CN114437799B - Hydrocracking method - Google Patents
Hydrocracking method Download PDFInfo
- Publication number
- CN114437799B CN114437799B CN202011115364.6A CN202011115364A CN114437799B CN 114437799 B CN114437799 B CN 114437799B CN 202011115364 A CN202011115364 A CN 202011115364A CN 114437799 B CN114437799 B CN 114437799B
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- reaction
- hydrogenation
- hydrocracking
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 77
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 125
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 239000003079 shale oil Substances 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000002283 diesel fuel Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 39
- 239000003921 oil Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- 238000005336 cracking Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000003223 protective agent Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 naphtha Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011959 amorphous silica alumina Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000004058 oil shale Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010724 circulating oil Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000003502 gasoline Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 9
- 238000004523 catalytic cracking Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000011800 void material Substances 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
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- 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
Abstract
The invention discloses a hydrocracking method, which comprises the following steps: (1) Mixing high-nitrogen raw oil and hydrogen to enter a hydrogenation pretreatment reaction zone for reaction; (2) The reaction effluent of the step (1) or the liquid phase obtained by separating the reaction flow of the step (1) enters a hydrofining reaction zone for reaction after heat exchange; (3) The effluent of the hydrofining reaction zone in the step (2) enters a hydrocracking reaction zone for hydrocracking reaction, wherein the outlet temperature of the hydrofining reaction zone is T1, the inlet temperature of the hydrocracking reaction zone is T2, T1-T2= delta T is set, and delta T is controlled to be larger than 5 ℃; (4) The reaction effluent of the step (3) passes through a separator to obtain different products. The method can directly process the full-fraction shale oil, adopts a one-pass process flow, and can produce high-quality diesel oil and gasoline in a long-period operation mode.
Description
Technical Field
The invention belongs to the field of hydrogenation processes, and relates to a hydrocracking method, in particular to a shale oil hydrocracking method.
Background
Shale oil is a liquid product obtained by heating and decomposing kerogen in oil shale, and contains a large amount of unsaturated hydrocarbon, non-hydrocarbon compounds such as sulfur, nitrogen, oxygen and the like, and also contains high-content metal impurities.
CN201711469253.3 discloses a flexible shale oil hydrocracking process, the shale oil raw material is subjected to gas-liquid separation after being subjected to hydrogenation pretreatment, the separated liquid phase firstly passes through a hydrocracking pretreatment reactor, then continuously enters the hydrocracking reactor, and the material after passing through a first hydrocracking catalyst bed is divided into two parts; one material is processed by a gas-liquid separator arranged in the middle of a bed layer to obtain a liquid phase, and is pumped out of a hydrocracking reactor, and enters the hydroisomerization cracking reactor to carry out isomerism cracking reaction; the materials after the liquid phase is extracted continuously flow downwards through the second hydrocracking catalyst bed layer; the hydrocracking reaction material and the hydroisomerization cracking reaction material are respectively subjected to gas-liquid separation and fractionation to obtain naphtha, aviation kerosene, diesel oil and tail oil products with different specifications.
CN201010517576.7 discloses a deep processing method of shale oil, catalytic cracking light cycle oil and catalytic cracking heavy cycle oil enter a shale oil hydrotreater together; the obtained hydrogenated oil and optional vacuum gas oil enter a catalytic cracking device, and the reaction product is separated to obtain dry gas containing ethylene, liquefied gas containing propylene and butylene, catalytic cracking gasoline rich in monocyclic aromatic hydrocarbon, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil; the obtained catalytic cracking light cycle oil and heavy cycle oil are circulated to a shale oil hydrotreater.
CN201010222059.7 discloses a shale oil one-stage serial hydrofining process method, shale oil raw material and hydrogen are firstly subjected to heat exchange with a heat medium to 200-280 ℃ for 0.5h -1 ～4.0h -1 The volume space velocity passes through a first reactor containing a high void fraction hydrofining catalyst; heating the effluent of the first reactor in a heating furnace at a volume space velocity of 0.3h -1 ～1.0h -1 Directly passing through a second reactor, wherein the average reaction temperature in the second reactor is 360-420 ℃, and the second reactor is filled with a conventional hydrofining catalyst. The method improves the hydrogenation reaction effect under the condition of ensuring the long-period stable operation of the shale oil hydrogenation device.
