ml/g, pore-size distribution 5-30nm.
(2) prepared by the mixed solution of tungsten salt and nickel salt
Prepare the mixed solution of 100ml tungsten salts and nickel salt, tungsten salt concentration 30g/ml, nickel salt concentration 5g/ml.By 2g charcoal nanometers
Pipe and 2g polyacrylic acid, which are added in tungsten salt and nickel salt mixed solution, to stir, and obtains the mixed solution of tungsten salt and nickel salt.
(3) prepared by hydrocracking catalyst
Y/ASA composite molecular screens 60g is well mixed with the mixed solution and 4.5g concentrated nitric acids of 50ml tungsten salts and nickel salt, added
It is well mixed after entering 8g boehmites, extruded moulding, is calcined 3h in 110 DEG C of dry 2h, in 450 DEG C, obtains multi-stage porous hydrogenation
Cracking catalyst.Specific surface area of catalyst is in 305m2/ g, pore volume is in 0.29ml/g, pore-size distribution 5-30nm.
Embodiment 2
(1) prepared by modified Y/ASA composite molecular screens
1. carrying out steam treatment to the Y/ASA composite molecular screens of 100g Hydrothermal Synthesiss, the temperature of steam treatment is 500
DEG C, keeping the flow velocity of vapor, processing time is in 6h in 25ml/min.
2. ammonium chloride and benzene sulfonic acid solution ion exchange
Ion exchange is carried out to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid.Take at 80g hydro-thermals
Y/ASA composite molecular screens after reason, are added in the mixed solution of 400g ammonium chlorides and benzene sulfonic acid, 90 DEG C of exchange temperature, chlorination
Ammonium concentration is in 0.1mol/L, and benzene sulfonic acid concentration is in 0.01mol/L, and exchange terminates rear product after filtering, in 110 DEG C of dry 2h.
Y/ASA composite molecular screen specific surface areas after gained processing are in 675m2/ g, pore volume is in 0.72ml/g, pore-size distribution 5-30nm.
(2) prepared by the mixed solution of tungsten salt and nickel salt
Prepare the mixed solution of 100ml tungsten salts and nickel salt, tungsten salt concentration 10g/ml, nickel salt concentration 30g/ml.2g charcoals are received
Mitron and 4g polyacrylic acid, which are added in tungsten salt and nickel salt mixed solution, to stir, and obtains the mixed solution of tungsten salt and nickel salt.
(3) prepared by hydrocracking catalyst
Y/ASA composite molecular screens 60g is well mixed with the mixed solution and 3.0g concentrated nitric acids of 70ml tungsten salts and nickel salt, then
It is well mixed after adding 10g boehmites, extruded moulding, is calcined 1h in 110 DEG C of dry 2h, in 550 DEG C, obtains multi-stage porous and add
Hydrogen Cracking catalyst.Specific surface area of catalyst is in 440m2/ g, pore volume is in 0.48ml/g, pore-size distribution 5-30nm.
Embodiment 3
(1) prepared by modified Y/ASA composite molecular screens
1. carrying out steam treatment to the Y/ASA composite molecular screens of 100g Hydrothermal Synthesiss, the temperature of steam treatment is 600
DEG C, keeping the flow velocity of vapor, processing time is in 1h in 10ml/min.
2. ammonium chloride and benzene sulfonic acid solution ion exchange
Ion exchange is carried out to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid.Take at 80g hydro-thermals
Y/ASA composite molecular screens after reason, are added in the mixed solution of 400g ammonium chlorides and benzene sulfonic acid, 90 DEG C of exchange temperature, chlorination
Ammonium concentration is in 0.1mol/L, and benzene sulfonic acid concentration is in 0.1mol/L, and exchange terminates rear product after filtering, in 110 DEG C of dry 2h.Institute
Y/ASA composite molecular screen specific surface areas after must handling are in 675m2/ g, pore volume is in 0.72ml/g, pore-size distribution 5-30nm.
