CN110404581A - A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked - Google Patents
A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked Download PDFInfo
- Publication number
- CN110404581A CN110404581A CN201810399344.2A CN201810399344A CN110404581A CN 110404581 A CN110404581 A CN 110404581A CN 201810399344 A CN201810399344 A CN 201810399344A CN 110404581 A CN110404581 A CN 110404581A
- Authority
- CN
- China
- Prior art keywords
- preparation
- molecular sieve
- hydrocracking catalyst
- catalyst
- catalyst according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 80
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 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 67
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000004898 kneading Methods 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 12
- 239000003350 kerosene Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 238000002803 maceration Methods 0.000 claims abstract description 7
- 238000005345 coagulation Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- 238000009938 salting Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims 1
- -1 kneading It forms Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 159000000013 aluminium salts Chemical class 0.000 description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000010742 number 1 fuel oil Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000372132 Hydrometridae Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VYOZKLLJJHRFNA-UHFFFAOYSA-N [F].N Chemical compound [F].N VYOZKLLJJHRFNA-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J29/084—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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of hydrocracking catalyst, include the following steps: to be added in property Y molecular sieve, beta-molecular sieve and macroporous aluminium oxide using small porous aluminum oxide as the binder of matrix, kneading and compacting, catalyst carrier is made after drying and roasting；Using vib metals and/or group VIII metal as active component, prepare the salting liquid containing active component, continuously add citric acid as maceration extract, by the catalyst carrier incipient impregnation after the maceration extract drying and roasting, obtain hydrocracking catalyst.The catalyst is hydrocracked production naphtha, aviation kerosine, low-coagulation diesel oil for bad, heavy diesel fuel.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst preparation methods, more particularly to one kind to add hydrogen to split for bad, heavy diesel fuel
Metaplasia produces the hydrocracking catalyst preparation method of naphtha, aviation kerosine, low-coagulation diesel oil, and a kind of bad/heavy diesel fuel adds hydrogen
The method of cracking, using the catalyst of above-mentioned preparation method preparation as catalyst.
Background technique
Currently, gasoline, boat coal, aromatic hydrocarbons demand growth are very fast on consumption market, diesel oil demand declines to a great extent, and consumes bavin vapour
It keeps falling behind peak than reaching 2.27:1 from 2005, drops to 1.64:1 within 2014.It is expected that the year two thousand twenty, Consumption of China
Diesel and gasoline ratio would fall to about 1.06:1, and the lower general who has surrendered's centering state oil refining apparatus structural adjustment for consuming diesel and gasoline ratio brings huge challenge.
Chinese naphtha market integrally shows the situation that supply falls short of demand, and 2015, the 2016 continuous China Liang Nian naphtha net importations are more than
6000000 tons.The correlative study work for carrying out diesel oil secondary operation device production reformer feed, aviation kerosine, reduces promotion
Diesel and gasoline ratio realizes that oil refining has important practical significance to chemical industry transition.
In the secondary operation technology of crude oil, distillate hydrocracking technology have adaptability to raw material strong, production operation and
The features such as products scheme flexibility is big, good product quality, various heavys, inferior raw material can be converted into market in urgent need
Naphtha and tail oil preparing ethylene by steam cracking raw material etc., play product distribution and product quality tune in full factory's production procedure
The effect for saving device is the core that oil refining " one change one fine " combines, oneself becomes most important in modern oil refining and petro chemical industry
One of heavy oil deep processing technique.
Hydrocracking catalyst has Hydrogenation and cracking performance as a kind of bifunctional catalyst.It generally selects non-
Your group vib and group VIII metal select molecular sieve and/or amorphous silicon aluminium as Cracking Component, molecular sieve as hydrogenation component
The key component of cracking is played in such catalyst.The main active component of hydrocracking catalyst is Y type molecular sieve, and Y divides
Son sieve silica alumina ratio will directly affect the hydrothermal stability of molecular sieve.Silica alumina ratio is improved, helps to reduce acid site density, improve
Acid strength can improve cracking and the ratio between react with hydrogen transfer activity, reduce coke and generate, improve product distribution.In addition, having
It can bear to be hydrocracked more stringent reaction condition compared with the molecular sieve of high silica alumina ratio, extend the service life of catalyst.
US4672048 describes a kind of light oil type hydrogen cracking catalyst, and molecular sieve silica alumina ratio used best 11~
15, preparation method is that common NaY molecular sieve obtains NH after ammonium exchanges4NaY molecular sieve, then to NH4NaY molecular sieve carries out fluorine
Ammonium silicate is modified, then carries out hydro-thermal process and obtain USSSY molecular sieve.Method for preparing catalyst is, modified Y molecular sieve with by small
Binder kneading and compacting made of porous aluminum oxide and nitric acid, carrier soak metal again after drying and roasting, obtain after drying and roasting
Finished catalyst.The catalyst of technology preparation light oil selectivity with higher and anti-nitrogen performance, but due to Y molecular sieve acid
Density is lower, causes catalyst activity relatively low, in addition impregnates the more steps of metal on a catalyst support using metal salt solution
Calcination procedure.