CN200810010251.2 discloses a process for hydrogenating shale oil, the shale oil raw material enters the reactor from the upper part, hydrogen enters the reactor from the lower part, the gas-liquid reversely passes through the hydrofining catalyst bed layer to hydrofining oil, the gas phase is discharged from the upper part of the reactor after the reaction, the liquid phase is refined shale oil after the reaction, and is discharged from the lower part of the reactor.
CN201010513745.X discloses a method for producing clean diesel oil in maximum through full-fraction hydrogenation of shale oil. The method adopts a hydrofining-hydrocracking combined process, comprises the steps of mixing shale oil full fraction with hydrogen to enter a hydrofining reaction section, enabling refined effluent to enter a separator for gas-liquid separation through heat exchange and cooling, enabling separated liquid material flow to enter a product fractionating tower, and cutting products such as naphtha, diesel oil and the like. The unconverted oil at the bottom of the fractionating tower enters an oxygenation cracking reaction section for hydrocracking, and the obtained hydrogenation reaction effluent is completely circulated and used as a hydrofining feed.
CN20090012479. X discloses a shale oil one-stage serial hydrocracking process method, wherein shale oil raw materials and hydrogen flow in parallel to enter a hydrofining reactor from the upper part, hydrofining reaction is carried out in the presence of a hydrofining catalyst, hydrofining reaction effluent enters the upper part of the hydrocracking reactor, gas-liquid separation is carried out at the upper part of the hydrocracking reactor, gas phase is discharged from the top of the hydrocracking reactor, liquid phase and hydrogen entering from the bottom of the hydrocracking reactor flow in reverse on the hydrocracking catalyst to carry out hydrocracking reaction, after the hydrocracking reaction, liquid phase products are discharged from the bottom of the hydrocracking reactor, and gas phase separated from the hydrofining reaction effluent is jointly discharged from the top of the hydrocracking reactor.
CN201010539090.3 discloses a processing method of shale oil. The method comprises the following steps: the shale oil is divided into light and heavy components, the heavy component and the hydrogen pass through an up-flow hydrogenation reactor, the obtained effluent reacts with the light component and the hydrogen through a conventional hydrofining reactor, and the hydrofining effluent is separated and fractionated to obtain a light product.
CN201711194923.5 discloses a method for preparing fuel oil by catalytic hydrogenation of shale oil. The method comprises the following steps: a) Removing impurities with the particle size of more than 20 microns from shale oil, mixing the shale oil with a sulfur-containing auxiliary agent, and then mixing the shale oil with hydrogen to obtain hydrogen-mixed raw oil; b) The mixed hydrogen raw oil sequentially enters a hydrogenation protection reactor and a hydrofining reactor for reaction, the reaction output is subjected to gas-liquid separation, and the liquid separation of the low-pressure separator is mixed with desalted water containing an ammonia capturing agent and then enters a hydro-upgrading reactor for reaction; c) The reaction output material is separated once through a second high-pressure separator, and the lower part of the second high-pressure separator enters a second low-pressure separator for secondary separation; d) After the materials are separated in the second low-pressure separator, the top gas separator is recovered, and the bottom liquid separator is sent to the fractionating tower; e) Fractionating by a fractionating tower to obtain the final product.
In summary, in the prior art, two-stage hydrocracking process is generally adopted for shale oil processing, namely, raw materials are hydrofined firstly and then enter a gas-liquid separation system, and ammonia and water in the reaction system are removed and then enter a hydrocracking reactor. Although the two-stage hydrocracking process flow is more complex, compared with the defects that the one-stage hydrocracking process flow in which refined materials directly enter the hydrocracking cannot run for a long period, the product quality is poor and the like, the two-stage hydrocracking is still the dominant process for processing shale oil at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrocracking method which can directly process full-fraction shale oil and can produce high-quality diesel oil and gasoline by adopting a one-pass process flow.