(2) prepared by the mixed solution of tungsten salt and nickel salt
Prepare the mixed solution of 100ml tungsten salts and nickel salt, tungsten salt concentration 20g/ml, nickel salt concentration 20g/ml.4g charcoals are received
Mitron and 2g polyacrylic acid, which are added in tungsten salt and nickel salt mixed solution, to stir, and obtains the mixed solution of tungsten salt and nickel salt.
(3) prepared by hydrocracking catalyst
Y/ASA composite molecular screens 60g is well mixed with the mixed solution and 3.0g concentrated nitric acids of 70ml tungsten salts and nickel salt, then
It is well mixed after adding 10g boehmites, extruded moulding, is calcined 6h in 110 DEG C of dry 2h, in 300 DEG C, obtains multi-stage porous and add
Hydrogen Cracking catalyst.Specific surface area of catalyst is in 445m2/ g, pore volume is in 0.49ml/g, pore-size distribution 5-30nm.
Embodiment 4
(1) prepared by modified Y/ASA composite molecular screens
1. carrying out steam treatment to the Y/ASA composite molecular screens of 100g Hydrothermal Synthesiss, the temperature of steam treatment is 550
DEG C, keeping the flow velocity of vapor, processing time is in 3h in 17ml/min.
2. ammonium chloride and benzene sulfonic acid solution ion exchange
Ion exchange is carried out to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid.Take at 80g hydro-thermals
Y/ASA composite molecular screens after reason, are added in the mixed solution of 240g ammonium chlorides and benzene sulfonic acid, 90 DEG C of exchange temperature, chlorination
Ammonium concentration is in 0.05mol/L, and benzene sulfonic acid concentration is in 0.05mol/L, and exchange terminates rear product after filtering, in 110 DEG C of dry 7h.
Y/ASA composite molecular screen specific surface areas after gained processing are in 632m2/ g, pore volume is in 0.65ml/g, pore-size distribution 5-30nm.
(2) prepared by the mixed solution of tungsten salt and nickel salt
Prepare the mixed solution of 100ml tungsten salts and nickel salt, tungsten salt concentration 17g/ml, nickel salt concentration 17g/ml.4g charcoals are received
Mitron and 4g polyacrylic acid, which are added in tungsten salt and nickel salt mixed solution, to stir, and obtains the mixed solution of tungsten salt and nickel salt.
(3) prepared by hydrocracking catalyst
Y/ASA composite molecular screens 60g is well mixed with the mixed solution and 4.5g concentrated nitric acids of 50ml tungsten salts and nickel salt, added
It is well mixed after entering 8g boehmites, extruded moulding, is calcined 3h in 110 DEG C of dry 6h, in 425 DEG C, obtains multi-stage porous hydrogenation
Cracking catalyst.Specific surface area of catalyst is in 430m2/ g, pore volume is in 0.42ml/g, pore-size distribution 5-30nm.
Claims (8)
1. a kind of preparation method of multi-stage porous hydrocracking catalyst, comprises the following steps：
(1) prepared by modified Y/ASA composite molecular screens
1. steam treatment is carried out to the Y/ASA composite molecular screens of Hydrothermal Synthesiss；
2. carrying out ion exchange to Y/ASA composite molecular screens using the mixed solution of ammonium chloride and benzene sulfonic acid, filter after 50~
120 DEG C of dry 1~4h, obtain being modified Y/ASA composite molecular screens；
(2) prepared by the mixed solution of tungsten salt and nickel salt
Carbon nanotube and polyacrylic acid are added in the mixed solution of tungsten salt and nickel salt and stirred, obtains the mixed of tungsten salt and nickel salt
Close solution；
(3) preparation of hydrocracking catalyst
1. tungsten salt and the mixed solution of nickel salt that the modification Y/ASA composite molecular screens prepared in step (1) are prepared with step (2)
Mixing, modified Y/ASA composite molecular screens and tungsten salt and the mixed solution ratio of nickel salt are:1g is modified Y/ASA composite molecular screens pair
Should be in 0.5~1.5ml tungsten salts and the mixed solution of nickel salt；
2. adding the concentrated nitric acid for accounting for modified Y/ASA composite molecular screens quality 1~8%, add and account for modified Y/ASA composite molecular screens
The boehmite of quality 10~20%, extruded moulding after being well mixed, in 50~120 DEG C of dry 1~4h, in 300~550 DEG C
1~6h is calcined, obtains multi-stage porous hydrocracking catalyst.
