CN113528181B - Combined method for producing heavy aviation kerosene - Google Patents
Combined method for producing heavy aviation kerosene Download PDFInfo
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- CN113528181B CN113528181B CN202010313349.6A CN202010313349A CN113528181B CN 113528181 B CN113528181 B CN 113528181B CN 202010313349 A CN202010313349 A CN 202010313349A CN 113528181 B CN113528181 B CN 113528181B
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- molecular sieve
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- oil
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- 239000003350 kerosene Substances 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 102
- 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 93
- 239000002808 molecular sieve Substances 0.000 claims abstract description 92
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 66
- 239000011574 phosphorus Substances 0.000 claims abstract description 66
- 238000007670 refining Methods 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 70
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 55
- 239000002253 acid Substances 0.000 claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 24
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003223 protective agent Substances 0.000 claims description 14
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- 239000000463 material Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 230000005484 gravity Effects 0.000 description 13
- 239000002283 diesel fuel Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000295 complement effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- 239000000203 mixture Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- -1 naphthenic diesel Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
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- 238000000926 separation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- 244000068988 Glycine max Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 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 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/16—Residues
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of aviation kerosene production, and discloses a combined method for producing heavy aviation kerosene, which comprises the following steps: (1) Carrying out a first contact reaction on hydrogen and heavy raw oil and a hydrofining catalyst to obtain a hydrotreating effluent with the organic nitrogen content of 50-600 mu g/g; (2) Carrying out a second contact reaction on the hydrotreated effluent and a hydrocracking catalyst to obtain a hydrocracking effluent, wherein the hydrocracking catalyst is a phosphorus-containing molecular sieve hydrocracking catalyst; (3) Carrying out a third contact reaction on the hydrocracking effluent and a post-refining catalyst to obtain a post-refining effluent; (4) Fractionating the post-refining effluent to obtain an aviation kerosene fraction, wherein the distillation range of the aviation kerosene fraction is 180-215 ℃; the density of the heavy raw oil is 0.9-1.05g/cm 3 And the fraction above 350 ℃ in the distillation range accounts for more than 10 percent by weight. The method has simple process flow and can obtain the high-quality large-specific-gravity aviation kerosene.
Description
Technical Field
The invention relates to the field of aviation kerosene production, in particular to a combination method for producing heavy aviation kerosene.
Background
The high-density jet fuel is also called large specific gravity aviation kerosene, and is a jet fuel with high density and high volume heat value. RJ-4, RJ-5, JP-5,JP-9 and JP-10, etc. series high density synthetic jet fuel with density over 0.935g/cm 3 . Compared with the common 3# jet fuel (the density is generally 0.77-0.81 g/cm) 3 ) Compared with the prior art, the fuel has the advantages of improving the heat value of the fuel in unit volume, providing 5-9% of endurance mileage, improving the flight speed, reducing the flight time and having wide application prospect. The domestic standard GJB1603-93 (Large specific gravity jet fuel specification) specifies the fuel standard suitable for high-speed turbine engines, and the main index requires that the density reaches 0.835g/cm 3 The weight heat value reaches or exceeds 42.9MJ/kg, the flash point is not lower than 60, the aromatic hydrocarbon content is not more than 10 and the like. In order to meet the domestic requirements, the Qilu petrochemical research institute uses naphthenic base kerosene fraction as raw material, and tests for producing large-specific gravity aviation kerosene by high-pressure hydrofining are carried out, so that the density of the aviation kerosene can be obtained to be 0.835g/cm 3 The product can obtain higher endurance mileage relative to common No. 3 aviation kerosene in flight test. Then, the preparation research of the large-specific gravity aviation kerosene in China makes a series of progress.
CN102304387B discloses a production method of coal-based high-density jet fuel, which comprises the following steps: the method comprises the following steps that coalification light oil and liquefied distillate oil from a direct coal liquefaction process enter an expansion bed hydrotreating reactor with forced internal circulation to contact with hydrogen and a hydrotreating catalyst, and outlet material flow of the expansion bed hydrotreating reactor is separated and fractionated to obtain light distillate oil, medium distillate oil and heavy distillate oil; mixing the light distillate oil and the medium distillate oil, then entering a deep hydrogenation refining fixed bed reactor, contacting and reacting with hydrogen and a hydrogenation refining catalyst, and separating and fractionating the material flow at the outlet of the deep hydrogenation refining fixed bed reactor to obtain the high-density jet fuel; wherein, a liquid collecting cup is arranged above the inside of the hydrotreating reactor, and the collected liquid is conveyed by a pipeline, is pressurized by a forced circulation pump and then is sent to the bottom of the hydrotreating reactor.
CN105733670A discloses a method for producing large-specific gravity aviation kerosene by hydrogenation of catalytic recycle oil, which comprises the steps of mixing the catalytic recycle oil with hydrogen, then introducing the mixture into a hydrotreating reaction zone, and sequentially contacting with a hydrogenation protective agent, a hydrofining catalyst and a hydrogenation modified catalyst A for hydrogenation reaction; the hydrotreating effluent enters a hydro-upgrading reaction zone, and a hydro-upgrading catalyst B containing amorphous silica-alumina and modified Y zeolite is used in the hydro-upgrading reaction zone to carry out hydro-upgrading reaction in the presence of hydrogen; and the obtained hydrogenation modified effluent enters a hydrogenation complementary refining reaction zone to carry out hydrogenation complementary refining reaction, and the hydrogenation complementary refining product is separated to obtain the aviation kerosene with large specific gravity. The application takes the catalytic recycle oil as the raw material to produce the large-specific-gravity aviation kerosene with high maximum density, high volume heat value, low aromatic hydrocarbon content and good low-temperature performance, and can widen the raw material sources of large-specific-gravity aviation kerosene products.
CN105419865A discloses a method for producing jet fuel, comprising the steps of: (1) Hydrogen and raw oil are in contact reaction with a hydrofining catalyst; optional step (2): separating a gas phase material flow from the effluent obtained in the step (1) to obtain a liquid phase material flow; and (3): contacting the liquid phase material flow obtained in the step (2) and hydrogen or effluent obtained in the step (1) with a hydrocracking catalyst for reaction; and (4): separating jet fuel and diesel oil from the effluent obtained in the step (3); and (5): sending at least part of diesel oil obtained in the step (4) into the step (1) to be mixed with the raw oil, or sending at least part of diesel oil obtained in the step (4) into the step (3) to be mixed with the liquid phase material flow or the effluent obtained in the step (1); wherein the aromatic hydrocarbon content of the raw oil is more than 40 wt%; the contact reaction conditions of the step (1) enable the saturation rate of bicyclic aromatics in raw oil to be 70-90%, and the contact reaction conditions of the step (3) enable the saturation rate of total aromatics in liquid feeding of the step (3) to be 75-95%.