A hydrocracking process comprising the following:
(1) Mixing high-nitrogen raw oil and hydrogen to enter a hydrogenation pretreatment reaction zone for desulfurization, denitrification, deoxidization, olefin removal and arene saturation reaction, preferably mixing full-fraction shale oil and hydrogen to enter the hydrogenation pretreatment reaction zone for desulfurization, denitrification, deoxidization, olefin removal, arene saturation reaction and the like;
(2) The reaction effluent of the step (1) or the liquid phase obtained by separating the reaction effluent of the step (1) in a gas-liquid separator enters a hydrofining reaction zone for deep hydrodesulfurization, single removal, deoxidation, aromatic hydrocarbon saturation and other reactions after heat exchange;
(3) The effluent of the hydrofining reaction zone in the step (2) enters a hydrocracking reaction zone for hydrocracking reaction, the outlet temperature of the hydrofining reaction zone is T1, the inlet temperature of the hydrocracking reaction zone is T2, T1-T2= delta T is set, delta T is controlled to be larger than 5 ℃, delta T is preferably 10-50 ℃, delta T is further preferably 20-30 ℃, and delta T can be adjusted by the amount of the introduced hydrogen;
(4) The hydrogen-rich gas obtained after the reaction effluent in the step (3) is subjected to gas-liquid separation by a separator is used as recycle hydrogen, and the liquid phase enters a fractionating tower to be fractionated to obtain gas, naphtha, diesel oil and tail oil; wherein, the tail oil can be used as circulating oil to be recycled to the inlet of the hydrofining reaction zone, and can also be used for directly producing the isomerization dewaxing raw material.
In the method of the present invention, the nitrogen content in the high nitrogen feedstock oil in step (1)More than 0.3m percent, preferably 0.5m percent to 2.0m percent; the oxygen content is more than 0.05m percent, preferably 0.3m percent to 1.5m percent; the olefin content is more than 1m%, preferably more than 5%, and more preferably 10-50%; the density of the raw oil is 0.86g/cm -3 ~0.99 g/cm -3 Preferably 0.88g/cm -3 ~0.95 g/cm -3 。
In the method, the full-fraction shale oil in the step (1) is all liquid products obtained by heating and decomposing kerogen in the oil shale, and the fraction range is generally 100-750 ℃; the density is generally 0.88g/cm -3 ~0.93 g/cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The nitrogen content is generally 0.6-2.0 m%, preferably 0.8-1.5 m%; the oxygen content is generally 0.5-1.5 m%, preferably 0.6-1.0 m%; the olefin content is more than 10m%, preferably 10m% -50 m%.
In the method of the present invention, the hydrotreating reaction zone of step (1) and the hydrofining reaction zone of step (2) are filled with a hydrofining catalyst, preferably a hydrogenation protecting agent and a hydrofining catalyst in sequence along the flow direction. The hydrogenation protective agent generally takes porous refractory inorganic oxide such as alumina as a carrier, oxide of metal of VIB group and/or VIII group such as W, mo, co, ni and the like as an active component, the mass content of the porous refractory inorganic oxide in the catalyst is 1-20 percent, preferably 3-15 percent, the mass content of the metal of VIII group in the catalyst is selected from nickel and/or cobalt, the mass content of the metal of VIII group in the catalyst is 1-6 percent, preferably 1.5-5 percent, and other various auxiliary agents such as P, si, F, B and the like are selectively added. The hydrofining catalyst comprises a carrier and hydrogenation active metal; wherein the carrier is inorganic refractory oxide, and is generally selected from one or more of alumina, amorphous silica-alumina, silicon dioxide or titanium oxide; the hydrogenation active metal comprises a group VIB and/or group VIII metal component, wherein the group VIB in the hydrofining catalyst is selected from tungsten and/or molybdenum, the content of the group VIB in the catalyst is 5-30 percent, preferably 10-20 percent, based on the oxidation mass, and the content of the group VIII in the catalyst is selected from nickel and/or cobalt, preferably 1.5-5 percent, based on the oxidation mass.