2. according to the preparation method of the multi-stage porous hydrocracking catalyst described in right 1, it is characterised in that the Y/ASA is compound
ASA in molecular sieve is amorphous silica-alumina.
3. according to the preparation method of the multi-stage porous hydrocracking catalyst described in right 1, it is characterised in that step (1) reclaimed water is steamed
The temperature of gas disposal is between 500-600 DEG C, and keeping the flow velocity of vapor, processing time is in 1-6h in 10-25ml/min.
4. according to the preparation method of the multi-stage porous hydrocracking catalyst described in right 1, it is characterised in that step (1) intermediate ion
Exchange process is the ammonium chloride concentration 0.01-0.1mol/L under the conditions of 80~100 DEG C, and benzene sulfonic acid concentration is 0.01-
0.1mol/L, Y/ASA composite molecular screen are 1 with the mass ratio of ammonium chloride and the mixed solution of benzene sulfonic acid:2-10.
5. according to the preparation method of the multi-stage porous hydrocracking catalyst described in any one of right 1~4, it is characterised in that described
The specific surface area of modified Y/ASA composite molecular screens is 500-700m2/ g, pore volume are 0.45~0.75ml/g, and pore-size distribution is in 5-
30nm。
6. according to the preparation method of the multi-stage porous hydrocracking catalyst described in any one of right 1~4, it is characterised in that step
(2) in, in the mixed solution of tungsten salt and nickel salt, tungsten salt 10~30g/ml of concentration, 5~30g/ml of nickel salt concentration, carbon nanotube are used
Amount accounts for 1~10wt% of modified Y/ASA composite molecular screens, polyacrylic acid dosage account for modified Y/ASA composite molecular screens 1~
10wt%.
7. according to the preparation method of the multi-stage porous hydrocracking catalyst described in any one of right 1~4, it is characterised in that step
(3) the multi-stage porous hydrocracking catalyst specific surface area obtained in is 300-450m2/ g, pore volume are 0.29~0.50ml/g, hole
Footpath is distributed in 5-30nm.
8. a kind of multi-stage porous hydrocracking catalyst, it is the multi-stage porous hydrocracking catalyst described in any one of claim 1~7
Multi-stage porous hydrocracking catalyst made from the preparation method of agent.
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| CN102451745A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof |
| CN102533317A (en) * | 2010-12-23 | 2012-07-04 | 中国石油天然气股份有限公司 | Method for producing chemical raw material by hydrocracking |
| CN102533316A (en) * | 2010-12-23 | 2012-07-04 | 中国石油天然气股份有限公司 | Method for selective hydrocracking of light oil |
| CN103100411A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing molecular sieve and amorphous silica-alumina |
| CN103252256A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Composite molecular sieve hydrocracking catalyst carrier |
| CN105618113A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing hydro-cracking catalyst composition |
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| CN102451745A (en) * | 2010-10-14 | 2012-05-16 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing Y-type molecular sieve/amorphous silica-alumina and preparation method thereof |
| CN102533317A (en) * | 2010-12-23 | 2012-07-04 | 中国石油天然气股份有限公司 | Method for producing chemical raw material by hydrocracking |
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| CN103100411A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing molecular sieve and amorphous silica-alumina |
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