CN103789034A discloses a method for producing large-specific gravity aviation kerosene by hydrogenation of medium-low temperature coal tar, which comprises the following steps: (1) Fractionating medium-low temperature coal tar to obtain light fraction and heavy fraction with the cutting point of 480-510 ℃; (2) Mixing the light fraction obtained in the step (1) with hydrogen, then feeding the mixture into a hydrotreating reaction zone, and sequentially contacting with a hydrogenation protective agent and a hydrofining catalyst to carry out hydrogenation reaction; (3) Carrying out gas-liquid separation on the hydrofining effluent obtained in the step (2), and enabling a liquid-phase product obtained by separation to enter a fractionating tower; (4) The kerosene fraction with the temperature of 140-290 ℃ obtained by fractionation in the step (3) enters a hydrogenation modification reaction zone, and hydrogenation modification reaction is carried out in the hydrogenation modification reaction zone in the presence of hydrogen by using a hydrogenation modification catalyst containing amorphous silica-alumina and modified Y zeolite; (5) And (4) enabling the hydrogenation modified effluent obtained in the step (4) to enter a hydrogenation complementary refining reaction zone, contacting with a hydrogenation complementary refining catalyst in the presence of hydrogen to perform hydrogenation complementary refining reaction, and separating a hydrogenation complementary refining product to obtain a large-specific-gravity aviation kerosene component.
The prior art research mainly focuses on the production of large-specific gravity aviation kerosene by using coal diesel oil fractions. The coal-diesel oil fractions mainly comprise secondary processing fractions such as catalytic diesel oil and coal tar. However, as aviation kerosene is special in use, the requirements on the quality of aviation kerosene are stricter than those of other finished oils in the world in order to ensure flight safety. China consistently attaches importance to flight safety and aviation kerosene quality, and establishes aviation kerosene production management methods, wherein clear requirements are provided for the doping proportion of secondary fractions in a production aviation kerosene hydrogenation device and the pressure grade of the device.
Disclosure of Invention
The invention aims to overcome the defect of high proportion of secondary processing heavy and poor fractions in the existing method for producing large-specific-gravity aviation kerosene, and provides a combined method for producing heavy aviation kerosene, which has simple process flow and can obtain high-quality large-specific-gravity aviation kerosene.
In order to achieve the above object, the present invention provides an integrated process for producing heavy aviation kerosene, the process comprising the steps of:
(1) Carrying out a first contact reaction on hydrogen and heavy raw oil and a hydrofining catalyst to obtain a hydrotreating effluent, wherein the content of organic nitrogen in the hydrotreating effluent is 50-600 mu g/g;
(2) Performing a second contact reaction on the hydrotreating effluent obtained in the step (1) and a hydrocracking catalyst to obtain a hydrocracking effluent, wherein the hydrocracking catalyst is a phosphorus-containing molecular sieve hydrocracking catalyst;
(3) Carrying out a third contact reaction on the hydrocracking effluent obtained in the step (2) and a post-refining catalyst to obtain a post-refining effluent;
(4) Fractionating the post-refining effluent obtained in the step (3) to obtain an aviation kerosene fraction, wherein the distillation range of the aviation kerosene fraction is 180-215 ℃;
wherein the density of the heavy raw oil is 0.9-1.05g/cm 3 And the fraction above 350 ℃ in the distillation range accounts for more than 10 percent by weight.
In the prior art, when the wax oil fraction is adopted to prepare the aviation kerosene, the product density is generally 0.79-0.81g/cm 3 It is difficult to achieve 0.82g/cm 3 Thus, aviation kerosene having a large specific gravity could not be obtained. In order to ensure the activity of the hydrocracking section, the nitrogen content at the inlet of the hydrocracking section is generally required to be controlled, however, the denitrification and the aromatic saturation reaction of the refining section are carried out on a metal center, so that the aromatic saturation performance is stronger when the nitrogen content is controlled to be lower, and the density of the aviation kerosene is reduced as an additional result, so that the aromatic saturation existing during denitrification becomes a technical obstacle, and the effective operation of a hydrocracking catalyst and the preparation of high-density aviation kerosene cannot be considered at the same time.
The invention adopts the density of 0.9-1.05g/cm 3 And the heavy raw oil with the fraction ratio of more than 10 wt% in the distillation range of more than 350 ℃ is used as a raw material, the high content of organic nitrogen in the effluent of hydrotreating is controlled, a phosphorus-containing molecular sieve hydrocracking catalyst is used as a hydrocracking catalyst, and a specific distillation range section is cut to be used as an aviation kerosene product, so that the aviation kerosene with large specific gravity with the smoke point and the freezing point meeting the requirements can be obtained.
The method according to the invention has the following advantages:
(1) The method can reduce the proportion of secondary processing heavy inferior distillate in the prior art, and is favorable for directly meeting the requirements of the prior laws and regulations;
(2) According to the method, the heavy inferior raw material is subjected to hydrocracking reaction to produce more branched alkanes in the aviation kerosene component, so that the aviation kerosene component has a higher smoke point while an ice point is ensured, the combustion performance and low-temperature performance of a product are ensured, and the product quality is ensured;
(3) Other fractions such as naphtha, diesel oil and tail oil obtained after hydrotreating by the method can be used as high-quality clean fuel or chemical raw oil, and have higher economic value.
Drawings
FIG. 1 shows XRD spectra of phosphorous containing high silicon molecular sieve Y-1 and phosphorous containing high silicon molecular sieve Y-2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the dry weight of a substance means the weight of a solid product obtained by calcining the substance at 600 ℃ for 3 hours.
In the present invention, "about" used in defining the positions of the diffraction angles of the diffraction peaks means that the diffraction angle positions may deviate by ± 0.5 °.
The invention provides a combined method for producing heavy aviation kerosene, which comprises the following steps:
(1) Carrying out a first contact reaction on hydrogen and heavy raw oil and a hydrofining catalyst to obtain a hydrotreating effluent, wherein the content of organic nitrogen in the hydrotreating effluent is 50-600 mu g/g;
(2) Carrying out a second contact reaction on the hydrotreated effluent obtained in the step (1) and a hydrocracking catalyst to obtain a hydrocracking effluent, wherein the hydrocracking catalyst is a phosphorus-containing molecular sieve hydrocracking catalyst;
(3) Carrying out a third contact reaction on the hydrocracking effluent obtained in the step (2) and a post-refining catalyst to obtain a post-refining effluent;
(4) Fractionating the post-refining effluent obtained in the step (3) to obtain an aviation kerosene fraction, wherein the distillation range of the aviation kerosene fraction is 180-215 ℃;
wherein the density of the heavy raw oil is 0.9-1.05g/cm 3 And the fraction above 350 ℃ in the distillation range accounts for more than 10 percent by weight.
In the method provided by the invention, the fraction with the distillation range above 350 ℃ is relatively large. Whereas the conventional raw materials used in the prior art are generally coal-diesel fractions (> 350 ℃ C. Represents less than 10% by weight).
The heavy feed oil satisfying the above requirements is within the usable range of the present invention. Preferably, the heavy feed oil contains a naphthenic wax oil fraction. The inventors of the present invention have found that the use of a naphthenic wax oil fraction is more beneficial in increasing the density of the jet fuel fraction.
The heavy raw oil of the present invention optionally contains other fractions selected from one or more of catalytic cracking cycle oil, coal tar, coal liquefaction oil, naphthenic diesel, heavy oil boiling bed diesel fraction, slurry bed diesel fraction and suspension bed diesel fraction. The catalytic cracking cycle oil, coal tar, coal liquefaction oil, naphthenic diesel oil, heavy oil boiling bed diesel oil fraction, slurry bed diesel oil fraction and suspension bed diesel oil fraction have conventional indications in the field, and the invention is not described herein.
According to a preferred embodiment of the present invention, the content of the naphthenic wax oil fraction in the heavy feedstock oil is not less than 30 wt%, preferably not less than 50 wt%, more preferably 50 to 100 wt%. By adopting the preferred embodiment, the aviation kerosene with large specific gravity meeting the quality requirement can be produced, the proportion of secondary processing heavy inferior distillate in the prior art can be further reduced, and the requirement of the existing regulation can be directly met.