In the method of the invention, the reaction conditions in the hydrotreating reaction zone in the step (1) are generally as follows: the reaction pressure is 1.0-6.0 MPa, preferably 3.0-5.0 MPa; flat plateThe average reaction temperature is 150-350 ℃, preferably 200-300 ℃; the liquid hourly space velocity is 0.1 to 15.0h -1 Preferably 0.2 to 3.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio is 100:1 to 2500:1, preferably 400:1 to 2000:1.
in the method, the operating pressure of the gas-liquid separator in the step (2) is equal to the reaction pressure of the hydrogenation pretreatment reaction zone in the step (1), and the temperature is 100-300 ℃, preferably 150-250 ℃.
In the method of the invention, the reaction conditions in the hydrofining reaction zone in the step (2) are generally as follows: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the liquid hourly space velocity is 0.1 to 15.0h -1 Preferably 0.2 to 3.0h -1 The average reaction temperature of the hydrofining reaction zone is 360-410 ℃, and the volume ratio of the hydrogen inlet of the hydrofining reaction zone to the hydrogen inlet of the hydrocracking reaction zone is 0.2-5.0, preferably 0.6-1.0.
In the method of the invention, the outlet temperature of the hydrofining reaction zone in the step (2) is 390-450 ℃, preferably 410-440 ℃.
In the process of the present invention, the hydrocracking catalyst described in step (3) generally comprises a cracking component, a hydrogenation component and a binder. The cracking component typically comprises amorphous silica alumina and/or molecular sieves, commonly used molecular sieves such as beta-type molecular sieves. The binder is typically alumina or silica. The hydrogenation component is a group VI, VII, VIB or VIII metal, metal oxide or metal sulfide, more preferably one or more of iron, chromium, molybdenum, tungsten, cobalt, nickel or sulfide or oxide thereof. The content of the hydrogenation component is usually 5-40 wt%, and the content of the cracking component is 1-20 wt%, preferably 5-10 wt%, based on the weight of the hydrocracking catalyst.
In the process of the present invention, the hydrocracking reaction zone operating conditions described in step (3) include: the reaction pressure is 5.0-35.0 MPa, preferably 6.0-19.0 MPa; the average reaction temperature is 200-480 ℃, preferably 270-450 ℃; the liquid hourly space velocity is 0.1 to 15.0h -1 Preferably 0.2 to 3.0h -1 。
Compared with the prior art, the method has the following advantages:
(1) The method adopts a series-connected process flow, the process flow is simple and easy to operate, the equipment investment is low, and the method has higher feasibility no matter a newly-built device or an existing device is modified;
(2) The organic amine is converted into ammonia gas after hydrofining, and a large amount of ammonia gas can seriously inhibit the cracking activity of a hydrocracking catalyst;
(3) The shale oil has high paraffin content and the naphtha component has low economic benefit as a chemical raw material, and the method can effectively reduce the content of light hydrocarbons (including dry gas, liquefied gas and naphtha) in the product, and can maximally produce diesel products and isomerism dewaxing raw materials;
(4) The raw materials can directly enter a hydrofining reaction zone after pretreatment, and also can enter the hydrofining reaction zone after gas-liquid separation, the hydrogenation pretreatment reaction zone carries out olefin saturation and shallow denitrification and deoxidation reaction on the raw materials under the low-temperature and low-pressure operation condition, thus being capable of preventing olefin from polymerizing and coking under the high-temperature environment, and the low-pressure gas-liquid separation can reduce the investment of the device and the operation risk.
Drawings
Fig. 1 is a schematic flow chart of one principle of the process of the present invention, and fig. 2 is a schematic flow chart of another principle of the process of the present invention.
In fig. 1, shale oil 1 and low-pressure hydrogen 2 are mixed and enter a hydrogenation pretreatment reaction zone 3, pretreatment effluent 4 enters a low-pressure gas-liquid separator 5, separated gas 6 is recycled, liquid 7 and high-pressure hydrogen 8 are mixed and enter a hydrofining reaction zone 9, hydrofining effluent 10 enters a hydrocracking reaction zone 11, cracking reaction effluent 12 enters a high-pressure separator 13, separated gas 14 is recycled, liquid 15 enters a fractionating tower 16, and separated gas 17, gasoline 18, diesel 19 and tail oil 20 are obtained.
