CN110237856A - Preparation method of poor quality/heavy diesel oil hydrocracking catalyst - Google Patents
Preparation method of poor quality/heavy diesel oil hydrocracking catalyst Download PDFInfo
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- CN110237856A CN110237856A CN201810191572.0A CN201810191572A CN110237856A CN 110237856 A CN110237856 A CN 110237856A CN 201810191572 A CN201810191572 A CN 201810191572A CN 110237856 A CN110237856 A CN 110237856A
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- Prior art keywords
- hydrocracking catalyst
- catalyst
- preparation
- poor quality
- diesel fuel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 48
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 33
- 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 64
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000006229 carbon black Substances 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 78
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 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 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 19
- 238000004898 kneading Methods 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 15
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 241000208340 Araliaceae Species 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 7
- 235000003140 Panax quinquefolius Nutrition 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 235000008434 ginseng Nutrition 0.000 description 7
- 229910021417 amorphous silicon Inorganic materials 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
- 238000005406 washing Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 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 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 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
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- -1 metals salt Chemical class 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
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000003313 weakening effect 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
- 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
- B01J29/08—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a white carbon black modified hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst adopts a Y molecular sieve acidic cracking component, adds VIB group and VIII group metal salts as a hydrogenation component, adopts white carbon black as a binder matrix, and adopts a method of combining kneading and dipping to prepare a catalyst finished product. Experimental results show that the white carbon black can well weaken the interaction between the metal component and the carrier. The catalyst is used for producing naphtha by hydrocracking of poor heavy diesel oil, has higher hydrogenation selectivity, and has the characteristics of high heavy naphtha aromatic potential, low tail oil BMCI value and high C5+ liquid yield.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, the special white carbon black that adds is for weakening catalysis
Agent carrier and intermetallic interaction power, improve the hydrogenation activity and hydrogenation selectivity of catalyst.More particularly to a kind of bad, again
Matter H-G hydrocracking fecund Gao Fangqian naphtha and low BMCI value hydrogenation tail oil catalyst and preparation method thereof.
Background technique
In recent years, with the rapid development of the devices such as China's ethylene, PX, catalytic reforming, Chinese naphtha market is integrally in
Reveal the situation that supply falls short of demand.2015, although Chinese naphtha import volume surges to 6,650,000 tons (increasing by 80% on a year-on-year basis),
Chinese naphtha supply gap is still maintained at 4,190,000 tons/year.Therefore, the problem of industrial chemicals shortage will become China downstream
One of the main restricting factor of work industry development is carried out and how to be ground from the correlation of oil refining secondary operation device more producing chemical industry raw material
Study carefully work, has important practical significance to promoting to realize to refine oil to chemical industry transition.It is expected that the year two thousand twenty, Consumption of China diesel and gasoline ratio
It would fall to about 1.06:1, the lower general who has surrendered's centering state oil refining apparatus structural adjustment for consuming diesel and gasoline ratio brings huge challenge, superfluous bavin
The process change of oil is extremely urgent！It is hydrocracked by bad, heavy diesel fuel, diesel oil is converted to naphtha, high-quality hydrogenation tail oil,
While reducing diesel and gasoline ratio, domestic market naphtha notch is made up, improves added value of product, is enterprise's upgrading synergy.
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 and acid resistance of molecular sieve.Silica alumina ratio is improved, it is close to facilitate reduction acid site
Degree improves acid strength, can improve cracking and the ratio between react with hydrogen transfer activity, reduces coke generation, improvement product distribution.This
Outside, having can bear to be hydrocracked more stringent reaction condition compared with the molecular sieve of high silica alumina ratio, extend the use of catalyst
Service life.Silica alumina ratio is higher, and heat-resisting, the resistance to steam and acid resistance of molecular sieve are better, and application field will also obtain further
It expands.
Patent CN200610134152.6 discloses a kind of preparation method of hydrocracking catalyst, the process employs
A kind of material containing molecular sieve and amorphous silicon aluminium loads hydrogenation metal active component using dipping or the method for co-precipitation
Final catalyst is made.Wherein carrier material is the method preparation that molecular sieve is directly added into during amorphous silicon aluminium plastic
, it is easy to cause amorphous silicon aluminium agglomeration occur, is also easy to enter to square duct or block the aperture of molecular sieve, influence
The distribution of amorphous silicon aluminium over a molecular sieve, molecular sieve and amorphous silicon aluminium duct connectivity are poor, so that the ratio table of catalyst
Area and hole, which hold, to be reduced, and active metal distribution is not easily controlled, so that the hydrogenating function of catalyst and cracking function are not
Matching, influences the performance of catalyst.