According to the present invention, preferably, the density of the heavy raw oil is 0.92 to 0.97g/cm 3 . The heavy raw oil with the optimized density is more beneficial to improving the density of the aviation kerosene fraction.
According to the present invention, it is preferable that the fraction having a temperature of more than 370 ℃ accounts for 30 wt% or more of the distillation range of the heavy feedstock oil.
In the present invention, the heavy feed oil further contains sulfur and/or nitrogen, and the sulfur and nitrogen content in the heavy feed oil is not particularly limited.
According to the method provided by the present invention, preferably, the method further comprises: removing mechanical impurities in the heavy raw oil, and then carrying out the step (1). The method for removing the mechanical impurities in the present invention is not particularly limited, and examples thereof include filtration.
In the present invention, the organic nitrogen content in the hydrotreating effluent can be adjusted by controlling the first contact reaction conditions. The invention has wider selection range of the first contact condition so as to take the hydrofining reaction as the standard, and the content of organic nitrogen in the obtained hydrotreating effluent is 50-600 mug/g.
Preferably, the organic nitrogen content of the hydrotreating effluent is in the range of 110 to 500. Mu.g/g, more preferably 250 to 400. Mu.g/g.
The conditions for the second contact are selected within a wide range, based on the possibility of a hydrocracking reaction, and the conditions for the third contact are selected within a wide range, based on the possibility of a refining reaction. Preferably, the conditions of the first contact reaction, the second contact reaction and the third contact reaction each independently comprise: the reaction pressure is 2.0-20.0MPa, the reaction temperature is 280-480 ℃, the volume ratio of hydrogen to oil is 500 -1 (ii) a Further preferably, the reaction pressure is 8.0-17.0MPa, the reaction temperature is 350-450 ℃, the volume ratio of hydrogen to oil is 700 -1 。
According to the method provided by the present invention, preferably, the conditions of the second contacting include: the reaction pressure is 6.0-17.0MPa, the reaction temperature is 350-450 ℃, the volume ratio of hydrogen to oil is 700-1500 -1 (ii) a Further preferably, the conditions of the second contacting include: the reaction pressure is 10.0-17.0MPa, the reaction temperature is 380-430 ℃, the volume ratio of hydrogen to oil is 800-1, and the volume space velocity is 0.5-4h -1 。
According to the process of the present invention, the ratio between the hydrocracking catalyst and the hydrofinishing catalyst may be selected according to specific reaction conditions. Preferably, the volume ratio of the hydrocracking catalyst to the hydrofinishing catalyst is 0.2 to 3. More preferably, the volume ratio of the hydrocracking catalyst to the hydrofinishing catalyst is from 0.5 to 1.5.
According to the method of the invention, the hydrofining catalyst can be a catalyst with catalytic activities of aromatic saturation, hydrodesulfurization and hydrodenitrogenation, and can be a noble metal catalyst or a non-noble metal catalyst. Preferably, the hydrofinishing catalyst is a non-noble metal catalyst.
Specifically, the hydrofining catalyst may contain a carrier and a group VIB metal component and a group VIII metal component supported on the carrier. The group VIB metal component may be present in an amount of from 5 to 50 wt.%, preferably from 7 to 35 wt.%, based on the total amount of hydrofinishing catalyst and calculated as oxide; the content of the group VIII metal component may be 1 to 10% by weight, preferably 1.5 to 7% by weight. Preferably, the hydrofining catalyst may further contain at least one auxiliary agent, and the auxiliary agent may be at least one of phosphorus, fluorine and boron. The content of the promoter may be 1 to 10% by weight, calculated as element, based on the total amount of the hydrorefining catalyst.
In the hydrofinishing catalyst, the VIB group metal is preferably Mo and/or W, and the VIII group metal is preferably Co and/or Ni.
The carrier of the hydrorefining catalyst is preferably at least one of alumina, silica and silica-alumina.
In the hydrofinishing catalyst, the group VIB metal component and the group VIII metal component may both be present in the form of oxides.
The hydrorefining catalyst may be an industrial catalyst (commercially available) or may be prepared by itself, and the present invention is not particularly limited thereto.
In the present invention, the method for producing the hydrotreating catalyst is not particularly limited as long as the hydrotreating reaction can be carried out, and the hydrotreating catalyst can be produced by, for example, an impregnation method. The impregnation method can be co-impregnation or step-by-step impregnation. The specific operation is well known to those skilled in the art, and the detailed description of the present invention is omitted here.
According to the method, the hydrocracking catalyst containing the phosphorus-containing molecular sieve refers to a hydrocracking catalyst containing the phosphorus-containing molecular sieve.
In the present invention, the hydrocracking catalyst may be a non-noble metal catalyst. Specifically, the hydrocracking catalyst preferably contains a carrier, and a group VIB metal component and a group VIII metal component supported on the carrier, wherein the carrier comprises a phosphorus-containing molecular sieve and a heat-resistant inorganic oxide. Preferably, the group VIII metal component is present in an amount of from 1 to 15 wt.%, preferably from 1.5 to 6 wt.%, based on the total amount of hydrocracking catalyst and calculated as oxide; the group VIB metal component is present in an amount of from 1 to 40 wt.%, preferably from 10 to 40 wt.%.
The selection of the group VIB metal and the group VIII metal components may be as described above, and are not described herein again.
According to a preferred embodiment of the invention, the molecular sieve contains 86.5 to 99.8 wt.%, preferably 90 to 99.8 wt.%, calculated as oxides and based on the dry weight of the molecular sieve, of silicon, 0.1 to 13.5 wt.%, preferably 0.1 to 9.0 wt.%, of aluminum and 0.01 to 6 wt.%, preferably 0.01 to 2.5 wt.%, of phosphorus. The adoption of the preferred phosphorus-containing high-silicon molecular sieve is more beneficial to improving the density of the obtained aviation kerosene fraction.
According to the invention, the phosphorus-containing molecular sieve preferably has a pore volume of 0.20-0.50mL/g, preferably 0.30-0.45mL/g, and a specific surface area of 250-670m 2 G, preferably from 260 to 600m 2 (ii) in terms of/g. The pore volume and specific surface area of the molecular sieve can be determined by static low temperature adsorption volumetric methods.
According to the present invention, preferably, the phosphorus-containing molecular sieve has an XRD pattern with at least three diffraction peaks, wherein the first intense peak has a diffraction angle position in the range of about 5.9-6.9 °, preferably in the range of about 6.1-6.8 °; the diffraction angle position of the second intense peak is in the range of about 10.0-11.0, preferably in the range of about 10.2-10.7; and the diffraction angle position of the third intensity peak is about 15.6 to 16.7 deg., preferably about 15.8 to 16.5 deg.. The phosphorus-containing molecular sieve with different structural characteristics from the conventional silicon-aluminum material is more favorable for preparing the high-specific-gravity aviation kerosene with higher density and meeting the requirements on smoke point and freezing point.
In the invention, the diffraction angle position refers to a 2 theta angle value of the highest peak value of a diffraction peak in an XRD spectrogram.
In the present application, the ordinal numbers "first", "second" and "third" etc. in the expressions first, second and third, etc. represent the relative order of magnitude of the diffraction peaks as determined by the peak heights, wherein the first intensity peak represents the diffraction peak having the highest peak height in the XRD spectrum, the second intensity peak represents the diffraction peak having the second highest peak height in the XRD spectrum, the third intensity peak represents the diffraction peak having the third highest peak height in the XRD spectrum, and so on.
It is well known to those skilled in the art that in the structural analysis of a substance by X-ray diffraction (XRD), the D value (interplanar distance) can be generally calculated from the wavelength and diffraction angle, and the primary phase identification is performed based on the features of the strongest three diffraction peaks, i.e., the first, second and third intensity peaks in the present application. The concept of the three strong peaks can be found in the literature, "research methods of heterogeneous catalysts", edited by Yi Yuan Gen, beijing: chemical industry publishers, 1988, pages 140-170.
According to a preferred embodiment of the present invention, the XRD spectrum of the phosphorous containing molecular sieve is I 1 /I 23.5-24.5° From 3.0 to 11.0, for example from 4.0 to 10.5 or from 4.6 to 10.1; I.C. A 2 /I 23.5-24.5° From 2.5 to 8.0, for example from 2.9 to 7.0 or from 3.0 to 6.4; I.C. A 3 /I 23.5-24.5° Is 1.0 to 4.5, for example 1.5 to 4.0 or 2.1 to 3.8, where I 1 Is the peak height of the first strong peak, I 2 Is the peak height of the second strong peak, I 3 Is the peak height of the third strong peak, I 23.5-24.5° Peak height, which is the peak at diffraction angle positions of about 23.5 to 24.5 °.
According to a more preferred embodiment of the present invention, the phosphorus-containing molecular sieve has an XRD pattern with at least five diffraction peaks, wherein the fourth intensity peak has a diffraction angle position between about 20.4 ° and 21.6 °, preferably between about 20.8 ° and 21.4 °; the diffraction angle position of the fifth intensity peak is in the range of about 11.8 to 12.8, preferably in the range of about 12.1 to 12.6; more preferably, in the XRD spectrum of the phosphorus-containing molecular sieve, I 4 /I 23.5-24.5° From 1.0 to 4.0, for example from 1.1 to 3.0 or from 1.2 to 2.3;I 5 /I 23.5-24.5° is 1.0 to 2.0, for example 1.0 to 1.6 or 1.0 to 1.2, where I 4 Is the peak height of the fourth strong peak, I 5 Is the peak height of the fifth strong peak, I 23.5-24.5° Peak height, which is the peak at diffraction angle positions of about 23.5 to 24.5 °. The concept of the fourth strong peak and the fifth strong peak can be understood according to the description of the three strong peaks, and will not be described herein again.
In the present invention, the crystal structure of the molecular sieve is determined using an X-ray diffractometer model D5005 from Siemens Germany, according to the method of the industry standard SH/T0339-92.
The hydrocracking catalyst containing the phosphorus-containing molecular sieve shows higher hydrocracking activity.
The invention has wider selection range of the preparation method of the phosphorus-containing molecular sieve, and preferably, the preparation method of the phosphorus-containing molecular sieve comprises the following steps:
(a) Carrying out hydro-thermal treatment on a phosphorus-containing molecular sieve raw material; the temperature of the hydrothermal treatment is 350-700 ℃;
(b) First contacting the molecular sieve material obtained in step (a) with a first acid solution; the temperature of the first contact is 40-95 ℃, and the addition amount of the first acid solution ensures that the pH value of the first contact product is 2.3-4.0, preferably 2.5-4.0;
(c) Second contacting the first solid product obtained in step (b) with a second acid solution; the temperature of the second contact is 40-95 ℃, and the second acid solution is added in an amount to make the pH value of the second contact product 0.8-2.0, preferably 1.0-2.0.
According to the present invention, the phosphorus content of the phosphorus-containing molecular sieve feedstock is preferably in the range of from 0.1 to 15 wt.%, preferably from 0.1 to 6 wt.%, for example 1.37 wt.%, calculated as oxides and based on the dry weight of the phosphorus-containing molecular sieve feedstock; the sodium content is from 0.5 to 4.5% by weight, preferably from 0.5 to 3.0% by weight, for example 1.44% by weight; the silicon content is from 70 to 85% by weight, preferably from 70 to 80% by weight, for example 76.7% by weight; the aluminum content is 16.0 to 21.0 wt.%, preferably 18.0 to 21.0 wt.%, for example 20.5 wt.%.
In the present invention, the phosphorus-containing molecular sieve raw material refers to a phosphorus-containing molecular sieve, and the phosphorus-containing molecular sieve raw material may have a faujasite molecular sieve structure, and is preferably a phosphorus-containing Y-type molecular sieve. The Y-type molecular sieve can be selected from NaY, HNaY (hydrogen Y-type molecular sieve), REY (rare earth Y-type molecular sieve), USY (ultra stable Y-type molecular sieve) and the like. The cation sites of the phosphorus-containing Y-type molecular sieve can be occupied by one or more of sodium ions, ammonium ions and hydrogen ions; alternatively, all or part of the sodium, ammonium and hydrogen ions may be replaced by other ions by conventional ion exchange before or after the molecular sieve is introduced with phosphorus. The phosphorus-containing molecular sieve raw material can be a commercial product or can be prepared by adopting any prior art.
Preferably, step (a) comprises: carrying out hydrothermal treatment on a phosphorus-containing molecular sieve raw material at the temperature of 350-700 ℃, under the pressure of 0.1-8.0MPa and in the presence of water vapor for about 0.5-10h to obtain a molecular sieve material subjected to hydrothermal treatment. More preferably, the temperature of the hydrothermal treatment is 400-650 ℃, e.g. 560 ℃. Preferably, the pressure of the hydrothermal treatment is in the range of 0.5 to 5MPa, for example 0.8MPa. Preferably, the hydrothermal treatment is carried out for a period of time of 1 to 7 hours, for example 3 hours.
According to the present invention, preferably, the step (b) comprises: adding water to the hydrothermally treated molecular sieve material obtained in step a) to form a first slurry, heating the first slurry to 40-95 ℃, preferably 50-85 ℃, for example about 80 ℃, then maintaining the temperature and adding a first acid solution to the first slurry in an amount such that the pH of the resulting acidified first slurry is 2.3-4.0, preferably 2.5-4.0, more preferably 2.5-3.5, for example about 2.8, and then reacting at constant temperature for 0.5-20h, preferably 1-10h, for example 4h, and collecting a first solid product.
According to the present invention, preferably, step (c) comprises: adding water to said first solid product obtained in step (b) to form a second slurry, heating the second slurry to a temperature of 40-95 ℃, preferably 50-85 ℃, e.g. about 80 ℃, then maintaining the temperature and adding a second acid solution to the second slurry in an amount such that the pH of the resulting acidified second slurry is 0.8-2.0, preferably 1.0-2.0, more preferably 1.0-1.8, e.g. 1.4, and then reacting at constant temperature for 0.5-20h, preferably 1-10h, e.g. 3h, and collecting the second solid product.
According to the present invention, the meaning of said beating with water in step (b) and step (c) is well known to the person skilled in the art. In a preferred embodiment, in step (b), the ratio of the weight of water to the weight of the phosphorus-containing molecular sieve feedstock on a dry basis in said first slurry obtained after pulping may be from 14 to 5, for example 10; and/or in step (b), the ratio of the weight of water in the second slurry to the weight of phosphorus-containing molecular sieve feedstock on a dry basis may be from 0.5.
The amount of the first acid solution added can vary widely depending on the nature of the phosphorus-containing molecular sieve feedstock and the hydrothermal treatment conditions of step (a). It will be appreciated by those skilled in the art that the first acid solution is desirably added in an amount such that the pH of the first slurry after addition of the acid satisfies the appropriate range described above. The rate of addition of the first acid solution is not particularly limited and may vary over a wide range.
In a preferred embodiment, in step (b), the addition of the first acid solution may be performed multiple times (e.g. 1-5 times), and each time after the addition of the acid, the isothermal reaction may be performed for a period of time and the next addition of the acid may be continued until the pH of the first slurry after the addition of the acid reaches the desired range.
According to the invention, in a preferred embodiment, the second acid solution may be added in a manner such that: based on 1L of the second slurry, taking H as reference + The second acid solution is added to the second slurry at a rate of from 0.05 to 15mol/h, preferably from 0.05 to 10mol/h, more preferably from 2 to 8mol/h, for example 5 mol/h. According to the invention, the slow acid adding speed is adopted in the step (c), so that the dealumination process can be more moderate, and the performance of the molecular sieve can be improved.
In a preferred embodiment, the addition of the second acid solution in step (c) may be performed several times (e.g. 1-5 times), and each time the acid is added, the reaction may be performed at constant temperature for a period of time and then the next addition of acid is continued until the pH of the second slurry after the addition of acid reaches the desired range.
The acid concentration of the first acid solution and the second acid solution may each independently be 0.1 to 15.0mol/L, preferably 0.1 to 5.0mol/L, for example 2.0mol/L. The acid in the first acid solution and the second acid solution may each independently be a conventional inorganic acid and/or organic acid, and for example, may be at least one selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartaric acid, formic acid, and acetic acid, and preferably sulfuric acid and/or nitric acid. The second acid solution may be the same as or different from the first acid solution in terms of kind and concentration, and is preferably the same acid solution.
According to the present invention, in a preferred embodiment, the method may further comprise: and collecting the second solid product, and then washing and drying to obtain the phosphorus-containing molecular sieve. The washing and drying are conventional steps for preparing the molecular sieve, and the present invention is not particularly limited. For example, the drying conditions may be: the temperature is 50 to 350 ℃, preferably 70 to 200 ℃, for example 180 ℃; the time is from 1 to 24h, preferably from 2 to 6h, for example 3h.
The invention has a wide selection range of the ratio of the phosphorus-containing molecular sieve to the heat-resistant inorganic oxide in the carrier, preferably, the weight ratio of the phosphorus-containing molecular sieve to the heat-resistant inorganic oxide is about 0.03 to 1, more preferably 0.1 to 1.
The heat-resistant inorganic oxide refers to a porous material with the highest use temperature of not lower than 600 ℃. Specific examples of the heat-resistant inorganic oxide may include, but are not limited to, one or two or more of alumina, silica, titania, magnesia, zirconia, thoria, and beryllia. Preferably, the heat-resistant inorganic oxide is at least one of alumina, silica, titania, zirconia, and magnesia.
The preparation method of the hydrocracking catalyst has a wide selection range, and preferably, the preparation method of the hydrocracking catalyst comprises the following steps:
(I) Mixing the phosphorus-containing molecular sieve and a heat-resistant inorganic oxide to prepare a carrier;
(II) introducing a group VIB metal component and a group VIII metal component onto the carrier by an impregnation method. As described above, the impregnation method may be a co-impregnation method or a step-impregnation method. The specific operation of the impregnation method is well known to those skilled in the art, and the detailed description of the present invention is omitted here.
The preparation method of the carrier is well known to those skilled in the art, and the present invention is not particularly limited. For example, the method may include: and mixing the phosphorus-containing molecular sieve with a heat-resistant inorganic oxide, and then molding and drying to obtain the carrier. The molding method can adopt various conventional methods, such as tabletting molding, rolling ball molding or extrusion molding.
According to the present invention, post-refining after the hydrocracking reaction can further reduce the content of olefins and mercaptan sulfur in the hydrocracking effluent.
The amount of the post-refining catalyst is selected from a wide range, and preferably is based on the amount of the post-refining catalyst which can reduce the content of the olefin and the mercaptan sulfur in the hydrocracking effluent to the expected content. Further preferably, the volume ratio of the hydrocracking catalyst to the post-refining catalyst is 3 to 20, preferably 5 to 10. The type of the post-refining catalyst is the same as the hydrofinishing catalyst described above and will not be described in detail herein. The post-purification catalyst may be the same as or different from the hydropurification catalyst.
According to a preferred embodiment of the present invention, in the step (1), a hydrogenation protecting agent is further provided upstream of the hydrorefining catalyst with respect to the flow direction of the heavy feedstock oil. By adopting the preferred embodiment, coking precursors such as olefin and/or colloid in the raw oil can be prevented from coking on the hydrofining catalyst to cause coking and inactivation of the hydrofining catalyst, and simultaneously, metal in the raw oil can be prevented from causing poisoning of the hydrofining catalyst. The dosage of the hydrogenation protective agent can be selected according to the composition of the raw oil. Preferably, the hydrogenation protector is 5-80 vol%, such as 5-30 vol% of the total amount of the hydrofinishing catalyst.
The hydrogenation protective agent can be various catalysts capable of realizing the functions. Specifically, the hydrogenation protective agent comprises a carrier, and a VIB metal component and a VIII metal component which are loaded on the carrier, wherein the content of the VIB metal component can be 5.5-10 wt% and the content of the VIII metal component can be 1-5 wt% based on the total amount of the hydrogenation protective agent and calculated by oxides. Preferably, the group VIB metal is Mo and/or W; the group VIII metal component is Co and/or Ni. Further preferably, the group VIB metal is Mo, and the group VIII metal is Ni. Preferably, the support is selected from at least one of alumina, silica and silica-alumina, more preferably alumina.
In the present invention, the aviation kerosene fraction having the distillation range described above may be obtained from the post-purification effluent obtained in step (3). The fractionation is not particularly limited. According to a particular embodiment of the invention, the process further comprises separating the post-purification effluent obtained in step (3) and then carrying out said fractionation.
The specific operation steps of the separation and fractionation are not particularly limited, and a person skilled in the art can perform the separation and fractionation by various methods conventionally used in the art, for example, in the invention, the post-refining effluent can be introduced into a high-pressure separator to obtain a hydrogen-rich gas and a liquid effluent, the hydrogen-rich gas can be recycled after the conventional operation, and the separated liquid effluent enters a fractionating tower to be fractionated, so that the target product can be obtained.
According to the method provided by the invention, in addition to obtaining the aviation kerosene, other additional products can be obtained, for example, the step (4) can be used for fractionating the after-refining effluent obtained in the step (3) to obtain naphtha fraction, the aviation kerosene fraction, diesel oil fraction and tail oil fraction.
The distillation range of each additional product can be selected by one skilled in the art by the particular use of the fraction. The distillation range of the naphtha fraction, the diesel fraction and the tail oil fraction can be selected conventionally in the art and will not be described herein.
Preferably, the aviation kerosene fraction has a distillation range of 180-215 ℃. The aviation kerosene in the preferred distillation range not only meets the requirements of smoke point and freezing point, but also has larger density. The distillation range of 180-215 ℃ does not mean that the initial boiling point is 180 ℃ and the final boiling point is 215 ℃, but means that the initial boiling point is not lower than 180 ℃ and the final boiling point is not higher than 215 ℃.
In the present invention, the hydrofining catalyst, the hydrocracking catalyst, the post-refining catalyst and the optional hydrogenation protecting agent may be filled in different reaction zones of the same reactor, or may be located in different reactors, and may be selected according to specific apparatuses, and are not particularly limited. In the present invention, "optionally" means optionally, and may be understood as containing or not containing.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the hydrogenation protecting agent in the hydrogenation protecting reaction zone was RG series protecting catalyst RG-10 developed by the institute of petrochemical science and technology, and the hydrofinishing catalyst in the hydrofinishing reaction zone and the post-refining catalyst in the post-refining reaction zone were RN-32V developed by the institute of petrochemical science and technology.
In the following preparation examples, the pore volume and the specific surface area of the molecular sieve were determined by the static low-temperature adsorption capacity method using an ASAP 2400 model automatic adsorption apparatus from micromeritics instruments USA (according to the method of GB/T5816-1995): vacuumizing and degassing the molecular sieve to be detected for 4h at 250 ℃ and 1.33Pa, and contacting the molecular sieve with nitrogen serving as adsorbate at-196 ℃, so that static adsorption reaches adsorption balance; the amount of nitrogen adsorbed by the adsorbent is calculated according to the difference between the nitrogen gas inflow and the amount of nitrogen remained in the gas phase after adsorption, then the pore size distribution is calculated by using a BJH formula, and the specific surface area and the pore volume are calculated by using a BET formula.
The crystal structure of the molecular sieve was determined using an X-ray diffractometer model D5005 from Siemens, germany, according to the method of the industry standard SH/T0339-92. The experimental conditions were: cu target, k alpha radiation, a solid detector, tube voltage of 40kV, tube current of 40mA, step scanning, step of 0.02 degrees, prefabrication time of 2s and scanning range of 5-70 degrees. The diffraction angle position refers to the 2 theta angle value of the highest value of the diffraction peak.
The silicon content, aluminum content, phosphorus content and sodium content of the molecular sieve are measured by a 3271E type X-ray fluorescence spectrometer of Nippon science and electronics industry, and the measuring method comprises the following steps: tabletting and forming a powder sample, carrying out rhodium target, detecting the spectral line intensity of each element by a scintillation counter and a proportional counter under the laser voltage of 50kV and the laser current of 50mA, and carrying out quantitative and semi-quantitative analysis on the element content by an external standard method.
Preparation of hydrocracking catalyst example 1
(1) Preparation of phosphorus-containing high-silicon molecular sieve
Taking phosphorus-containing molecular sieve raw material (USY molecular sieve produced by China petrochemical catalyst Chang Ling division, with unit cell constant of 2.456nm and specific surface area of 672 m) 2 Perg, pore volume of 0.357mL/g, na 2 O content 1.44 wt%, P 2 O 5 1.37 wt.% of SiO 2 Content 76.7 wt.% and Al 2 O 3 Content 20.5 wt%) was put into a hydrothermal kettle, 100% steam was introduced, hydrothermal treatment was carried out at 560 ℃ and 0.8MPa for 3 hours, and then the hydrothermally treated molecular sieve material was taken out.
Taking 50g (dry basis) of the molecular sieve material subjected to the hydrothermal treatment, adding 500mL of deionized water, and stirring and pulping to obtain first slurry. Heating the mixture to 80 ℃, adding 2.0mol/L sulfuric acid solution, stopping adding the acid when the pH value of the first slurry after adding the acid is detected to be 2.8, then reacting for 4 hours at constant temperature, and filtering to obtain 40g of a first solid product.
And adding 400mL of deionized water into the first solid product, and stirring and pulping to obtain second slurry. Heating to 80 deg.C, and taking 1L second slurry as reference and H + Adding 2mol/L sulfuric acid solution into the second slurry at the speed of 5mol/h, stopping adding acid when the pH value of the acid-added second slurry is detected to be 1.4, then reacting for 3h at constant temperature, filtering and collecting a second solid product.
Drying the obtained solid product at 180 ℃ for 3h to obtain the phosphorus-containing high-silicon molecular sieve Y-1, wherein an XRD spectrogram of the phosphorus-containing high-silicon molecular sieve Y-1 is shown in figure 1. The XRD diffraction peak positions of the obtained molecular sieve are shown in Table 1, the diffraction peak heights are shown in Table 2, and other properties are shown in Table 3.
(2) Preparation of the catalyst
Mixing 80g of molecular sieve Y-1 in dry basis with 28.8g of pseudo-boehmite (trade name PB90, dry basis 70 wt%) in China petrochemical catalyst ChangLing division, extruding into trilobal strips with the circumscribed circle diameter of 1.6 mm, drying at 120 ℃ for 3h, and roasting at 600 ℃ for 3h to obtain the carrier CS-1.
After the temperature is reduced to room temperature, 100g of CS-1 carrier is taken and dipped in 70mL of aqueous solution containing 34.65g of ammonium metatungstate (Sichuan tribute cemented carbide factory, with the content of tungsten oxide of 82 wt%) and 24.37g of nickel nitrate (Beijing New photochemical reagent factory, with the content of nickel oxide of 27.85 wt%), dried at 120 ℃ for 3h, and roasted at 480 ℃ for 4h, thus obtaining the hydrocracking catalyst C-1. Composition of C-1 of the catalyst: 74 wt% of carrier, calculated by oxide, the content of VIII group metal is 5 wt%, the content of VIB group metal is 21 wt%, and in the carrier, the content of phosphorus-containing molecular sieve is 80 wt%, and the content of heat-resisting inorganic oxide is 20%.
Preparation example 2 of hydrocracking catalyst
The preparation method is carried out according to preparation example 1 of the hydrocracking catalyst, except that in the preparation process of the phosphorus-containing high-silicon molecular sieve, when the second acid solution is added, the phosphorus-containing high-silicon molecular sieve Y-2 is prepared according to the speed of 15mol/h, and the XRD spectrogram is shown in figure 1. The XRD diffraction peak positions of the obtained molecular sieve are shown in Table 1, the diffraction peak heights are shown in Table 2, and other properties are shown in Table 3. To prepare the hydrocracking catalyst C-2.
TABLE 1 XRD diffraction peak positions of molecular sieves
TABLE 2 XRD diffraction peak heights of molecular sieves
TABLE 3 other Properties of the molecular sieves
Preparation of hydrocracking catalyst example 3
20g of a phosphorus-containing ultrastable molecular sieve (product name USY-5, phosphorus pentoxide content of 1.2%, unit cell constant of 24.44nm, pore volume of 0.40mL/g, dry basis of 81 wt%) and 80g of pseudo-boehmite (product name PB90, dry basis of 70 wt%) were mixed, extruded into trilobal strips with a circumscribed circle diameter of 1.6 mm, dried at 120 ℃ and calcined at 600 ℃ for 3 hours to obtain the carrier CS-3. After the temperature is reduced to room temperature, 100g of CS-3 carrier is taken and dipped in 70mL of aqueous solution containing 34.65g of ammonium metatungstate (Sichuan tribute cemented carbide factory, tungsten oxide content is 82 wt%) and 24.37g of nickel nitrate (product of Beijing New photochemical reagent factory, nickel oxide content is 27.85 wt%), dried at 120 ℃ and roasted at 480 ℃ for 4h, thus obtaining the hydrocracking catalyst C-3.
Comparative example 1
The hydrogenation reaction zone is sequentially filled with a hydrogenation protective agent RG-10, a hydrofining catalyst RN-32V, a hydrocracking catalyst C-3 and a post-refining catalyst RN-32V. Wherein, the filling volume ratio of the hydrocracking catalyst to the post-refining catalyst is 5, the filling volume ratio of the hydrocracking catalyst to the hydrofining catalyst is 0.92, and the hydrogenation protective agent accounts for 2.27 volume percent of the hydrofining catalyst.
The middle east VGO raw material (properties are shown in Table 4) is mixed with hydrogen and enters a hydrogenation reaction zone, and specific reaction conditions and product properties are shown in Table 5.
Example 1
According to the method of comparative example 1, except that the process conditions of the hydrorefining stage were different and the organic nitrogen content in the effluent from the hydrotreating was higher, the specific reaction conditions and product properties are shown in Table 5.
Comparative example 2
The process of example 1 was followed except that the jet fuel cut distillation range was 145-250 ℃ and the specific reaction conditions and product properties are shown in Table 5.
Comparative example 3
The procedure of example 1 was followed except that the hydrocracking catalyst C-3 was replaced with a commercial hydrocracking catalyst RT-5, and the specific reaction conditions and product properties are shown in Table 5.
Example 2
The procedure of example 1 was followed except that the hydrocracking catalyst C-3 was replaced with a hydrocracking catalyst C-1.
Example 3
The procedure of example 1 was followed except that the hydrocracking catalyst C-3 was replaced with a hydrocracking catalyst C-2. Specific reaction conditions and product properties are shown in Table 5.
Example 4
The procedure of example 1 was followed except that the middle east VGO feedstock was replaced with a soyabean mix (properties are shown in Table 4) and the specific reaction conditions and product properties are shown in Table 5.
Example 5
The process of example 1 was followed except that the middle east VGO feed was replaced with a mixed oil of soyabean hybrid and catalytic diesel (properties see table 4), the mass ratio of soyabean hybrid and catalytic diesel being 50. Specific reaction conditions and product properties are shown in Table 5.
Example 6
Following the procedure of example 1 except that the hydrofinishing section process conditions were different and the organic nitrogen content of the hydrotreated effluent was higher, the specific reaction conditions and product properties are shown in table 5.
TABLE 4
TABLE 5
As can be seen from the results in Table 5, the large-specific gravity aviation kerosene which has the smoke point and the freezing point meeting the standards can be prepared by the production method provided by the invention. Comparative example 1 the hydrotreated effluent had a lower organic nitrogen content and the jet fuel obtained using the conventional density feed had a lower density. The cutting method of comparative example 2 failed to obtain aviation kerosene of a large specific gravity that met the requirements.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (48)
1. An integrated process for producing heavy aviation kerosene, the process comprising the steps of:
(1) Carrying out a first contact reaction on hydrogen and heavy raw oil and a hydrofining catalyst to obtain a hydrotreating effluent, wherein the content of organic nitrogen in the hydrotreating effluent is 50-600 mu g/g; the conditions of the first contact reaction include: the reaction pressure is 2.0-20.0MPa, the reaction temperature is 280-480 ℃, the volume ratio of hydrogen to oil is 500-5000 -1 ；
(2) Performing a second contact reaction on the hydrotreating effluent obtained in the step (1) and a hydrocracking catalyst to obtain a hydrocracking effluent, wherein the hydrocracking catalyst is a phosphorus-containing molecular sieve hydrocracking catalyst;
(3) Carrying out a third contact reaction on the hydrocracking effluent obtained in the step (2) and a post-refining catalyst to obtain a post-refining effluent;
(4) Fractionating the post-refining effluent obtained in the step (3) to obtain aviation kerosene fraction, wherein the distillation range of the aviation kerosene fraction is 180-215 ℃;
wherein the density of the heavy raw oil is 0.9-1.05g/cm 3 And the fraction above 350 ℃ accounts for more than 10 percent by weight in the distillation range;
the conditions of the second contact reaction and the third contact reaction each independently comprise: the reaction pressure is 2.0-20.0MPa, the reaction temperature is 280-480 ℃, the volume ratio of hydrogen to oil is 500 -1 。
2. The process of claim 1, wherein the organic nitrogen content of the hydrotreated effluent is from 110 to 500 μ g/g.
3. The process according to claim 1, wherein the heavy raw oil contains naphthenic wax oil fraction and optionally other fractions selected from one or more of catalytically cracked cycle oil, coal tar, coal liquefaction oil, naphthenic diesel, heavy boiling bed diesel fraction, slurry bed diesel fraction and suspended bed diesel fraction.
4. The process according to claim 3, wherein the content of naphthenic wax oil fraction in the heavy raw oil is not less than 30 wt%.
5. A process according to claim 4, wherein the content of the naphthenic wax oil fraction in the heavy raw oil is 50 wt% or more.
6. The process according to claim 5, wherein the content of naphthenic wax oil fraction in the heavy raw oil is 50 to 100 wt%.
7. The process according to claim 1, wherein the density of the heavy feed oil is 0.92-0.97g/cm 3 。
8. The process according to claim 1, wherein the fraction of the heavy feedstock oil having a boiling point of more than 370 ℃ is more than 30 wt%.
9. The method of claim 1, wherein the conditions of the second contacting comprise: the reaction pressure is 6.0-17.0MPa, the reaction temperature is 350-450 ℃, the volume ratio of hydrogen to oil is 700-1500 -1 。
10. The process of any one of claims 1 to 8, wherein the volume ratio of hydrocracking catalyst to hydrofinishing catalyst is 0.2 to 3.
11. The process of claim 10, wherein the volume ratio of hydrocracking catalyst to hydrofinishing catalyst is 0.5-1.5.
12. The process of any one of claims 1 to 8, wherein the volume ratio of hydrocracking catalyst to post-refining catalyst is 3 to 20.
13. The process of claim 12, wherein the volume ratio of hydrocracking catalyst to post-refining catalyst is 5-10.
14. The process of any of claims 1-8, wherein the hydrofinishing catalyst comprises a support and a group VIB metal component and a group VIII metal component supported on the support.
15. The process of claim 14, wherein the group VIII metal component is present in an amount of from 1 to 10 wt.% and the group VIB metal component is present in an amount of from 5 to 50 wt.%, based on the total amount of hydrofinishing catalyst and calculated as oxides.
16. The process according to claim 14, wherein the group VIB metal is Mo and/or W; the group VIII metal component is Co and/or Ni.
17. The method of claim 14, wherein the support is selected from at least one of alumina, silica, and silica-alumina.
18. The process of any of claims 1-8, wherein the hydrocracking catalyst contains a support and a group VIB metal component and a group VIII metal component supported on the support; the carrier comprises a phosphorus-containing molecular sieve and a heat-resistant inorganic oxide.
19. The method of claim 18, wherein the weight ratio of the phosphorus-containing molecular sieve to the heat-resistant inorganic oxide is 0.03.
20. The method of claim 18, wherein the refractory inorganic oxide is selected from at least one of alumina, silica, titania, zirconia, and magnesia.
21. The process of claim 18 wherein the group VIII metal component is present in an amount of from 1 to 15 wt.% on an oxide basis based on the total amount of hydrocracking catalyst; the content of the VIB group metal component is 1-40 wt%.
22. The process of claim 21, wherein the group VIII metal component is present in an amount of from 1.5 to 6 wt.% on an oxide basis based on the total amount of hydrocracking catalyst; the content of the VIB group metal component is 10-40 wt%.
23. The process according to claim 18, wherein the group VIB metal is Mo and/or W; the group VIII metal component is Co and/or Ni.
24. The process of claim 18, wherein the phosphorus-containing molecular sieve contains 86.5 to 99.8 wt.% silicon, 0.1 to 13.5 wt.% aluminum, and 0.01 to 6 wt.% phosphorus, calculated as oxides and based on the dry weight of the phosphorus-containing molecular sieve.
25. The process of claim 24, wherein the phosphorus-containing molecular sieve contains 90 to 99.8 wt.% silicon, 0.1 to 9.0 wt.% aluminum, and 0.01 to 2.5 wt.% phosphorus, calculated as oxides and based on the dry weight of the phosphorus-containing molecular sieve.
26. The process of claim 18, wherein the phosphorus-containing molecular sieve has a pore volume of 0.20 to 0.50mL/g and a specific surface area of 250 to 670m 2 /g。
27. The process of claim 26, wherein the phosphorus-containing molecular sieve has a pore volume of 0.30 to 0.45mL/g and a specific surface area of 260 to 600m 2 /g。
28. The process of claim 18, wherein the phosphorus-containing molecular sieve has an XRD pattern with at least three diffraction peaks, wherein the first intensity peak has a diffraction angle position in the range of 5.9-6.9 °; the diffraction angle position of the second strong peak is 10.0-11.0 degrees; and the diffraction angle position of the third intensity peak is 15.6 to 16.7 deg.
29. The process of claim 28, wherein the phosphorus-containing molecular sieve has an XRD pattern with at least three diffraction peaks, wherein the first intensity peak has a diffraction angle position between 6.1 and 6.8 °; the diffraction angle position of the second intense peak is between 10.2 and 10.7 degrees; and the diffraction angle position of the third intensity peak is 15.8 to 16.5 deg.
30. The method of claim 28, wherein the phosphorous containing molecular sieve has an XRD pattern of I 1 /I 23.5-24.5° Is 3.0 to 11.0 2 /I 23.5-24.5° Is 2.5 to 8.0 3 /I 23.5-24.5° Is 1.0 to 4.5, wherein I 1 Is the peak height of the first strong peak, I 2 Is the peak height of the second strong peak, I 3 Is the peak height of the third strong peak, I 23.5-24.5° The peak height of the peak at a diffraction angle position of 23.5 to 24.5 degrees.
31. The process of any one of claims 24-30, wherein the phosphorus-containing molecular sieve has an XRD pattern with at least five diffraction peaks, wherein the fourth intensity peak has a diffraction angle position between 20.4 and 21.6 °; the diffraction angle position of the fifth intensity peak is 11.8-12.8 deg.
32. The process of claim 31, wherein the phosphorus-containing molecular sieve has an XRD pattern with at least five diffraction peaks, wherein the fourth intensity peak has a diffraction angle position between 20.8-21.4 °; the diffraction angle position of the fifth intensity peak is 12.1 to 12.6 deg.
33. The process of claim 31, wherein I is the XRD spectrum of the phosphorus-containing molecular sieve 4 /I 23.5-24.5° 1.0-4.0, and I 5 /I 23.5-24.5° Is 1.0 to 2.0, wherein I 4 Is the peak height of the fourth strong peak, I 5 Is the peak height of the fifth strong peak, I 23.5-24.5° The peak height of the peak at a diffraction angle position of 23.5 to 24.5 degrees.
34. The method of any of claims 24-30, wherein the method of making the phosphorus-containing molecular sieve comprises:
(a) Carrying out hydrothermal treatment on a phosphorus-containing molecular sieve raw material; the temperature of the hydrothermal treatment is 350-700 ℃;
(b) First contacting the first solid product obtained in step (a) with a first acid solution; the temperature of the first contact is 40-95 ℃, and the first acid solution is added in an amount to ensure that the pH value of the first contact product is 2.3-4.0;
(c) Carrying out second contact on the molecular sieve material obtained in the step (b) and a second acid solution; the temperature of the second contact is 40-95 ℃, and the addition amount of the second acid solution ensures that the pH value of the second contact product is 0.8-2.0.
35. The method of claim 34, wherein in step (b), the first acid solution is added in an amount such that the first contact product has a pH of 2.5 to 4.0.
36. The process as in claim 34, wherein in step (c), the second acid solution is added in an amount such that the second contact product has a pH of 1.0-2.0.
37. The process of claim 18, wherein the hydrocracking catalyst is prepared by a process comprising the steps of:
(I) Mixing the phosphorus-containing molecular sieve and a heat-resistant inorganic oxide to prepare a carrier;
(II) introducing a group VIB metal component and a group VIII metal component onto the carrier by an impregnation method.
38. The process of any of claims 1-8, wherein the post-refining catalyst comprises a support and a group VIB metal component and a group VIII metal component supported on the support.
39. The process of claim 38 wherein the group VIII metal component is present in an amount of from 1 to 10 wt.% and the group VIB metal component is present in an amount of from 5 to 50 wt.% based on the total amount of post-refining catalyst and calculated as oxides.
40. The process according to claim 38, wherein the group VIB metal is Mo and/or W; the group VIII metal component is Co and/or Ni.
41. The method of claim 38, wherein the support is selected from at least one of alumina, silica, and silica-alumina.
42. The process according to any one of claims 1 to 8, wherein in step (1), a hydrogenation protecting agent is further provided upstream of the hydrorefining catalyst based on the flow direction of the heavy feedstock oil.
43. The process of claim 42, wherein the hydro-protectant is from 5 to 80 volume percent of the total amount of hydrofinishing catalyst.
44. The process of claim 43, wherein the hydro-protectant is 5-30 vol% of the total amount of hydrofinishing catalyst.
45. The method of claim 42, wherein the hydrogenation protective agent comprises a carrier and a VIB group metal component and a VIII group metal component which are loaded on the carrier, and the content of the VIB group metal component is 5.5-10 wt% and the content of the VIII group metal component is 1-5 wt% based on the total amount of the hydrogenation protective agent and calculated by oxides.
46. The process according to claim 45, wherein the group VIB metal is Mo and/or W; the group VIII metal component is Co and/or Ni.
47. The method of claim 45, wherein the support is selected from at least one of alumina, silica, and silica-alumina.
48. The process according to any one of claims 1 to 8, wherein step (4) fractionates the post-refining effluent obtained in step (3) to obtain a naphtha fraction, the jet fuel fraction, a diesel fraction and a tail oil fraction.
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| CN105462609A (en) * | 2014-09-12 | 2016-04-06 | 中国石油化工股份有限公司 | Aviation kerosene production method |
| CN109504435A (en) * | 2017-09-15 | 2019-03-22 | 中国石油天然气股份有限公司 | A method of being hydrocracked fecund boat coal |
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| CN103059985A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Middle-pressure hydrocracking method for producing aviation kerosene and low-freezing point diesel |
| CN105462609A (en) * | 2014-09-12 | 2016-04-06 | 中国石油化工股份有限公司 | Aviation kerosene production method |
| CN109504435A (en) * | 2017-09-15 | 2019-03-22 | 中国石油天然气股份有限公司 | A method of being hydrocracked fecund boat coal |
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