In fig. 2, shale oil 1 and hydrogen 2 are mixed and enter a hydrogenation pretreatment reaction zone 3, pretreatment effluent 4 enters a hydrogenation refining reaction zone 5, hydrogenation refining effluent 6 enters a hydrocracking reaction zone 7, cracking reaction effluent 8 enters a high-pressure separator 9, separated gas 10 is recycled, liquid 11 enters a fractionating tower 12, and gas 13, gasoline 14, diesel 15 and tail oil 16 are separated.
Detailed Description
The operation and effect of the present invention will be further illustrated by the following examples, which are not to be construed as limiting the process of the present invention, and are all percentages by mass unless otherwise specified.
The protecting agent adopted in the hydrocracking pretreatment reaction zone in the embodiment and the comparative example is FDM-21, the hydrofining catalyst is FF-33, the protecting agent adopted in the hydrofining reaction zone is FDM-21, the hydrofining catalyst is FF-46, the hydrocracking catalyst adopted in the hydrocracking reaction zone is FC-14, and manufacturers of the catalysts are all China petrochemical catalyst Co.
TABLE 1 catalyst physicochemical Properties
TABLE 2 Main Properties of raw oil
Table 3 example process conditions and test results
Table 3 comparative example process conditions and test results
The embodiment shows that the method can realize the purpose of producing more diesel oil by adopting the full-fraction shale oil, and simultaneously reduce the condensation point of the diesel oil product and improve the cetane number.
Claims (20)
1. A hydrocracking process characterized by: the method comprises the following steps:
(1) Mixing high-nitrogen raw oil and hydrogen to enter a hydrogenation pretreatment reaction zone for reaction;
(2) The reaction effluent of the step (1) or the liquid phase obtained by separating the reaction effluent of the step (1) in a gas-liquid separator enters a hydrofining reaction zone for reaction after heat exchange;
(3) The effluent of the hydrofining reaction zone in the step (2) enters a hydrocracking reaction zone for hydrocracking reaction, wherein the outlet temperature of the hydrofining reaction zone is T1, the inlet temperature of the hydrocracking reaction zone is T2, T1-T2= delta T is set, and delta T is controlled to be larger than 5 ℃;
(4) The hydrogen-rich gas obtained after the reaction effluent in the step (3) is subjected to gas-liquid separation by a separator is used as recycle hydrogen, and the liquid phase enters a fractionating tower to be fractionated to obtain gas, naphtha, diesel oil and tail oil; wherein, tail oil is used as circulating oil to circulate to the inlet of the hydrofining reaction zone, or isomerism dewaxing raw material is directly produced;
the nitrogen content in the high-nitrogen raw oil in the step (1) is more than 0.3 m%; oxygen content is above 0.05 m%; the olefin content is more than 1 m%; the density of the raw oil is 0.86g/cm 3 ~0.99 g/cm 3 ；
The reaction conditions of the hydrofining reaction zone in the step (2) are as follows: the reaction pressure is 5.0-35.0 MPa; the liquid hourly space velocity is 0.1 to 15.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The average reaction temperature of the hydrofining reaction zone is 360-410 ℃, and the volume ratio of the hydrogen inlet of the hydrofining reaction zone to the hydrogen inlet of the hydrocracking reaction zone is 0.2-5.0;
the hydrocracking reaction zone operating conditions described in step (3) include: reverse-rotationThe stress is 5.0-35.0 MPa; the average reaction temperature is 200-480 ℃; the liquid hourly space velocity is 0.1 to 15.0h -1 。
2. The method according to claim 1, characterized in that: the delta T is controlled to be 10-50 ℃.
3. The method according to claim 1, characterized in that: the delta T is controlled to be 20-30 ℃.
4. The method according to claim 1, characterized in that: the full fraction shale oil and hydrogen are mixed and enter a hydrogenation pretreatment reaction zone for reaction.