Patent US4762813 and US4860803 propose to roast after aluminium oxide and molecular sieve mixed-forming, then under high temperature
Processing, then impregnates hydrogenation metal, the purpose is to voluminous intermediate oil and solves the problems, such as unstable product quality.Y used
Molecular sieve first passes through super stabilizing processing, and brilliant packet constant is between 2.440~2.465nm, and depth steam treatment makes again after molding
Brilliant packet constant is further reduced between 2.420~2.435nm, so that molecular sieve super-hydrophobicization, carrier secondary pore increases, acid
Density reduces, intensity improves, to achieve the purpose that improve the highly selective of intermediate oil.With molecular sieve elder generation hydro-thermal process
After form and soak metal phase ratio again, molecular sieve forms hydro-thermal process again prior to aluminium oxide, and sieve particle can be made more uniformly to connect
Vapor is touched, so that quality between every batch materials be made to be easier to ensure that.This method is the disadvantage is that aluminium oxide and molecular sieve mixed-forming
Hydro-thermal process energy consumption is higher afterwards.
Patent CN200710158361.9 gives a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, using mixed
The catalyst of pinching method preparation contains nonionic surface active agent in the active metal solution of the catalyst, this method preparation
The characteristics of there is catalyst macropore to hold, specific surface area is suitable for, and active metal is uniformly dispersed.
Add hydrogen disclosed in the patents such as patent CN200810117102.6, CN200710012770.8, CN00109747.4
Cracking catalyst is all to prepare the single raw material mechanical mixture such as molecular sieve, aluminium oxide.Catalyst prepared by this method
The performance of each component performance can be influenced because the mixing of various raw materials is uneven.
Summary of the invention
Place for overcome the deficiencies in the prior art, can be used for bad, heavy diesel the present invention provides one kind and hydrogen is added to split
Change catalyst and preparation method thereof.The catalyst of this method preparation is hydrocracked production naphtha for bad heavy diesel fuel, have compared with
High hydrogenation selectivity has the latent height of heavy naphtha virtue, and tail oil BMCI value is low, C5+ liquid receives high feature.
For this purpose, the present invention provides a kind of preparation method of poor quality/heavy diesel fuel hydrocracking catalyst, which is used for
Production Gao Fangqian naphtha and low BMCI value tail oil, the preparation method of the hydrocracking catalyst include the following steps:
S1 is added using white carbon black as the binder of matrix in modified Y molecular sieve and macroporous aluminium oxide, extruded moulding, is done
Catalyst carrier is made after dry roasting；
S2 prepares the salting liquid for containing vib metals and group VIII metal as maceration extract, and the catalyst is carried
Body incipient impregnation drying and roasting after the maceration extract, obtains hydrocracking catalyst.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein described be hydrocracked is urged
Agent specific surface area is preferably 200~500m2/ g, it is preferably 0.2~0.6ml/g that hole, which holds,.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein dry with catalyst carrier
Base gross mass is percentages, and wherein each component content is preferably modified Y molecular sieve 30.0%~80.0%, macroporous aluminium oxide
10.0%~60.0%, white carbon black 10.0%~60.0%.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the group vib metal
Preferably tungsten accounts for the 15.0~30.0% of catalyst gross mass in terms of tungsten oxide；Section VIII race metal is preferably nickel, with
Nickel oxide meter accounts for the 3.0~15.0% of catalyst gross mass.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the tungsten, with tungsten oxide
Meter, preferably accounts for the 22.0~26.0% of catalyst gross mass；The nickel preferably accounts for catalyst gross mass in terms of nickel oxide
4.0~8.0%.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the modified Y molecular sieve
Brilliant packet constant is preferably 2.430~2.460nm, and silica alumina ratio is preferably 5~20, sodium oxide content preferably≤0.2wt%.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the macroporous aluminium oxide
Specific surface area is preferably 200~400m2/ g, it is preferably 0.5~1.0ml/g that hole, which holds,.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the white carbon black compares table
Area preferably 100~500m2/G, partial size preferably 5~30nm.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the system of the binder
Preparation Method is preferred are as follows: is dissolved in after mixing in deionized water with white carbon black and being stirred with inorganic acid, pasty masses are made；
Nitric acid accounts for the 5%~45% of white carbon black quality in binder, and binder butt ratio is 5wt%~40wt%.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the inorganic acid is selected from
At least one of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.