US4831002 and US5122258 discloses a kind of smart as metallo-organic complex preparation plus hydrogen using ethylenediamine
The method of catalyst processed can significantly improve hydrodesulfurization, the denitrification activity of catalyst.Due to after catalyst carried metal not
It carries out roasting direct vulcanization, the activity of sulphurized catalyst is higher and long period stability is poor.
CN101618347A discloses a kind of hydrocracking catalyst and preparation method thereof containing modified Y molecular sieve, this changes
Property is mentioned using aluminium salt and inorganic acid combined treatment NH4NaY molecular sieve, then carry out ammonium fluosilicate dealumination complement silicon and hydro-thermal process.
The removing of part framework aluminum is be easy to cause when removing molecular sieve non-framework aluminum using inorganic acid, it is non-using aluminium salt removing molecular sieve
Since aluminium salt pH value is relatively low when framework aluminum, it is difficult to remove the non-framework aluminum in micropore, and use inorganic acid and aluminium salt combination de-
Aluminium can not only guarantee largely to remove non-framework aluminum but also can reduce the destruction to framework aluminum.But the isomery performance of Y molecular sieve
Lower, the cryogenic property of produced intermediate oil is poor.
Patent CN101433848B gives a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, using kneading method
The catalyst of preparation contains nonionic surface active agent, the catalysis of this method preparation in the active metal solution of the catalyst
The characteristics of there is macropore to hold for agent, specific surface area is suitable for, and active metal is uniformly dispersed.But the heavy oil hydrogenating treatment catalyst is not
With pour-point depressing process, it is unobvious that produced diesel oil distillate condensation point reduces amplitude.
CN1015640B gives a kind of preparation method of supported non-noble metal hydrocracking catalyst, active group
It is divided into group vib and/or group VIIIB non-noble metal j element, metal incorporation way in the periodic table of elements and mainly uses infusion process.It produces
Gas generating amount is few, activity stabilized in object, is suitable for mild hydrocracking.But the catalyst of this method preparation is to reaction temperature
Spend it is insensitive, latter stage by temperature raising improve catalyst activity effect it is unobvious.
Summary of the invention
In order to overcome the shortage of prior art, the object of the present invention is to provide a kind of hydrocracking catalyst preparation methods, use
It is hydrocracked production naphtha, aviation kerosine, low-coagulation diesel oil in bad, heavy diesel fuel, can be changed while improving diesel quality
The cryogenic property of kind boat coal and diesel oil.
For this purpose, the present invention provides a kind of preparation method of hydrocracking catalyst, include the following steps:
(1) it is added in modified Y molecular sieve, beta-molecular sieve and macroporous aluminium oxide using small porous aluminum oxide as the bonding of matrix
Catalyst carrier is made after drying and roasting for agent, kneading and compacting；
(2) using vib metals and/or group VIII metal as active component, the salting liquid containing active component is prepared,
Citric acid is continuously added as maceration extract, by the catalyst carrier incipient impregnation after the maceration extract drying and roasting, obtain
To hydrocracking catalyst.
The preparation method of hydrocracking catalyst of the present invention, wherein the specific surface of the hydrocracking catalyst
Product is preferably 220~550m2/ g, it is preferably 0.25~0.75ml/g that hole, which holds,.
The preparation method of hydrocracking catalyst of the present invention, wherein using catalyst carrier butt gross mass as base
Standard, wherein each component content is preferred are as follows: modified Y molecular sieve 20.0%~60.0%, beta-molecular sieve 10.0%~50.0%, macropore
Aluminium oxide 20.0%~60.0%, small porous aluminum oxide 10.0~50.0%；Further preferably are as follows: modified Y molecular sieve 30.0%~
60.0%, beta-molecular sieve 10.0%~30.0%, macroporous aluminium oxide 20.0%~35.0%, small porous aluminum oxide 15.0~
30.0%.
The preparation method of hydrocracking catalyst of the present invention, wherein the active component preferably accounts for catalyst weight
15~the 40wt%, further preferably 22wt%~35wt% of amount.
The preparation method of hydrocracking catalyst of the present invention, wherein the active component is preferably group VIB
Metal and group VIII metal, the salt containing active component are the salt containing vib metals and the metal containing group VIII
Salt；Salt containing vib metals can be the one or more of wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate, preferably metatungstic acid
Ammonium；Group VIII metal salt can be the one or more of nickel nitrate, nickel acetate, basic carbonate nickel salt, preferably nickel nitrate.
The preparation method of hydrocracking catalyst of the present invention, wherein the vib metals are preferably tungsten, with
Tungsten oxide meter preferably accounts for 14~30wt% of catalyst weight, further preferably 18wt%~27wt%；The Section VIII
Race's metal is preferably nickel, in terms of nickel oxide, preferably accounts for 3~10wt% of catalyst weight, further preferably 4~8wt%.
The preparation method of hydrocracking catalyst of the present invention, in step (2), in the maceration extract citric acid with
The molar ratio of nickel is preferably 0.1~1.0:1, further preferably 0.2~0.8:1.
The preparation method of hydrocracking catalyst of the present invention, wherein the modified Y molecular sieve crystalline substance packet constant is excellent
It is selected as 2.430~2.460nm, silica alumina ratio is preferably 5~20.
The preparation method of hydrocracking catalyst of the present invention, wherein the modified Y molecular sieve is preferably by NaY
Molecular sieve successively carries out what ammonium exchange, hydro-thermal process and acid processing obtained, and the modified Y molecular sieve crystalline substance packet constant is preferably
2.435~2.455nm, silica alumina ratio are preferably 8~15.
The preparation method of hydrocracking catalyst of the present invention, wherein the silica alumina ratio of the beta-molecular sieve is preferably
40~120, further preferably 40~80.
The preparation method of hydrocracking catalyst of the present invention, wherein the specific surface area of the small porous aluminum oxide is excellent
It is selected as 200~500m2/ g, further preferably 200~400m2/ g is still more preferably 200~300m2/g；Hole Rong Youxuan
It is still more preferably 0.3~0.5ml/g for 0.2~0.7ml/g, further preferably 0.3~0.6ml/g.
The preparation method of hydrocracking catalyst of the present invention, wherein the specific surface area of the macroporous aluminium oxide is excellent
It is selected as 200~600m2/ g, further preferably 200~500m2/ g is still more preferably 300~380m2/g；Hole Rong Youxuan
It is still more preferably 0.6~0.9ml/g for 0.4~1.2ml/g, further preferably 0.4~1.0ml/g.
The preparation method of hydrocracking catalyst of the present invention, wherein the preparation process of the binder is preferred
Are as follows: it is dissolved in deionized water using inorganic acid and being stirred with small porous aluminum oxide, pasty masses are made；The inorganic acid
It is preferably selected from one or more of nitric acid, phosphoric acid, hydrochloric acid, further preferred nitric acid.Nitric acid accounts for aperture oxygen in the binder
Change 5%~45wt% of aluminium mass fraction, preferably 10 wt%~30wt%, binder burns residual 10~30wt%, preferably 15~
25wt%.
The preparation method of hydrocracking catalyst of the present invention, in step (1) and (2), the temperature of the drying is equal
Preferably 80~140 DEG C, further preferably 110~130 DEG C, being dried the time is 2~8 hours, further preferably
4~6 hours；In step (1), the condition of the roasting is preferably to roast 4~8 hours at 400~600 DEG C, further preferably
It is roasted 3~7 hours at 450~550 DEG C；In step (2), the condition of the roasting is to roast 2~8 hours at 400~600 DEG C,
It is roasted 3~7 hours at further preferably 450~550 DEG C.
The present invention also provides the methods that the bad/heavy diesel fuel of one kind is hydrocracked, with normal, vacuum distillate or secondary operation oil
For feedstock oil, using hydrocracking catalyst made from above-mentioned preparation method as catalyst, hydrocracking reaction condition are as follows: anti-
Answer 6.0~10.0MPa of pressure, hydrogen to oil volume ratio 600~1200, production heavy naphtha, aviation kerosine and low-coagulation diesel oil.
Specifically, modified Y molecular sieve used is common commercially available NaY molecular sieve in carrier of hydrocracking catalyst of the present invention
(silica alumina ratio 4.2:1, Na2O content 12.5%, brilliant packet constant 2.468nm, relative crystallinity 96%), pass through hydro-thermal and sour group
Modification is closed to obtain, it is specific the preparation method is as follows:
(A1) ammonium exchanges, and the exchange of NaY original powder ammonium is obtained Y molecular sieve for 3 times, and 80~110 DEG C of ammonium exchange temperature, preferably 85
~95 DEG C, ammonium salt used is the one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, and preferably ammonium chloride, ammonium salt concentration used is
0.1~2.0mol/L, preferably 0.5~1.0mol/L；Ammonium exchange liquid consolidates mass ratio 5:1~30:1, preferably 10:1~20:1；Ammonium
Swap time 0.5~3 hour, preferably 1~2 hour.
(A2) hydro-thermal process, Y molecular sieve hydro-thermal process 2 times that step (A1) is obtained, hydro-thermal process temperature 500~
Between 750 DEG C, preferably between 550~650 DEG C；Hydrothermal conditions 0.5~4 hour, preferably 1.0~2.0 hours；At hydro-thermal
0.05~0.5MPa of pressure, preferably 0.1~0.3MPa are managed, above-mentioned hydrothermal treatment process preferably carries out under the conditions of water filling, fills the water
Measure 50~600ml/h, preferably 100~400ml/h.
(A3) acid processing handles the Y molecular sieve acid after step (A2) hydro-thermal process 1 time, and sour treatment temperature is in 60-100
Between DEG C, preferably between 80-100 DEG C；Between acid 0.5~4.0 hour time of processing, preferably between 1.0~3.0 hours；At acid
It manages between solid-to-liquid ratio 1:5~1:20, preferably 1:10~1:15；It includes hydrochloric acid, nitric acid, phosphoric acid that acid, which handles used inorganic acid,
One or more, preferably hydrochloric acid；Acid handles acidic aqueous solution H used+Molar concentration is between 0.01~1.0mool/L, preferably
0.05~0.2mol/L.
The present invention using the stronger Y molecular sieve of open loop ability and the stronger beta-molecular sieve of isomerization ability as Cracking Component,
The synergistic effect for giving full play to open loop, isomery is hydrocracked production naphtha, aviation kerosine, low solidifying bavin for bad, heavy diesel fuel
Oil, improving boat coal and diesel oil distillate section cryogenic property by isomerization reaction can improve while improving diesel quality
The cryogenic property of boat coal and diesel oil；Meanwhile being made using one or more of elements of vib metals and/or group VIII metal
By the way of incipient impregnation, catalysis is made by dry using citric acid as metal organic complexing agent for active component
Agent finished product.The hydrocracking catalyst prepared using this method is capable of forming more Ni-W- S after over cure and adds hydrogen living
Property center, significantly improve W state of cure (vulcanization), catalyst prepared by this method has stronger Hydrogenation.It is particularly suitable for
Bad, heavy diesel fuel is hydrocracked production heavy naphtha, aviation kerosine and low-coagulation diesel oil.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the present invention.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following
Test method without specific conditions in embodiment, usually according to normal condition.
As shown in Figure 1, the detailed process of hydrocracking catalyst preparation of the present invention are as follows:
(1) small porous aluminum oxide being added in the deionized water solution containing nitric acid, binder is made in kneading to paste shape,
It is sealed stand-by；NaY original powder is passed sequentially through into amine exchange, hydro-thermal process and acid processing and obtains modified Y molecular sieve.
(2) by modified Y molecular sieve, beta-molecular sieve, macroporous aluminium oxide, binder, after kneading extruded moulding, drying and roasting
Afterwards, catalyst carrier is made.Metal salt is loaded to carrier, drying and roasting in a manner of isometric step impregnation.
(3) serial various concentration aqueous citric acid solution is prepared, incipient impregnation passes through in step (2) calcined catalyst
The finished catalysts such as dry.
Embodiment 1
(1) by commercially available NaY molecular sieve (silica alumina ratio 4.2:1, Na2O content 12.5wt%, brilliant packet constant 2.468nm, phase
To crystallinity 96%) it is mixed with the oronain solution that concentration is 0.5mol/L, solvent and solute weight ratio 10:1 is warming up to 85 DEG C, is stirring
Lower progress ion exchange 1.0 hours is mixed, mother liquor is filtered off, repeats washing 3 times, is filtered.It repeats the above process 1 time, filters, washing,
Obtain NH4Y molecular sieve.
(2) by NH in step (1)4Y molecular sieve is handled under hydrothermal conditions.Hydro-thermal process temperature is at 550 DEG C, water
Heat treatment time 1.0 hours, hydro-thermal process pressure 0.1MPa, water injection rate 100ml/h obtained a hydrothermal modification Y molecular sieve.
(3) preparating acid molar concentration 0.05mol/L deionized water solution, according to the ratio of solid-liquid mass ratio 1:10,
Y molecular sieve processed in step (2) is added in aqueous solution, is warming up to 80 DEG C, constant temperature stirs 3 hours.Filter off mother liquor, water
It washes 3 times, filters.It repeats the above process 1 time, filters, washing obtains sour modified Y molecular sieve.
(4) modified Y molecular sieve sour in step (3) is subjected to a hydro-thermal process according to step (2) sequence, obtains modified Y
Molecular sieve is denoted as Y-1.
Embodiment 2
(1) by commercially available NaY molecular sieve (silica alumina ratio 4.2:1, Na2O content 12.5wt%, brilliant packet constant 2.468nm, phase
To crystallinity 96%) it is mixed with the oronain solution that concentration is 1.0mol/L, solvent and solute weight ratio 20:1 is warming up to 95 DEG C, is stirring
Lower progress ion exchange 2.0 hours is mixed, mother liquor is filtered off, repeats washing 3 times, is filtered.It repeats the above process 3 times, filters, washing,
Obtain NH4Y molecular sieve.
(2) by NH in step (1)4Y molecular sieve is handled under hydrothermal conditions.Hydro-thermal process temperature is at 650 DEG C, water
Heat treatment time 2.0 hours, hydro-thermal process pressure 0.3MPa, water injection rate 400ml/h.Obtain a hydrothermal modification Y molecular sieve.
(3) preparating acid molar concentration 0.1mol/L deionized water solution, according to the ratio of solid-liquid mass ratio 1:12,
Y molecular sieve processed in step (2) is added in aqueous solution, is warming up to 90 DEG C, constant temperature stirs 2 hours.Filter off mother liquor, water
It washes 3 times, filters.It repeats the above process 1 time, filters, washing obtains sour modified Y molecular sieve.
(4) modified Y molecular sieve sour in step (3) is subjected to a hydro-thermal process according to step (2) sequence, obtains modified Y
Molecular sieve is denoted as Y-2.
Embodiment 3
(1) by commercially available NaY molecular sieve (silica alumina ratio 4.2:1, Na2O content 12.5wt%, brilliant packet constant 2.468nm, phase
To crystallinity 96%) it is mixed with the oronain solution that concentration is 0.8mol/L, solvent and solute weight ratio 15:1 is warming up to 90 DEG C, is stirring
Lower progress ion exchange 1.5 hours is mixed, mother liquor is filtered off, repeats washing 3 times, is filtered.It repeats the above process 3 times, filters, washing,
Obtain NH4Y molecular sieve.
(2) by NH in step (1)4Y molecular sieve is handled under hydrothermal conditions.Hydro-thermal process temperature is at 600 DEG C, water
Heat treatment time 1.5 hours, hydro-thermal process pressure 0.2MPa, water injection rate 200ml/h.Obtain a hydrothermal modification Y molecular sieve.
(3) preparating acid molar concentration 0.2mol/L deionized water solution, according to the ratio of solid-liquid mass ratio 1:15,
Y molecular sieve processed in step (2) is added in aqueous solution, is warming up to 100 DEG C, constant temperature stirs 2 hours.Filter off mother liquor, water
It washes 3 times, filters.It repeats the above process 1 time, filters, washing obtains sour modified Y molecular sieve.
(4) modified Y molecular sieve sour in step (3) is subjected to a hydro-thermal process according to step (2) sequence, obtains modified Y
Molecular sieve is denoted as Y-3.
The property of modified Y molecular sieve made from embodiment 1-3 is listed in such as the following table 1.
1 modified molecular screen property of table
| Molecular sieve number | Y-1 | Y-2 | Y-3 |
| Brilliant packet constant, nm | 2.462 | 2.447 | 2.454 |
| Framework si-al ratio | 6.7 | 11.5 | 15.5 |
| Relative crystallinity, % | 86 | 84 | 77 |
| Specific surface area, m2/g | 521.5 | 518.8 | 526.9 |
| Kong Rong, ml/g | 0.343 | 0.356 | 0.322 |
| Aperture, nm | 3.3 | 3.6 | 3.7 |
Seen from table 1, the brilliant packet constant of modified Y molecular sieve is between 2.43~2.47nm, framework si-al ratio 6.0~
Between 16.0, specific surface area is in 515~530m2Between/g, Kong Rong between 0.320~0.360, aperture 3.3~3.7 it
Between.Also, with the increase of hydro-thermal process pressure and temperature, Y molecular sieve degree of dealumination is continuously increased, and silica alumina ratio is from Y-1's
6.6 increase to the 15.5 of Y-3, and brilliant packet constant is also contracted to the 2.447 of Y-2 by the 2.462 of Y-1.Y points after hydro-thermal process
Sub- sifter device has flourishing Secondary Channel, and most probable pore size is between 3.3~3.7nm.
Embodiment 4
31.0g nitric acid solution (65wt%) is taken, after the dilution of 1023.39g Purified Water, is slowly added to small equipped with 278.94g
In the kneading machine of porous aluminum oxide (butt 71.7wt%), abundant kneading to paste shape is prepared into nitric acid content 10wt%, butt
The binder B-1 of 15wt%.
Wherein, the specific surface area of small porous aluminum oxide is 200m2/ g, Kong Rongwei 0.5ml/g.
20.36 gram molecules sieve Y-1 (butt 98.5wt%), 30.99 grams of beta-molecular sieves (silica alumina ratio 40:1), 200 grams are glued
Tie agent B-1 (binder burns residual 15%), 27.78g macroporous aluminium oxide (butt 72wt%) kneading extrusion, 110 DEG C drying 4 hours,
450 DEG C roast 4 hours, obtain catalyst carrier S-1.
Wherein, the specific surface area of macroporous aluminium oxide is 300m2/ g, Kong Rongwei 0.9ml/g.
It takes 15.57g nickel nitrate, 19.7g ammonium metatungstate to be dissolved in deionized water, is stirred at room temperature to after being completely dissolved, wait bodies
Product is impregnated in 78g carrier S -1,110 DEG C of 450 DEG C roasting 4 hours after drying 4 hours.2.06g citric acid is taken to be dissolved in deionization
In water, incipient impregnation in catalyst, 110 DEG C drying 4 hours, obtain catalyst C-1.
Embodiment 5
92.3g nitric acid solution (65wt%) is taken, after the dilution of 428.8g Purified Water, is slowly added to equipped with 278.94g aperture
In the kneading machine of aluminium oxide (butt 71.7wt%), abundant kneading to paste shape is prepared into nitric acid content 30wt%, butt
The binder B-2 of 25wt%.
Wherein, the specific surface area of small porous aluminum oxide is 300m2/ g, Kong Rongwei 0.3ml/g.
30.46 gram molecules are sieved into Y-2 (butt 98.5wt%), 20.66 grams of beta-molecular sieves (silica alumina ratio 60:1), 80 grams of bondings
Agent B-2 (binder burn residual 25wt%), 41.67g macroporous aluminium oxide (butt 72wt%) kneading extrusion, 130 DEG C drying 6 hours,
550 DEG C roast 7 hours, obtain catalyst carrier S-2.
Wherein, the specific surface area of macroporous aluminium oxide is 380m2/ g, Kong Rongwei 0.6ml/g.
31.14g nickel nitrate, 29.54g ammonium metatungstate is taken to be dissolved in deionized water, incipient impregnation is in 65g carrier S -2
In, 130 DEG C after drying 6 hours 550 DEG C roast 7 hours, take 10.2g citric acid to be dissolved in deionized water, incipient impregnation is in dry
In dry rear catalyst, 130 DEG C drying 6 hours, obtain catalyst C-2.
Embodiment 6
61.5g nitric acid solution (65%) is taken, after the dilution of 659.56g Purified Water, is slowly added to equipped with 278.94g aperture
In the kneading machine of aluminium oxide (butt 71.7%), abundant kneading to paste shape is prepared into nitric acid content 20%, butt 20%
Binder B-3.
Wherein, the specific surface area of small porous aluminum oxide is 255m2/ g, Kong Rongwei 0.4ml/g.
40.61 gram molecules are sieved into Y-3 (butt 98.5wt%), 10.33 grams of beta-molecular sieves (silica alumina ratio 80:1), 75 grams of bondings
Agent B-3 (binder burns residual 20%), 48.61g macroporous aluminium oxide (butt 72wt%) kneading extrusion, 115 DEG C drying 5 hours,
500 DEG C roast 5 hours, obtain catalyst carrier S-3.
Wherein, the specific surface area of macroporous aluminium oxide is 355m2/ g, Kong Rongwei 0.85ml/g.
It takes 23.36g nickel nitrate, 26.26g ammonium metatungstate to be dissolved in deionized water, is stirred at room temperature to after being completely dissolved, etc.
Volume impregnation in 70g carrier S -3,115 DEG C after drying 5 hours 500 DEG C roast 5 hours, take 12.3g citric acid be dissolved in from
In sub- water, incipient impregnation in dry rear catalyst, 115 DEG C drying 5 hours, obtain catalyst C-3.
Comparative example 1
23.36g nickel nitrate, 26.26g ammonium metatungstate is taken to be dissolved in deionized water, incipient impregnation is in 70g carrier S -3
In, 115 DEG C drying 5 hours, 500 DEG C roast 5 hours, obtain catalyst C-4.
The property of catalyst made from embodiment 4-6 and comparative example 1 is listed in such as the following table 2.
2 catalyst property of table
As can be seen from Table 2, the specific surface area of catalyst C1~C4 is in 318.2~362.3m2Between/g, catalytic mechanical is strong
Degree is between 208~266N/cm.
Embodiment 7
Using catalytic diesel oil and straight-run diesel oil miscella as raw material, catalyst C-1, C-2, C- 3, C-4 evaluation are carried out,
Mixed raw material oil nature is as shown in table 3 below:
3 raw material oil nature of table
| Analysis project | Analyze data |
| Density, g/ml | 0.862 |
| S,μg/g | 1688 |
| N,μg/g | 556 |
| Boiling range, DEG C | |
| Initial boiling point | 212.2 |
| 10% | 254.5 |
| 50% | 360.2 |
| 90% | 3692 |
| It does | 387.5 |
Operating condition is as shown in table 4 below, and evaluation result is as shown in table 5.
Table 4
Table 5 plus hydrogen evaluation result
Evaluation result is as shown in table 5, and in C-1, C-2, C-3, C-4 catalyst, C-1 catalyst boat coal with higher is received
Rate, heavy naphtha virtue is latent higher, can be used as good reformer feed, hydrogenation tail oil condensation point is lower.C-2 catalyst has higher
Hydrogenation activity, boat coal aromatic hydrocarbons it is lower be 10.9.The catalyst cracking activity of C-3 is higher, heavy naphtha yield 41.5%, and virtue is latent
48.5.Compare C-3 and reference agent C- 4, it can be seen that the Hydrogenation of C-4 is poor, and boat coal arene content is up to 18.5.
Compare tetra- kinds of catalyst of C-1, C-2, C-3, C-4, it can be seen that using citric acid as metallo-organic complex
Catalyst has stronger hydrogenation activity, and produced aviation kerosine has the characteristics that smoke point is high, arene content is low.Y, β compound molecule
The synergistic effect of sieve significantly improves the cryogenic property of aviation kerosine and diesel oil while improving diesel quality.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention,
Those skilled in the art can make various corresponding changes and modifications according to the present invention, but these it is corresponding change and
Deformation all should belong to the protection scope of the claims in the present invention.
Claims (15)
1. a kind of preparation method of hydrocracking catalyst, which comprises the steps of:
(1) it is added in modified Y molecular sieve, beta-molecular sieve and macroporous aluminium oxide using small porous aluminum oxide as the binder of matrix, kneading
It forms, catalyst carrier is made after drying and roasting；
(2) using vib metals and/or group VIII metal as active component, the salting liquid containing active component is prepared, continues to add
Enter citric acid as maceration extract, by the catalyst carrier incipient impregnation after the maceration extract drying and roasting, obtain plus hydrogen
Cracking catalyst.
2. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the hydrocracking catalyst
The specific surface area of agent is 220~550m20.25~0.75ml/g of/g, Kong Rongwei.
3. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that with catalyst carrier butt
On the basis of gross mass, wherein each component content are as follows: modified Y molecular sieve 20.0%~60.0%, beta-molecular sieve 10.0%~
50.0%, macroporous aluminium oxide 20.0%~60.0%, small porous aluminum oxide 10.0~50.0%.
4. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the active component, which accounts for, urges
15~40wt% of agent weight.
5. the preparation method of hydrocracking catalyst according to claim 1 or 4, which is characterized in that the active component
For vib metals and group VIII metal.
6. the preparation method of hydrocracking catalyst according to claim 5, which is characterized in that the vib metals
14~30wt% of catalyst weight is accounted in terms of tungsten oxide for tungsten；The group VIII metal is that nickel is accounted for and urged in terms of nickel oxide
3~10wt% of agent weight.
7. the preparation method of hydrocracking catalyst according to claim 6, which is characterized in that in step (2), the leaching
The molar ratio of citric acid and nickel is 0.1~1.0:1 in stain liquid.
8. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the modified Y molecular sieve
Brilliant packet constant is 2.430~2.460nm, and silica alumina ratio is 5~20.
9. the preparation method of hydrocracking catalyst according to claim 8, which is characterized in that the modified Y molecular sieve
It is successively to carry out ammonium exchange, hydro-thermal process and acid processing by NaY molecular sieve to obtain, the modified Y molecular sieve crystalline substance packet constant is
2.435~2.455nm, silica alumina ratio are 8~15.
10. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the silicon of the beta-molecular sieve
Aluminium ratio is 40~120.
11. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the small porous aluminum oxide
Specific surface area be 200~500m20.2~0.7ml/g of/g, Kong Rongwei.
12. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the macroporous aluminium oxide
Specific surface area be 200~600m20.4~1.2ml/g of/g, Kong Rongwei.
13. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that the system of the binder
Standby process are as follows: be dissolved in deionized water using inorganic acid and being stirred with small porous aluminum oxide, pasty masses are made；The nothing
Machine acid is selected from one or more of nitric acid, phosphoric acid, hydrochloric acid.
14. the preparation method of hydrocracking catalyst according to claim 1, which is characterized in that in step (1) and (2),
The temperature of the drying is 80~140 DEG C, and being dried the time is 2~8 hours；In step (1), the condition of the roasting
It is to be roasted 4~8 hours at 400~600 DEG C；In step (1), the condition of the roasting is that roasting 2~8 is small at 400~600 DEG C
When.
15. a kind of method that bad/heavy diesel fuel is hydrocracked, which is characterized in that with normal, vacuum distillate or secondary operation oil be original
Material oil, using hydrocracking catalyst made from the described in any item preparation methods of claim 1-14 as catalyst, is hydrocracked
Reaction condition are as follows: 6.0~10.0MPa of reaction pressure, hydrogen to oil volume ratio 600~1200, production heavy naphtha, aviation kerosine and low
Coagulation diesel oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810399344.2A CN110404581A (en) | 2018-04-28 | 2018-04-28 | A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810399344.2A CN110404581A (en) | 2018-04-28 | 2018-04-28 | A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110404581A true CN110404581A (en) | 2019-11-05 |
Family
ID=68357240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810399344.2A Pending CN110404581A (en) | 2018-04-28 | 2018-04-28 | A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110404581A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115283005A (en) * | 2022-08-15 | 2022-11-04 | 太原理工大学 | Preparation method of metal-coated supported nano zeolite alumina catalyst |
| CN116023990A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Hydrocracking method for producing jet fuel by using straight-run diesel oil in high yield |
| CN116060091A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1462167A1 (en) * | 2003-03-24 | 2004-09-29 | Institut Francais Du Petrole | Catalyst comprising at least one zeolite selected from ZBM-30, ZSM-48, EU-2 and EU-11 and at least a zeolite Y and a process for the hydroconversion of hydrocarbons using such a zeolite |
| US20070102322A1 (en) * | 2005-11-04 | 2007-05-10 | Li Wang | Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make jet fuel or distillate |
| CN102909082A (en) * | 2012-09-20 | 2013-02-06 | 中国海洋石油总公司 | Preparation method for middle oil type hydrocracking catalyst carrier |
| CN102950020A (en) * | 2012-09-20 | 2013-03-06 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst containing hierarchical pore Beta molecular sieve |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103215065A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Inferior catalytic cracking gasoline hydrotreatment method |
| CN104588077A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN104667969A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A hydrocracking catalyst and a preparing method thereof |
| CN106140281A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of middle oil type hydrocracking catalyst |
-
2018
- 2018-04-28 CN CN201810399344.2A patent/CN110404581A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1462167A1 (en) * | 2003-03-24 | 2004-09-29 | Institut Francais Du Petrole | Catalyst comprising at least one zeolite selected from ZBM-30, ZSM-48, EU-2 and EU-11 and at least a zeolite Y and a process for the hydroconversion of hydrocarbons using such a zeolite |
| US20070102322A1 (en) * | 2005-11-04 | 2007-05-10 | Li Wang | Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make jet fuel or distillate |
| CN103100417A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103215065A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Inferior catalytic cracking gasoline hydrotreatment method |
| CN102909082A (en) * | 2012-09-20 | 2013-02-06 | 中国海洋石油总公司 | Preparation method for middle oil type hydrocracking catalyst carrier |
| CN102950020A (en) * | 2012-09-20 | 2013-03-06 | 中国海洋石油总公司 | Method for preparing hydrocracking catalyst containing hierarchical pore Beta molecular sieve |
| CN104588077A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN104667969A (en) * | 2013-11-26 | 2015-06-03 | 中国石油化工股份有限公司 | A hydrocracking catalyst and a preparing method thereof |
| CN106140281A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of middle oil type hydrocracking catalyst |
Non-Patent Citations (2)
| Title |
|---|
| ZHANG, XUEJUN ET AL.: ""Hydrocracking of heavy oil using zeolites Y/Al-SBA-15 composites as catalyst supports"", 《JOURNAL OF POROUS MATERIALS》 * |
| 王健: ""多级孔Y和Beta分子筛加氢裂化催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116023990A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Hydrocracking method for producing jet fuel by using straight-run diesel oil in high yield |
| CN116060091A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method and application thereof |
| CN115283005A (en) * | 2022-08-15 | 2022-11-04 | 太原理工大学 | Preparation method of metal-coated supported nano zeolite alumina catalyst |
| CN115283005B (en) * | 2022-08-15 | 2024-03-12 | 太原理工大学 | Preparation method of metal-coated nano zeolite-loaded alumina catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103100417B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN101450320B (en) | Hydrocracking catalyst containing Y molecular sieve and preparation method thereof | |
| CN103100427B (en) | Hydrocracking catalyst carrier containing beta molecular sieve and preparation method thereof | |
| CN102309975A (en) | Method for preparing hydrocracking catalyst | |
| CN106669780B (en) | A kind of chemical industry type hydrocracking catalyst and preparation method thereof | |
| CN110404581A (en) | A kind of method that the preparation method of hydrocracking catalyst, bad/heavy diesel fuel are hydrocracked | |
| CN103191773B (en) | Method for preparing hydrocracking catalyst | |
| CN109423336B (en) | Hydrocracking method | |
| CN102872908B (en) | Preparation method for low-quality diesel hydrofining catalyst | |
| CN104667984B (en) | A kind of catalyst for hydro-upgrading carrier and preparation method thereof | |
| CN103100416A (en) | Diesel oil hydro-upgrading catalyst and preparation method thereof | |
| CN101618334B (en) | In situ type molecular sieve hydrogenation cracking catalyst and method for preparing same | |
| CN103191774B (en) | Method for preparing hydrocracking catalyst | |
| CN107344720B (en) | A kind of Y type molecular sieve and preparation method thereof | |
| CN105709820B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN107345155B (en) | A kind of method for hydrogen cracking | |
| CN107345161B (en) | A kind of method for hydrogen cracking of coal tar | |
| CN110237856A (en) | A kind of preparation method of poor quality/heavy diesel fuel hydrocracking catalyst | |
| CN105713657B (en) | Hydrocracking method | |
| CN107345154B (en) | A kind of method for hydrogen cracking of poor ignition quality fuel | |
| CN107344102B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN107344105B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN104667958B (en) | A hydrocracking catalyst and a preparing method thereof | |
| CN107344117B (en) | Hydrocracking catalyst and its preparation method | |
| CN107344120B (en) | Carrier of hydrocracking catalyst and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191105 |