5. The method according to claim 1, characterized in that: the nitrogen content in the high-nitrogen raw oil in the step (1) is 0.5-2.0 m%; the oxygen content is 0.3-1.5 m%; the olefin content is 10-50 m%; the density of the raw oil is 0.88g/cm 3 ~0.95 g/cm 3 。
6. The method according to claim 1, characterized in that: the full-fraction shale oil in the step (1) is all liquid products obtained by heating and decomposing kerogen in the oil shale, and the fraction range is 100-750 ℃; density of 0.88g/cm 3 ~0.93 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The nitrogen content is 0.6-2.0 m%; the oxygen content is 0.5-1.5 m%; the olefin content is more than 10 m%.
7. The method according to claim 6, wherein: the nitrogen content is 0.8-1.5 m%; the oxygen content is 0.6 m-1.0 m; the olefin content is 10-50 m%.
8. The method according to claim 1, characterized in that: the hydrogenation pretreatment reaction zone in the step (1) and the hydrogenation refining reaction zone in the step (2) are filled with a hydrogenation refining catalyst, and the hydrogenation refining catalyst comprises a carrier and hydrogenation active metals; wherein the carrier is inorganic refractory oxide, and is selected from one or more of alumina, amorphous silica-alumina, silicon dioxide or titanium oxide; the hydrogenation active metal comprises a VIB and/or VIII metal component, wherein the VIB is selected from tungsten and/or molybdenum, the weight content of the VIB in the catalyst is 5-30% based on oxide, the VIII is selected from nickel and/or cobalt, the weight content of the VIII in the catalyst is 1-6% based on oxide, and the catalyst contains one or more auxiliary elements of P, si, F, B.
9. The method according to claim 8, wherein: the hydrofining catalyst comprises 10% -20% of a VIB metal component in terms of oxide in the catalyst; the weight content of the VIII group metal component in the catalyst is 1.5-5% based on oxide.
10. The method according to claim 1, characterized in that: the hydrogenation pretreatment reaction zone in the step (1) and the hydrogenation refining reaction zone in the step (2) are sequentially filled with a hydrogenation protecting agent and a hydrogenation refining catalyst along the flow direction, wherein the hydrogenation protecting agent takes porous refractory inorganic oxide as a carrier, metal of the VIB group and/or metal of the VIII group is taken as an active component, the mass content of the metal of the VIB group and/or the metal of the VIII group in the catalyst is 1-20% based on oxide, the VIII group is selected from nickel and/or cobalt, the mass content of the metal of the VIII group in the catalyst is 1-6% based on oxide, and one or more auxiliary elements in P, si, F, B are contained in the catalyst.
11. The method according to claim 10, wherein: the hydrogenation protective agent comprises 3-15% of metal of VIB group and/or metal of VIII group in terms of oxide, and 1.5-5% of metal of VIII group in terms of oxide in the catalyst.
12. The method according to claim 1, characterized in that: the reaction conditions of the hydrogenation pretreatment reaction zone in the step (1) are as follows: the reaction pressure is 1.0-6.0 MPa; the average reaction temperature is 150-350 ℃; the liquid hourly space velocity is 0.1 to 15.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio is 100:1 to 2500:1.
13. the method according to claim 12, wherein: the reaction conditions of the hydrogenation pretreatment reaction zone in the step (1) are as follows: the reaction pressure is 3.0-5.0 MPa; the average reaction temperature is 200-300 ℃; the liquid hourly space velocity is 0.2 to 3.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen oil volume ratio is 400:1 to 2000:1.
14. the method according to claim 1, characterized in that: in the step (2), the operating pressure of the gas-liquid separator is 1.0-6.0 MPa, and the temperature is 100-300 ℃.
15. The method according to claim 1, characterized in that: the reaction conditions of the hydrofining reaction zone in the step (2) are as follows: the reaction pressure is 6.0-19.0 MPa; the liquid hourly space velocity is 0.2 to 3.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of the hydrogen inlet of the hydrofining reaction zone to the hydrogen inlet of the hydrocracking reaction zone is 0.6-1.0.