Poor quality of the present invention/heavy diesel fuel hydrocracking catalyst preparation method, wherein the group vib metal
Salt be preferably selected from one or more of wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate；The salt of the group VIII metal is excellent
Choosing is selected from one or more of nitrate, acetate, carbonate.
The preparation method of hydrocracking catalyst of the present invention, specifically includes following content: by modified Y molecular sieve, macropore oxygen
Change aluminium, be first dried 2~8 hours at 80~150 DEG C after the binder progress kneading extruded moulding that white carbon black is matrix,
Then carrier after drying is placed in Muffle furnace, is roasted 2~8 hours at 400~600 DEG C；By group VIB, group VIII gold
Belong to salting liquid to be added in carrier strip in a manner of incipient impregnation, is first dried 2~8 hours at 80~150 DEG C, then
Dry rear catalyst is placed in Muffle furnace, is roasted 2~8 hours at 400~600 DEG C, finished catalyst is made.
Hydrocracking catalyst of the present invention includes modified Y molecular sieve, macroporous aluminium oxide, white carbon black, using Ni-W as plus hydrogen
Metal component, with catalyst butt quality percentages, catalyst support component includes modified Y molecular sieve 30%~80%, excellent
Select 40%~60%；Macroporous aluminium oxide 10%~60%, preferably 10%~50%；White carbon black 10.0%~40.0%, preferably
10%~30%；WO3Content 15~30%, preferably 22%~26%, NiO content 3~15%, preferably 4~8%.
Modified Y molecular sieve crystalline substance packet 2.430~2.460nm of constant used in the present invention, silica alumina ratio 5~20, preferably brilliant packet are normal
2.440~2.455nm of number, silica alumina ratio 8~15.
The preparation method of hydrocracking catalyst of the present invention, in step S1, the modified Y molecular sieve is by general
Lead to commercially available NaY molecular sieve to combine made from modification as hydro-thermal with sour, the physical parameter of common commercially available NaY molecular sieve is preferably
Silica alumina ratio 4.2:1, Na2O content 12.5wt%, brilliant packet constant 2.468nm, relative crystallinity 96%.
The preparation of the modified Y molecular sieve is handed over the following steps are included: common commercially available NaY molecular sieve is passed sequentially through ammonium
It changes, first time hydro-thermal process, acid is modified and second of hydro-thermal process obtains modified Y molecular sieve.Its it is specific the preparation method is as follows:
(1) ammonium exchanges, NaY original powder ammonium exchange 3 times in the method for the present invention, 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, preferably ammonium chloride, and ammonium salt concentration used is 0.1
~2.0mol/L, preferably 0.5~1.0mol/L, ammonium exchange liquid consolidate mass ratio 5:1~30:1, preferably 10:1~20:1, ammonium exchange
Time 0.5~3 hour, preferably 1~2 hour.
(2) hydro-thermal process, the present invention in Y molecular sieve hydro-thermal process 3 times, hydro-thermal process temperature between 500~750 DEG C,
It is preferred that between 550~650 DEG C, hydrothermal conditions 0.5~4 hour, preferably 1.0~2.0 hours, hydro-thermal process pressure 0.05
~0.5MPa, preferably 0.1~0.3MPa, above-mentioned hydrothermal treatment process preferably carry out under the conditions of water filling, and water injection rate 50~
600ml/h, preferably 100~400ml/h.
200~400m of big pore alumina ratio surface area in the present invention20.5~1.0ml/g of/g, Kong Rong, preferably compares table
250~380m of area20.6~0.9ml/g of/g, Kong Rong.
White carbon black specific surface area used is in 100~500m in the present invention2/ g, 5~30nm of partial size, preferably specific surface area exist
150~300m2/ g, 8~20nm of partial size.
Acid used in binder uses inorganic acid in the present invention, can make one of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid or several
Kind, preferably nitric acid.Nitric acid accounts for white carbon black mass fraction 5%~45%, preferably 10%~30%, binder butt in binder
Than in 5wt%~40wt%, preferably 15wt%~25wt%.
Vib metals salt used in the present invention can be the one or more of wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate,
It is preferred that ammonium metatungstate；Group VIII metal salt can be the one or more of nickel nitrate, nickel acetate, basic carbonate nickel salt, preferably
Nickel nitrate.
The drying temperature of carrier and catalyst of the present invention is 80~150 DEG C, preferably 110~130 DEG C；It is dried the time 2
~8 hours, preferably 4~6 hours.Carrier calcination condition is to roast at 4~8 hours, preferably 450~550 DEG C at 400~600 DEG C
Roasting 3~7 hours；Catalyst roasting condition is to roast to roast 3 at 2~8 hours, preferably 450~550 DEG C at 400~600 DEG C
~7 hours.
The present invention has the beneficial effect that:
In the step S1 of preparation method of the invention, addition is in modified Y molecular sieve and macroporous aluminium oxide with white carbon black
Catalyst carrier is made after drying and roasting for the binder of matrix, extruded moulding.
Wherein, being added can weaken between hydrogenation metal component and carrier by the binder of matrix of white carbon black well
Interaction, form the II type hydrogenation sites that more crystallite numbers of plies are 2~5 layers, length is 6~12nm.
Catalyst made from preparation method of the invention is hydrocracked production naphtha for bad heavy diesel fuel, has higher
Hydrogenation selectivity, there is the latent height of heavy naphtha virtue, tail oil BMCI value is low, C5+ liquid receives high feature.
Detailed description of the invention
Fig. 1 is the NH of C-1 catalyst and C-4 catalyst3- TPD spectrogram.
Specific embodiment
It is further described and proves by the following examples technical effect of the present invention, but should not be understood as pair
Limitation of the invention.
The detailed process of hydrocracking catalyst preparation of the present invention are as follows:
(1) by commercially available NaY molecular sieve (silica alumina ratio 4.2:1, Na2O content 12.5wt%, brilliant packet constant 2.468nm,
Relative crystallinity 96%) pass sequentially through that ammonium exchange, first time hydro-thermal process, acid is modified and second of hydro-thermal process obtains modified Y
Molecular sieve；
(2) white carbon black is added in the deionized water solution containing nitric acid, binder is made in kneading to paste shape, sealing
It saves stand-by.
(3) by modified Y molecular sieve, macroporous aluminium oxide, the binder that white carbon black is matrix, after kneading extruded moulding, first exist
It is dried 2~8 hours at 80~150 DEG C, then carrier after drying is placed in Muffle furnace, roasts 2 at 400~600 DEG C
~8 hours, catalyst carrier is made；
(4) group VIB, group VIII metal salt solution are added in carrier strip in a manner of incipient impregnation, first 80
It is dried at~150 DEG C 2~8 hours, then dry rear catalyst is placed in Muffle furnace, roasts 2 at 400~600 DEG C
~8 hours, finished catalyst is made.
Wherein, the hydrocracking catalyst specific surface area is preferably 200~500m2/ g, hole appearance preferably 0.2~
0.6ml/g；
Wherein, using catalyst carrier butt gross mass as percentages, wherein each component content is preferably, modified Y molecule
Sieve 30.0%~80.0%, macroporous aluminium oxide 10.0%~60.0%, white carbon black 10.0%~60.0%；
Wherein, the vib metals are preferably tungsten, in terms of tungsten oxide, account for catalyst gross mass 15.0~
30.0%；The group VIII metal is preferably nickel, in terms of nickel oxide, accounts for the 3.0~15.0% of catalyst gross mass；
Wherein, the tungsten preferably accounts for the 22.0~26.0% of catalyst gross mass in terms of tungsten oxide；The nickel, with oxygen
Change nickel meter, preferably accounts for the 4.0~8.0% of catalyst gross mass；
Wherein, the modified Y molecular sieve crystalline substance packet constant is preferably 2.430~2.460nm, and silica alumina ratio is preferably 5~20,
Sodium oxide content preferably≤0.2wt%；
Wherein, the macroporous aluminium oxide specific surface area is preferably 200~400m2/ g, it is preferably 0.5~1.0ml/ that hole, which holds,
g；
Wherein, the white carbon black specific surface area preferably 100~500m2/G, partial size preferably 5~30nm.
Wherein, the preparation method of the binder is preferred are as follows: is dissolved in after mixing in deionized water with white carbon black with inorganic acid
It stirs, pasty masses is made；Nitric acid accounts for the 5%~45% of white carbon black quality in binder, and binder butt ratio is
5wt%~40wt%；
Wherein, the inorganic acid is selected from least one of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.
Wherein, the salt of the vib metals be preferably selected from one of wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate or
It is several；The salt of the group VIII metal is preferably selected from one or more of nitrate, acetate, carbonate.
The preparation of the modified Y molecular sieve is handed over the following steps are included: common commercially available NaY molecular sieve is passed sequentially through ammonium
It changes, first time hydro-thermal process, acid is modified and second of hydro-thermal process obtains modified Y molecular sieve.Its it is specific the preparation method is as follows:
(1) ammonium exchanges, NaY original powder ammonium exchange 3 times in the method for the present invention, 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, preferably ammonium chloride, and ammonium salt concentration used is 0.1
~2.0mol/L, preferably 0.5~1.0mol/L, ammonium exchange liquid consolidate mass ratio 5:1~30:1, preferably 10:1~20:1, ammonium exchange
Time 0.5~3 hour, preferably 1~2 hour.
(2) hydro-thermal process, the present invention in Y molecular sieve hydro-thermal process 3 times, hydro-thermal process temperature between 500~750 DEG C,
It is preferred that between 550~650 DEG C, hydrothermal conditions 0.5~4 hour, preferably 1.0~2.0 hours, hydro-thermal process pressure 0.05
~0.5MPa, preferably 0.1~0.3MPa, above-mentioned hydrothermal treatment process preferably carry out under the conditions of water filling, and water injection rate 50~
600ml/h, preferably 100~400ml/h.
Embodiment 1
The preparation of modified Y molecular sieve
(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 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 550 DEG C, water
Heat treatment time 1.0 hours, hydro-thermal process pressure 0.1MPa, water injection rate 100ml/h.After the completion of first time hydro-thermal process, repeat
Step (1) carries out ammonium exchange, then repeats hydro-thermal process twice by above-mentioned hydrothermal condition, obtains hydrothermal modification Y molecular sieve,
It is denoted as Y-1, property ginseng is shown in Table 1.
Embodiment 2
The preparation of modified Y molecular sieve
(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.After the completion of first time hydro-thermal process, repeat
Step (1) carries out ammonium exchange, then repeats hydro-thermal process twice by above-mentioned hydrothermal condition, obtains hydrothermal modification Y molecular sieve,
It is denoted as Y-2, property ginseng is shown in Table 1.
Embodiment 3
The preparation of modified Y molecular sieve
(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.After the completion of first time hydro-thermal process, repeat
Step (1) carries out ammonium exchange, then repeats hydro-thermal process twice by above-mentioned hydrothermal condition, obtains hydrothermal modification Y molecular sieve,
It is denoted as Y-3, property ginseng is shown in Table 1.
1 modified molecular screen property of table
| Molecular sieve number | Y-1 | Y-2 | Y-3 |
| Brilliant packet constant, nm | 2.460 | 2.449 | 2.455 |
| Framework si-al ratio | 6.7 | 11.5 | 8.5 |
| Relative crystallinity, % | 79 | 78 | 85 |
| Specific surface area, m2/g | 621.5 | 588.9 | 576.7 |
| Kong Rong, ml/g | 0.334 | 0.456 | 0.422 |
| Aperture, nm | 3.4 | 3.6 | 3.8 |
Seen from table 1, with the increase of hydro-thermal process pressure and temperature, Y molecular sieve degree of dealumination is continuously increased, sial
Than increasing to the 12.5 of Y-2 from the 6.6 of Y-1, brilliant packet constant is also contracted to the 2.449 of Y-2 by the 2.460 of Y-1.By hydro-thermal
Y molecular sieve has flourishing Secondary Channel after processing, and most probable pore size is between 3.4~3.8nm.
Embodiment 4
The preparation of hydrocracking catalyst
31.0g nitric acid solution (65wt%) is taken, after the dilution of 1302.33g Purified Water, is slowly added to equipped with 200g hard charcoal
In black kneading machine, abundant kneading to paste shape is prepared into nitric acid content 10wt%, the binder B-1 of butt 15wt%.
41.45 gram molecules are sieved into Y-1 (butt 98wt%), 66.67 grams of binder B-1,69.44g macroporous aluminium oxide kneadings
Extrusion, 110 DEG C drying 4 hours, 450 DEG C roast 4 hours, obtain catalyst carrier S-1.
It takes 15.57g nickel nitrate, 30.2g ammonium metatungstate to be dissolved in deionized water, is completely dissolved rear incipient impregnation in 70g
In carrier S -1,110 DEG C drying 4 hours, 450 DEG C roast 4 hours, obtain catalyst C-1, and property ginseng is shown in Table 2.
Embodiment 5
The preparation of hydrocracking catalyst
92.3g nitric acid solution (65wt%) is taken, after the dilution of 707.7g Purified Water, is slowly added to equipped with 200g white carbon black
Kneading machine in, abundant kneading to paste shape is prepared into nitric acid content 30wt%, the binder B-2 of butt 25wt%.
62.18 gram molecules are sieved into Y-2 (butt 98wt%), 120 grams of binder B-2,13.89g macroporous aluminium oxide kneadings are squeezed
Item, 130 DEG C drying 6 hours, 550 DEG C roast 7 hours, obtain catalyst carrier S-2.
It takes 31.14g nickel nitrate, 25.6g ammonium metatungstate to be dissolved in deionized water, is completely dissolved rear incipient impregnation in 70g
In carrier S -2,130 DEG C drying 6 hours, 550 DEG C roast 7 hours, obtain catalyst C-2, and property ginseng is shown in Table 2.
Embodiment 6
The preparation of hydrocracking catalyst
61.5g nitric acid solution (65wt%) is taken, after the dilution of 938.5g Purified Water, is slowly added to equipped with 200g white carbon black
Kneading machine in, abundant kneading to paste shape is prepared into nitric acid content 20wt%, the binder B-3 of butt 20wt%.
58.81 gram molecules are sieved into Y-3 (butt 98wt%), 100 grams of binder B-3,27.78g macroporous aluminium oxide kneadings are squeezed
Item, 115 DEG C drying 5 hours, 500 DEG C roast 5 hours, obtain catalyst carrier S-3.
It takes 19.46g nickel nitrate, 29.1g ammonium metatungstate to be dissolved in deionized water, is completely dissolved rear incipient impregnation in 70g
In carrier S -3,115 DEG C drying 5 hours, 500 DEG C roast 5 hours, obtain catalyst C-3, and property ginseng is shown in Table 2.
Comparative example 1
The preparation of hydrocracking catalyst
31.0g nitric acid solution (65wt%) is taken, after the dilution of 1302.33g Purified Water, is slowly added to equipped with 200g aperture
In the kneading machine of aluminium oxide, abundant kneading to paste shape is prepared into nitric acid content 10wt%, the binder D- of butt 15wt%
1。
41.45 gram molecules are sieved into Y-1 (butt 98wt%), 66.67 grams of binder D-1,69.44g macroporous aluminium oxide kneadings
Extrusion, 110 DEG C drying 4 hours, 450 DEG C roast 4 hours, obtain catalyst carrier S-4.
It takes 15.57g nickel nitrate, 30.2g ammonium metatungstate to be dissolved in deionized water, is completely dissolved rear incipient impregnation in 70g
In carrier S -4,110 DEG C drying 4 hours, 450 DEG C roast 4 hours, obtain catalyst C-4, and property ginseng is shown in Table 2.
2 catalyst property of table
| Catalyst number | C-1 | C-2 | C-3 | C-4 |
| Specific surface area, m2/g | 333.7 | 331.8 | 363.8 | 321.2 |
| Kong Rong, ml/g | 0.355 | 0.367 | 0.356 | 0.366 |
| Aperture, nm | 3.87 | 3.46 | 3.55 | 3.68 |
| NiO, wt% | 4.1 | 7.9 | 4.9 | 4.0 |
| WO3, wt% | 26.2 | 22.5 | 25.0 | 26.5 |
| Mechanical strength, N/cm | 232 | 235 | 244 | 242 |
As can be seen from Table 2, the specific surface area of catalyst C1~C4 is in 331.8~363.8m2Between/g, catalytic mechanical is strong
Degree is between 232~244N/cm.Thus result illustrates, specific surface area of the white carbon black to catalyst, hole are added in a binder
The material properties affects such as appearance are little.Catalyst has preferable mechanical strength simultaneously.
Embodiment 7
The evaluation of hydrocracking catalyst
On 200ml plus hydrogen evaluating apparatus, C1~C4 catalyst is carried out using straight-run diesel oil and catalytic diesel oil miscella
Evaluation.
Feedstock oil enters cracking zone after 1 anti-refining stage hydrofinishing, and raw material oil nature is referring to shown in table 3.Cracking zone work
Skill condition are as follows: reaction pressure 8.0MPa, hydrogen to oil volume ratio 700:1,1.5 h of volume sky-1, evaluation result, which is joined, to be shown in Table 4.
3 raw material oil nature of table
Table 4 plus hydrogen evaluation result
For table 4 as a result, in C-1, C-2, C-3, C-4 catalyst, the catalyst cracking activity of C-1 is moderate, and C5+ liquid receipts are up to
97.8%, heavy naphtha virtue is latent higher, reaches 54；C-2 catalyst cracking activity with higher, heavy naphtha yield reach
55%, hydrogenation tail oil BMCI value is lower, can be used as good ethylene cracking material；C-3 catalyst hydrogenation cracking activity is between C-1
Between C-2.Comparison C-1 and reference agent C-4, which can be seen that using white carbon black as binder, can effectively improve catalyst
Hydrogenation cracking activity and selectivity.Compare four kinds of catalyst, it can be seen that using the modified hydrocracking catalyst of white carbon black
Hydrogenation activity and selectivity are higher, while the exploitation of mesoporous Y molecular sieve, can satisfy naphtha cut selectivity appropriateness plus hydrogen
Maximum retains mononuclear aromatics and cycloalkane, and it is latent to improve naphtha virtue.Diesel oil distillate selectivity deep hydrogenation aromatic hydrocarbons largely adds hydrogen
Saturation improves hydrogenation tail oil property, can be used as high-quality ethylene cracking material and fine-quality diesel oil fraction.
Also, the acid amount that as seen from Figure 1, can effectively improve catalyst using white carbon black as binder, is urged to improve
Agent is hydrocracked performance.
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 protection scope of the present invention.
Claims (11)
1. a kind of poor quality/heavy diesel fuel hydrocracking catalyst preparation method, the catalyst for produce Gao Fangqian naphtha and
Low BMCI value tail oil, which is characterized in that the preparation method of the hydrocracking catalyst includes the following steps:
S1 is added in modified Y molecular sieve and macroporous aluminium oxide using white carbon black as the binder of matrix, extruded moulding, drying and roasting
Catalyst carrier is made afterwards；
S2 prepares the salting liquid for containing vib metals and group VIII metal as maceration extract, by described catalyst carrier etc.
Volume impregnation drying and roasting after the maceration extract, obtains hydrocracking catalyst.
2. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Hydrocracking catalyst specific surface area is 200~500m20.2~0.6ml/g of/g, Kong Rongwei.
3. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that urge
Agent carrier butt gross mass is percentages, and wherein each component content is modified Y molecular sieve 30.0%~80.0%, macropore
Aluminium oxide 10.0%~60.0%, white carbon black 10.0%~60.0%.
4. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Vib metals are tungsten, in terms of tungsten oxide, account for the 15.0~30.0% of catalyst gross mass；The group VIII metal is nickel,
In terms of nickel oxide, the 3.0~15.0% of catalyst gross mass are accounted for.
5. poor quality according to claim 4/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Tungsten accounts for the 22.0~26.0% of catalyst gross mass in terms of tungsten oxide；The nickel accounts for catalyst gross mass in terms of nickel oxide
4.0~8.0%.
6. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Modified Y molecular sieve crystalline substance packet constant is 2.430~2.460nm, and silica alumina ratio is 5~20, sodium oxide content≤0.2wt%.
7. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Macroporous aluminium oxide specific surface area is 200~400m20.5~1.0ml/g of/g, Kong Rongwei.
8. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
100~500m of white carbon black specific surface area2/G, 5~30nm of partial size.
9. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Binder the preparation method comprises the following steps: be dissolved in inorganic acid mixed in deionized water with white carbon black after stir, be made paste
Substance；Nitric acid accounts for the 5%~45% of white carbon black quality in binder, and binder butt ratio is 5wt%~40wt%.
10. poor quality according to claim 9/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
Inorganic acid is selected from least one of nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid.
11. poor quality according to claim 1/heavy diesel fuel hydrocracking catalyst preparation method, which is characterized in that described
The salt of vib metals is selected from one or more of wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate；The group VIII metal
Salt be selected from one or more of nitrate, acetate, carbonate.
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| CN114471669A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114471670A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for hydrocracking and preparation method and application thereof |
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