16. The method according to claim 1, characterized in that: the outlet temperature of the hydrofining reaction zone in the step (2) is 390-450 ℃.
17. The method according to claim 16, wherein: the outlet temperature of the hydrofining reaction zone in the step (2) is 410-440 ℃.
18. The method according to claim 1, characterized in that: the hydrocracking catalyst of step (3) comprises a cracking component, a hydrogenation component and a binder.
19. The method according to claim 18, wherein: the cracking component comprises amorphous silica-alumina and/or molecular sieve, the adhesive is alumina or silica, the hydrogenation component is VIB and/or VIII metal, the content of the hydrogenation component is 5-40wt% based on the weight of the hydrocracking catalyst, and the content of the cracking component is 1-20wt%.
20. According to claimThe method of claim 1, characterized in that: the hydrocracking reaction zone operating conditions described in step (3) include: the reaction pressure is 6.0-19.0 MPa; the average reaction temperature is 270-450 ℃; the liquid hourly space velocity is 0.2 to 3.0h -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115364.6A CN114437799B (en) | 2020-10-19 | 2020-10-19 | Hydrocracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011115364.6A CN114437799B (en) | 2020-10-19 | 2020-10-19 | Hydrocracking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437799A CN114437799A (en) | 2022-05-06 |
| CN114437799B true CN114437799B (en) | 2023-05-30 |
Family
ID=81358368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011115364.6A Active CN114437799B (en) | 2020-10-19 | 2020-10-19 | Hydrocracking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437799B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453537A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation |
| CN109988641A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible hydrogenation of shale oil process |
| CN109988609A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible hydrogenation of shale oil process |
-
2020
- 2020-10-19 CN CN202011115364.6A patent/CN114437799B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453537A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation |
| CN109988641A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible hydrogenation of shale oil process |
| CN109988609A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible hydrogenation of shale oil process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437799A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111321005B (en) | Hydrogenation process for producing diesel oil with low energy consumption and long period | |
| CN109988631B (en) | Method for producing gasoline and base oil by catalyst grading technology | |
| CN114437799B (en) | Hydrocracking method | |
| CN114437798B (en) | Shale oil hydrocracking method | |
| CN102344826A (en) | Combined hydrogenation method for producing catalytic raw material and high-quality diesel oil | |
| CN114437804B (en) | Hydrocracking method of high-nitrogen raw oil | |
| CN110408429B (en) | Method for treating heavy oil by combined process | |
| CN109988651B (en) | Method for producing gasoline by catalyst grading technology | |
| CN102807898B (en) | Hydrocracking method for increasing production of high-quality middle distillates | |
| CN114437790B (en) | Hydrocracking method for producing ethylene raw material | |
| CN114437777B (en) | Method for producing lubricating oil base oil | |
| CN114437778B (en) | Fischer-Tropsch synthetic oil hydrocracking process | |
| CN109988630B (en) | Wax oil hydrogenation method and system | |
| CN113122321B (en) | Hydrocracking method for improving aromatic hydrocarbon potential of heavy naphtha | |
| CN110408428B (en) | Method for treating residual oil by combined process | |
| CN112342059B (en) | Method for blending catalytic cracking slurry oil in delayed coking unit | |
| CN102807896B (en) | Hydrotreating method for maximum production of middle distillates | |
| CN113122319B (en) | Hydrocracking process for producing high-quality reforming raw material | |
| CN110408430B (en) | Method for treating heavy hydrocarbon by combined process | |
| CN102533327A (en) | Single-stage inferior gasoline fraction hydrotreatment process method | |
| CN114437774A (en) | Hydrocracking method for producing high-quality diesel oil and lubricating oil base oil | |
| CN113462431B (en) | Method for producing diesel oil and jet fuel | |
| CN103059965A (en) | Catalytic gasoline deep hydrodesulfurization method | |
| CN111321006B (en) | Step-by-step diesel oil hydrogenation method based on different types of aromatic hydrocarbon compositions | |
| CN109777490B (en) | Oil refinery gas hydrogenation combined process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231121 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |