CN111321005B - Hydrogenation process for producing diesel oil with low energy consumption and long period - Google Patents
Hydrogenation process for producing diesel oil with low energy consumption and long period Download PDFInfo
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- CN111321005B CN111321005B CN201811522009.3A CN201811522009A CN111321005B CN 111321005 B CN111321005 B CN 111321005B CN 201811522009 A CN201811522009 A CN 201811522009A CN 111321005 B CN111321005 B CN 111321005B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 182
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 27
- 238000005265 energy consumption Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 115
- 238000006243 chemical reaction Methods 0.000 claims abstract description 109
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000012071 phase Substances 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 23
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 39
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 35
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 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 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910017318 Mo—Ni Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 17
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 13
- 238000006477 desulfuration reaction Methods 0.000 description 12
- 230000023556 desulfurization Effects 0.000 description 12
- 150000003568 thioethers Chemical class 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation process for producing ultralow-sulfur diesel oil with low energy consumption and long period, which comprises the following steps: (a) fractionating the diesel raw oil to obtain a light fraction and a heavy fraction; (b) carrying out hydrodesulfurization reaction on the heavy fraction diesel raw oil obtained in the step (a) in a first hydrogenation reaction zone under the action of a hydrodesulfurization catalyst; (c) reacting the material flow obtained in the step (b) with the light fraction diesel raw oil obtained in the step (a) in a second hydrogenation reaction zone under the action of a hydrodesulfurization catalyst; (d) separating the material flow obtained in the step (c) into a gas phase and a liquid phase, and separating the liquid phase to obtain gas, naphtha and diesel oil products. The hydrogenation process has the advantages of low energy consumption, long running period and the like.
Description
Technical Field
The invention belongs to a hydrogenation process in an oil refining technology, and particularly relates to a hydrogenation process for producing diesel oil with low energy consumption and long period.
Background
Energy currently worldwide is derived primarily from fossil energy sources, with petroleum being the most prominent source of motor fuel. As the world economy continues to evolve, environmental regulations become more stringent requiring the production of large quantities of light, clean motor fuels, which require improvements and modifications to existing refinery technologies. The quality requirements of diesel oil as important motor fuel are more and more high, and the indexes such as sulfur content, density, cetane number, polycyclic aromatic hydrocarbon and the like are strictly limited.
The diesel hydrogenation technology is the most important means for improving the quality of diesel products. CN102465021A discloses a diesel oil combined hydrogenation process, in which diesel oil fraction is cut into light and heavy components, the light component is processed by liquid phase hydrogenation method, the heavy component is reversed by gas phase circulation hydrogenationProcessing should be performed. CN102851067A discloses a hydrogenation method for producing ultra-low sulfur clean diesel, diesel fraction cutting 280～340 light and heavy components, wherein the heavy component is subjected to countercurrent hydrogenation, and the light component is subjected to conventional gas phase circulating hydrogenation. CN102051219A discloses a hydrotreating method of diesel fraction, wherein the diesel fraction is fractionated to obtain light and heavy fractions, the light fraction is hydrogenated conventionally, and the heavy fraction is hydrogenated by using a bulk phase catalyst. CN200410050729.6 discloses a diesel fraction hydrotreating method, which comprises fractionating raw oil into light fraction and heavy fraction, feeding the light fraction into a first reaction zone to contact with a hydrofining catalyst, feeding the heavy fraction into a second reaction zone to contact with the hydrofining catalyst, and mixing the liquid phase products of the two reaction zones to obtain refined distillate, wherein the catalysts and/or process conditions used in the two reaction zones are different. CN102041071A discloses a diesel hydrogenation process, which comprises fractionating a diesel raw material into a light component and a heavy component, subjecting the heavy component to a hydrofining reaction in a first reaction zone under the hydrofining condition, mixing the effluent of the first reaction zone and the light component, and introducing the mixture into a second reaction zone to perform the hydrofining reaction, and separating the effluent of the second reaction zone. The method adopts the process of firstly hydrodearomatizing and then desulfurizing, the first reaction zone can lead the hydrodearomatizing to be limited by thermodynamics because of high reaction temperature at the later stage of the operation of the device, namely, the temperature raising space of the catalyst is relatively small, the operation period of the catalyst is shortened, the initial reaction temperature of the second reaction zone is higher than that of the first hydrogenation zone, and the temperature raising space of the catalyst is smaller.
In summary, in the prior art, because the diesel raw material contains a large amount of sulfur in the form of organic sulfur, a certain reaction temperature is required in the hydrodesulfurization process, and particularly, in order to maintain the sulfur removal rate after long-period operation, temperature raising operation is often required, so that energy consumption is high, and the operation period of the device is affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation process for producing diesel oil with low energy consumption and long period.
The invention relates to a hydrogenation process for producing ultralow-sulfur diesel oil with low energy consumption and long period, which comprises the following steps:
(a) fractionating the diesel raw oil to obtain a light fraction and a heavy fraction;
(b) carrying out hydrodesulfurization reaction on the heavy fraction diesel raw oil obtained in the step (a) in a first hydrogenation reaction zone under the action of a hydrodesulfurization catalyst, wherein the sulfur content in a liquid stream flowing out of the first hydrogenation reaction zone is not more than 35 mug/g, and preferably 8 mug/g-30 mug/g;
(c) carrying out hydrodesulfurization reaction on the material flow of the first hydrogenation reaction zone obtained in the step (b) and the light fraction diesel raw oil obtained in the step (a) in a second hydrogenation reaction zone under the action of a hydrodesulfurization catalyst to obtain material flow of the second hydrogenation reaction zone;
(d) and (c) separating the material flow of the second hydrogenation reaction zone obtained in the step (c) into a gas phase and a liquid phase, recycling the obtained hydrogen-rich gas directly or after removing hydrogen sulfide, and separating the obtained liquid phase to obtain gas, naphtha and diesel oil products.
In the method, the proportion of the hydrogen sulfide increase value of the first hydrogenation reaction zone (the content difference value between the outlet of the first hydrogenation reaction zone and the inlet of the first hydrogenation reaction zone) to the total hydrogen sulfide increase value (the content difference value between the outlet of the second hydrogenation reaction zone and the inlet of the first hydrogenation reaction zone) is 45-70%.
In the above method, one of the following schemes is preferably adopted:
1) the heavy fraction firstly passes through an upper part hydrofining catalyst bed layer in a first hydrogenation reaction zone, one part of generated material flow enters a gas-liquid separator to be separated into a gas phase and a liquid phase, the other part of generated material flow and the liquid phase continuously pass through a lower part of hydrofining catalyst bed layer, and the generated material flow, the light fraction and the gas phase are mixed and then continuously hydrofined in a second hydrogenation reaction zone;
2) firstly, carrying out hydrofining and hydro-upgrading on heavy fractions in a first hydrogenation reaction zone through a hydrofining catalyst bed and a hydro-upgrading catalyst bed, mixing the generated material flow and light fractions, and then continuously carrying out hydrofining in a second hydrogenation reaction zone through the hydrofining catalyst bed;
3) the heavy fraction firstly passes through the upper part of a hydrofining catalyst bed layer in the first hydrogenation reaction zone, one part of generated material flow enters a gas-liquid separator to be separated into a gas phase and a liquid phase, the other part of generated material flow and the liquid phase continuously pass through the lower part of the hydrofining catalyst bed layer and the hydrofining catalyst bed layer to be subjected to hydrofining and hydro-upgrading, and the generated material flow, the light fraction and the gas phase are mixed and then continuously pass through the hydrofining catalyst bed layer in the second hydrogenation reaction zone to be subjected to hydrofining.
In the method, the used diesel raw oil can comprise one or more of straight-run diesel, catalytic diesel, coking diesel, thermal cracking diesel, visbreaking diesel, synthetic diesel, coal tar diesel fraction, coal direct liquefaction diesel, shale oil diesel and other diesel fractions.
In the method, the weight ratio of the light fraction to the heavy fraction obtained by fractionating the diesel raw material is 35: 65-55: 45.
In the method, the sulfur content in the heavy fraction obtained by fractionating the diesel raw material accounts for 45-70%, preferably 47-65% of the total sulfur content in the diesel raw material.
In the above method, the first hydrogenation reaction zone may be one reactor or may be composed of a plurality of reactors, and if a plurality of reactors are selected, it is preferable that 2 to 4 reactors are selected. One catalyst bed layer or a plurality of catalyst bed layers can be arranged in the reactor, and preferably 2-5 catalyst bed layers are selected if a plurality of catalyst bed layers are selected. The amount of cold hydrogen between the catalyst beds, or between the reactors, is determined by the reactant stream flow rate and the temperature difference that needs to be reduced. The operating conditions of the first hydrogenation reaction zone are generally reversedThe stress is 3.0-13.0 MPa, and the volume space velocity of the heavy fraction diesel oil raw material oil is 0.2h-1~10.0h-1The average reaction temperature is 220-440 ℃, and the volume ratio of hydrogen to oil is 200: 1-1500: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-12.0 MPa, and the volume space velocity of the heavy fraction raw oil is 0.3h-1~8.0h-1The average reaction temperature is 230-433 ℃, and the volume ratio of hydrogen to oil is 300: 1-1200: 1.
In the above method, the second hydrogenation reaction zone may be one reactor or may be composed of a plurality of reactors, and if a plurality of reactors are selected, it is preferable that 2 to 4 reactors are selected. One catalyst bed layer or a plurality of catalyst bed layers can be arranged in the reactor, and preferably 2-5 catalyst bed layers are selected if a plurality of catalyst bed layers are selected. The amount of cold hydrogen between the catalyst beds, or between the reactors, is determined by the flow rate of the stream and the temperature difference that needs to be reduced. The operating conditions of the second hydrogenation reaction zone are that the reaction pressure is 3.0 MPa-13.0 MPa, and the total volume space velocity of the light fraction and heavy fraction diesel oil raw oil is 0.2h-1~20.0h-1The average reaction temperature is 190-437 ℃, and the volume ratio of the total hydrogen to the oil is 150: 1-1200: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-12.0 MPa, and the total volume airspeed of the diesel raw oil is 0.3h-1~16.0h-1The average reaction temperature is 200-430 ℃, and the volume ratio of the total hydrogen to the oil is 200: 1-1000: 1.
In the method, the average reaction temperature of the first hydrogenation reaction zone is higher than that of the second hydrogenation reaction zone, and the difference between the two average reaction temperatures is 3-40 ℃, preferably 5-35 ℃.
In the method, the hydrogenation reaction is an exothermic reaction, and the reaction temperature in the reaction zone tends to increase, namely the outlet temperature of the first reaction zone is higher than the inlet temperature of the first reaction zone, and the outlet temperature of the second reaction zone is higher than the inlet reaction temperature. The outlet temperature of the first reaction zone is controlled to be higher than the inlet temperature of the second reaction zone, and the difference between the two temperatures is 10-100 ℃, and preferably 20-90 ℃. The greater the difference between these two temperatures, the lower the temperature to which the light fraction needs to be increased and the lower the overall energy consumption of the plant. The difference between the two temperatures is adjusted by the weight and the temperature of the light fraction, and can also be adjusted by injecting recycle hydrogen, wherein the temperature of the light fraction can be obtained by heat exchange or heating.
In the above process, in order to reduce the effect of hydrogen sulfide on hydrodesulfurization, particularly heavy fraction hydrodesulfurization, it is necessary to control the total amount of sulfur entering the first hydrogenation reaction zone. And controlling the proportion of the hydrogen sulfide increase value of the first hydrogenation reaction zone (the content difference between the outlet of the first hydrogenation reaction zone and the inlet of the first hydrogenation reaction zone) to the total hydrogen sulfide increase value (the content difference between the outlet of the second hydrogenation reaction zone and the inlet of the first hydrogenation reaction zone) to be 45-70%, preferably 47-65%.
In the above method, the hydrodesulfurization catalyst contains Co as the hydrogenation active component, and one or more selected from Mo, W and Ni may be added, the weight content of the oxide is 5-70%, the carrier of the hydrodesulfurization catalyst is alumina, amorphous silica-alumina, silica, titania, etc., and other auxiliary agents, such as P, Si, B, Ti, Zr, etc., may be added. The catalyst may be used commercially or may be prepared by methods known in the art. The hydrogenation active component is a catalyst in an oxidation state, and is subjected to conventional vulcanization treatment before use, so that the hydrogenation active component is converted into a vulcanization state. The commercial hydrogenation catalysts mainly include hydrogenation catalysts such as FHUDS-3, FHUDS-5, FF-14, FF-24 and the like developed by the Fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as DC-2118, DC-2318, DC-2531 and the like of Criterion corporation, hydrogenation catalysts such as TK-570, TK-576, TK-578 and the like developed by the Tops coffee corporation, and hydrogenation catalysts such as KF-767, KF-770 and the like of the AKZO corporation. The hydrogenation catalyst used in the first hydrogenation reaction zone and the hydrogenation catalyst used in the second hydrogenation reaction zone can be the same or different.
In the above method, the preferred hydro-upgrading catalyst used in the schemes 2) and 3) is a conventional diesel hydro-upgrading catalyst, and generally takes a metal in the VIB group and/or VIII group as an active component, the metal in the VIB group is generally Mo and/or W, and the metal in the VIII group is generally Co and/or Ni. The catalyst carrier contains one or more of alumina, siliceous alumina and molecular sieve, preferably containing molecular sieve; the molecular sieve can be a Y-type molecular sieve. To hastenThe catalyst is characterized in that the catalyst comprises, by weight, 10-35 wt% of a VIB group metal, 3-15 wt% of a VIII group metal, 5-40 wt% of a molecular sieve and 10-80 wt% of alumina, wherein the VIB group metal is calculated by oxides; its specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g. The main catalysts comprise 3963, FC-18, FC-32 catalysts and the like which are developed by the petrochemical research institute. For the hydrogenation modification catalyst, certain hydrogenation activity and certain cracking activity are required, and both hydrogenation saturation of olefin and aromatic hydrocarbon in diesel oil fraction and ring-opening reaction of saturated aromatic hydrocarbon are required. The operating conditions for the hydro-upgrading can be conventional and are generally: the reaction pressure is 3.0MPa to 13.0MPa, the reaction temperature is 300 ℃ to 433 ℃, and the liquid hourly volume space velocity is 0.3h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
The method further optimizes the grading of the catalyst, namely uses a small amount of Mo-Ni type hydrogenation catalyst in the low-temperature zone of the first hydrogenation reaction zone, controls the volume ratio of the Mo-Ni type hydrogenation catalyst to the Co-containing type hydrogenation catalyst in the first hydrogenation reaction zone to be 5: 95-20: 80, and uses the Co-containing type hydrogenation catalyst in the second hydrogenation reaction zone. The advantage of such selection is that under the condition of relatively low temperature in the first hydrogenation reaction zone, the saturation depth of polycyclic aromatic hydrocarbon is controlled, the desulfurization depth of complex sulfide is reduced, sulfur in heavy fraction is removed continuously through Co-containing hydrogenation catalyst under the condition of relatively low hydrogen sulfide concentration, even if the final operating temperature is higher, the requirement of controlling the polycyclic aromatic hydrocarbon hydrogenation saturation of the refractory sulfide in a lower temperature zone and further achieving the deep hydrodesulfurization of the heavy fraction can be achieved, and in the second reaction hydrogenation reaction zone, even if the final operating temperature is relatively lower, the requirement of deep desulfurization can be completely met, the limitation by thermodynamics is smaller, the service temperature space of the catalyst in the two reaction zones is larger, thereby prolonging the operation period of the device, or saving the equipment investment.
In the above method, the gas-liquid separator in preferred embodiments 1) and 3) is a device disposed between the first hydrofining reaction zone and the hydrofining catalyst bed. The gas-liquid separator at least comprises a reaction material flow inlet, a liquid phase conduit, a gas phase conduit and the like, wherein the gas phase conduit extracts a gas phase obtained by separation out of the first hydrofining reaction zone, and the liquid phase conduit continuously introduces a liquid phase obtained by separation downwards into the hydrofining catalyst bed layer at the lower part.
In the above method, the gas-phase stream extracted by the gas-liquid separator in preferred embodiments 1) and 3) accounts for 10 v% to 50% of the volume of the gas-phase stream at the inlet of each reaction zone.
In the method, the effluent separation of the second hydrogenation reaction zone adopts a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. And the material flow of the second hydrogenation reaction zone is separated in a high-pressure separator to obtain high-pressure hydrogen-rich gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The liquid obtained by separation in the high-pressure separator is separated in the high-low pressure separator to obtain gas and liquid.
In the method, the hydrogen-rich gas obtained by the separation of the high-pressure separator can be directly recycled by a recycle compressor, and can also be recycled after hydrogen sulfide is removed by a desulfurizing tower.
In the above method, the fresh hydrogen of the apparatus is pressurized by the fresh hydrogen compressor and then mixed with the recycle hydrogen at the inlet or outlet of the recycle hydrogen compressor, preferably at the outlet.
In the method, the fractionating system used for fractionating comprises a stripping tower and/or a fractionating tower. And the liquid obtained by separation in the low-pressure separator is subjected to steam stripping and/or fractionation in a fractionation system to obtain a naphtha product and a diesel product.
In the above method, the gas separator used for gas separation is a conventional separator. And after the gas obtained by separation in the low-pressure separator is mixed, the gas is separated in a gas separator to obtain hydrogen, dry gas, liquefied gas and the like, and if a liquid product exists, the gas directly enters a stripping tower and/or a fractionating tower.
Research finds that sulfur in raw oil in a diesel hydrogenation process generates hydrogen sulfide through hydrogenation reaction, the hydrogen sulfide is an important factor for restricting hydrodesulfurization, particularly deep desulfurization, when a diesel raw material passes through a catalyst bed layer, easily-reacted sulfides preferentially react, difficultly-reacted complex sulfides finally react, the concentration of the hydrogen sulfide gradually increases along with the flowing direction of a reactant flow, the difficulty of the deep hydrodesulfurization reaction is further increased under the double action, and the specification requirement of a target product is met by increasing the reaction temperature and reducing the volume airspeed, so that the operation period is shortened, or the device is operated in a reduced amount. Even if the diesel fraction is fractionated to obtain light and heavy fractions, if only the heavy fraction is subjected to hydrogenation and dearomatization in the first hydrogenation reaction zone to reduce the difficulty of continuous hydrodesulfurization of the refractory sulfides, the mixture of the product stream of the first reaction zone after dearomatization and the light fraction in the second hydrogenation reaction zone is subjected to hydrodesulfurization, so that the reaction of the refractory complex sulfides in the high-hydrogen-sulfide atmosphere cannot be avoided. Heavy fractions with high content of complex sulfides difficult to react enter a catalyst bed layer of a first reaction zone, most of sulfur of the sulfides difficult to react is directly removed through a Co-containing hydrogenation catalyst (the sulfur content in liquid products in the first hydrogenation reaction zone is controlled to be not more than 30 microgram/g), materials after reaction and light fractions with high content of sulfides easy to react are mixed and enter a Co-containing catalyst bed layer of a second hydrogenation reaction zone, the hydrogen sulfide concentration and the difficulty degree of the reaction sulfides are optimally combined, and the hydrodesulfurization efficiency is improved on the premise of not influencing the quality of diesel products by controlling the difference of average reaction temperatures of the two reaction zones and the difference of hydrogen-oil volume ratios of the two reaction zones, so that the energy consumption and the operation cost are reduced, the operation period is generally prolonged, or the equipment investment is reduced.
The method of the invention fractionates the raw oil into light and heavy fractions, and obviously reduces the average reaction temperature when the total airspeed is the same to achieve the same target product quality by controlling the reaction temperature of the two reaction zones and reducing the influence of the concentration of hydrogen sulfide on the hydrodesulfurization of the components difficult to react, thereby reducing the energy consumption, reducing the total equipment investment cost and prolonging the operation period of the device.
In the preferred schemes 2) and 3) of the method, part of the hydrogenation modified catalyst is continuously used after the heavy fraction is hydrofined, so that the difficulty of hydrodesulfurization can be reduced by utilizing the acidity in the modified catalyst, and the outermost ring of the polycyclic aromatic hydrocarbon can be opened after being subjected to hydrogenation saturation, so that the density of a diesel product can be further reduced and the cetane number can be increased on the basis of keeping the advantages of reducing energy consumption and overall equipment investment cost, prolonging the operation period of a device and the like.
In the preferable schemes 1) and 3) of the method, part of the generated material flow is separated by a gas-liquid separator after the heavy fraction passes through the upper part of the first hydrogenation reaction zone and is subjected to hydrorefining, and the separated gas phase rich in hydrogen sulfide is led out of the heavy fraction hydrogenation reaction zone, so that the content of hydrogen sulfide in a system during deep desulfurization of sulfide difficult to react is further reduced, the deep hydrodesulfurization reaction of sulfide difficult to react is facilitated, the gas phase rich in hydrogen sulfide does not have great influence on the hydrodesulfurization of the introduced light fraction in the second hydrogenation reaction zone, certain heat can be brought, the two reaction zones form coupling operation, and the energy consumption of the device is further reduced.
In the prior art, the diesel raw material can be hydrogenated by a fixed bed to produce clean diesel, in the whole hydrogenation reaction process, particularly, the diesel raw oil is in the initial period of contact with a catalyst, wherein the easily-reacted sulfide in the light fraction is firstly subjected to hydrogenation reaction, so that the concentration of hydrogen sulfide is rapidly increased, namely, the concentration of hydrogen sulfide in the whole reaction process is very high and gradually increases along with the flowing direction of material flow, when the subsequent difficultly-reacted sulfide is subjected to hydrogenation reaction, particularly, the most difficult reactant mainly comprising 4, 6-dimethyldibenzothiophene is frequently generated at the extreme end of all catalysts during deep hydrodesulfurization, at this time, the concentration of hydrogen sulfide almost reaches the maximum, the difficulty of deep hydrodesulfurization is obviously increased, and therefore, the aim requirements are met at higher reaction temperature, lower volume space velocity or higher reaction pressure, even if the diesel raw oil is fractionated into light and heavy fractions, the heavy fraction is subjected to aromatic hydrogenation saturation in the first hydrogenation reaction zone, the material flow generated in the first hydrogenation reaction zone and the light fraction are mixed in the second hydrogenation reaction zone for hydrodesulfurization, and although the desulfurization difficulty is reduced after hydrogenation of aromatic hydrocarbon on the sulfide which is difficult to react, the desulfurization difficulty of the sulfide which is difficult to react is increased due to competitive adsorption of hydrogen sulfide in a high hydrogen sulfide atmosphere generated by desulfurization of the sulfide which is easy to react on the light fraction. The invention fully utilizes the complex sulfide which is difficult to react when the concentration of the hydrogen sulfide is low to react firstly, and the sulfide which is easy to react when the concentration of the hydrogen sulfide is high to react again, thereby reducing the influence of the hydrogen sulfide on the hydrogenation reaction on the whole, and controlling the average reaction temperature of the first hydrogenation reaction zone to be higher than the average reaction temperature of the second hydrogenation reaction zone to realize the hydrodesulfurization under the condition of low hydrogen consumption. The method is characterized in that firstly, diesel raw oil is fractionated into light and heavy fractions, the heavy fraction is contacted with a hydrogenation catalyst containing Co, sulfides which are difficult to react are subjected to hydrodesulfurization reaction in a lower hydrogen sulfide atmosphere of a first hydrogenation reaction zone, the increase of the concentration of hydrogen sulfide in a catalyst bed layer which is more at first is slow due to the high hydrodesulfurization difficulty, the desulfurization reaction performance of the catalyst is correspondingly enhanced due to the fact that competitive adsorption of the sulfides of the light fraction is not carried out even if the volume space velocity of the heavy fraction is the same, deep desulfurization is easy to realize, and chemical hydrogen consumption is low due to the low hydrogenation saturation degree of aromatic hydrocarbon. The hydrogenation reaction material flow of the heavy fraction in the first hydrogenation reaction zone is continuously mixed with the light fraction and then contacts with the Co-containing catalyst in the second hydrogenation reaction zone, the easy-reaction sulfide continuously performs the hydrodesulfurization reaction under the hydrogenation condition, and the requirement of producing clean diesel oil products can be easily met at a lower reaction temperature. The average temperature of the second hydrogenation reaction zone is further reduced by 3-40 ℃ compared with the average temperature of the first reaction zone, namely, the deep removal of heavy fraction sulfides is realized under the condition of higher reaction temperature in the first hydrogenation reaction zone, and the deep hydrodesulfurization of light fraction is realized under the condition of lower reaction temperature in the second hydrogenation reaction zone, namely, the purpose of deep desulfurization is achieved through different reaction conditions of the two reaction zones; and the outlet temperature of the first hydrogenation reaction zone is controlled to be higher than the inlet temperature of the second hydrogenation reaction zone, the difference value of the two temperatures is 10-100 ℃, more methods are used for controlling the temperature difference of the two reaction zones, preferably, the heavy fraction raw oil can reach higher temperature requirements by using a heat exchange and heating method, the light fraction raw oil can reach lower temperature requirements by using the heat exchange method only, and the comprehensive energy consumption of the device is greatly reduced. Because the catalyst containing Co is used in the first hydrogenation reaction zone, the direct desulfurization can be carried out, the reaction temperature is not limited by thermodynamic equilibrium, the temperature application range of the catalyst is larger, the catalyst in the second hydrogenation reaction zone is used at a lower reaction temperature, the temperature application space is larger, the temperature raising space of the catalyst is large, the operation period is long, and the service life of the catalyst is prolonged. In addition, because the raw oil in the first hydrogenation reaction zone is only heavy fraction raw oil, hydrogen required by hydrogenation reaction is relatively less, less circulating hydrogen can be used when the same hydrogen-oil volume ratio is reached, and if cold hydrogen is not used or used in a reduced way at the inlet of the second hydrogenation reaction zone, the usage amount of the circulating hydrogen can be reduced totally, so that the operation cost is saved, or a larger hydrogen-oil volume ratio is provided under the condition of using the same circulating hydrogen, the advantages of relatively high hydrogen partial pressure in the surface environment of a catalyst pore channel and relatively low hydrogen sulfide partial pressure are achieved, and the desulfurization reaction of sulfide which is difficult to react can be facilitated. The hydrogenation process of the technology is generally characterized in that the internal reaction environment is optimized on the premise of not influencing the quality of diesel products, so that the average reaction temperature is reduced, the energy consumption and the operation cost are reduced, the operation period can be prolonged, or the equipment investment is saved.
Drawings
FIG. 1 is a schematic flow diagram of a hydrogenation process according to the present invention.
FIG. 2 is another schematic flow diagram of the hydrogenation process of the present invention.
Wherein in fig. 1 or fig. 2: 1-heavy fraction raw oil, 2-first raw oil pump, 3-pressurized heavy fraction raw oil, 4-first hydrogenation reactor, 5-first hydrogenation reaction effluent, 6-light fraction raw oil, 7-second raw oil pump, 8-second hydrogenation reactor, 9-second hydrogenation reaction effluent, 10-high-pressure separator, 11-stripping/fractionating system, 12-naphtha, 13-diesel, 14-high-pressure hydrogen-rich gas, 15-recycle hydrogen compressor, 16-new hydrogen, 17-gas-liquid separator and 18-gas-liquid separator gas-phase material flow.
Detailed Description
The flow and effect of the hydrogenation process for producing ultra-low sulfur diesel oil with low energy consumption and long cycle according to the present invention will be further illustrated with reference to the following examples, wherein the first hydrogenation reaction zone is a hydrogenation reactor, and the second hydrogenation reaction zone is a hydrogenation reactor, but the following examples do not limit the method according to the present invention.
The specific implementation of the hydrogenation process for producing ultra-low sulfur diesel oil with low energy consumption and long cycle as shown in FIG. 1 is as follows: pressurizing the heavy fraction raw oil 1 by a first raw oil pump to obtain pressurized heavy fraction raw oil 3, continuously mixing the pressurized heavy fraction raw oil 3 with circulating hydrogen, then feeding the mixture into a first hydrogenation reactor 4, and passes through a catalyst bed (a refined catalyst bed or a refined catalyst/modified catalyst bed) to obtain a first hydrogenation reaction effluent 5, the light fraction raw oil 6 is pressurized by a second raw oil pump 7, mixed with the first hydrogenation reaction effluent 5 and then enters a second hydrogenation reactor 12, and passes through a catalyst bed layer, the obtained second hydrogenation reaction effluent 9 enters a high-pressure separator 10, high pressure hydrogen-rich gas 14 and liquid are separated in a high pressure separator 10, the liquid enters a stripping/fractionation system 11, naphtha 12 and diesel oil 13 are obtained by fractionation in a fractionation system, and high-pressure hydrogen-rich gas 14 is pressurized by a recycle hydrogen compressor 15 after hydrogen sulfide is removed and is mixed with new hydrogen 16 to be used as recycle hydrogen.
The specific implementation of the hydrogenation process for producing ultra-low sulfur diesel oil with low energy consumption and long cycle as shown in FIG. 2 is as follows: the heavy fraction raw oil 1 is pressurized by a first raw oil pump to obtain a pressurized heavy fraction raw oil 3, the pressurized heavy fraction raw oil 3 is continuously mixed with circulating hydrogen and then enters a first hydrogenation reactor 4, one part of the generated material flow passes through an upper part catalyst bed layer (refined catalyst) and enters a gas-liquid separator 17 for gas-liquid separation to obtain a gas-liquid separator gas-phase material flow 18, the gas-liquid separator gas-phase material flow is led out of the first hydrogenation reactor 4, the rest material flow is mixed with cold hydrogen and then continuously passes through a lower part catalyst bed layer (refined catalyst bed layer or refined catalyst/modified catalyst bed layer) to obtain a first hydrogenation reaction effluent 5, the light fraction raw oil 6 is pressurized by a second raw oil pump 7 and then is mixed with a first hydrogenation reaction effluent 5 and the gas-liquid separator gas-phase material flow 18 and then enters a second hydrogenation reactor 8 and passes through the catalyst bed layer, and the obtained second hydrogenation reaction effluent 9 enters a high-pressure separator 10, high-pressure hydrogen-rich gas 14 and liquid are obtained by separation in a high-pressure separator 10, the liquid enters a stripping/fractionating system 11 and is fractionated in the fractionating system to obtain naphtha 12 and diesel oil 13, and the high-pressure hydrogen-rich gas 14 is pressurized by a recycle hydrogen compressor 15 after hydrogen sulfide is removed and is mixed with new hydrogen 16 to be used as recycle hydrogen.
The following examples further illustrate specific aspects of the present invention. The FHUDS-5, FHUDS-6 and 3963 catalysts developed and produced by FRIPP are used for experimental research, wherein the FHUDS-5 catalyst takes Mo-Co as a hydrogenation active center, the FHUDS-6 catalyst takes Mo-Ni as a hydrogenation active center, the 3963 catalyst is a hydrogenation modified catalyst and contains a Y-type molecular sieve.
TABLE 1 Main Properties of Diesel feedstocks
Table 2 examples process conditions and main product properties
TABLE 2
| Catalyst and process for preparing same | FHUD S-5 | FHUD S-5 | FHUD S-5 | FHUD S-5 | FHUD S-5 | FHUD S-5 |
| Volume ratio of hydrogen to oil | 500 | 500 | 450 | 350 | 400 | 450 |
| Total volume space velocity, h-1 | 4.3 | 4.3 | 2.0 | 4.8 | 3.8 | 3.8 |
| Inlet temperature of low DEG C | 342 | 360 | 320 | 340 | 335 | 335 |
| Average reaction temperature,. degree.C | 360 | 385 | 340 | 350 | 353 | 353 |
| Hydrogen sulfide increment in the first hydrogenation reaction zone (first addition)The difference between the contents of the outlet of the hydrogen reaction zone and the inlet of the first hydrogenation reaction zone) in the total hydrogen sulfide increase value (second hydrogenation reaction) The difference in the contents of the outlet of the reaction zone and the inlet of the first hydrogenation reaction zone) based on the ratio of the contents of the outlet of the reaction zone and the inlet of the first hydrogenation reaction zone, based on the ratio of the outlet of the reaction zone to the inlet of the first hydrogenation reaction zone, based on the ratio of the outlet of the ratio of the outlet of the reaction zone to the inlet of the ratio of the outlet of the ratio of the outlet of the ratio of the outlet of the ratio of the inlet of the ratio of the outlet of the ratio of the outlet of the ratio of the inlet of the outlet of the ratio of the inlet of the ratio of the outlet of the ratio of the inlet of the outlet of the reaction zone to the inlet of the ratio of the inlet of the ratio of the outlet of the inlet of the reaction zone to the inlet of the outlet of the inlet of the ratio of the reaction zone to the inlet of the reaction zone to the | 50.1 | 48.6 | 50.1 | 58.7 | 58.7 | 58.7 |
| Diesel oil product | ||||||
| Density, g/cm3 | 0.84 0 | 0.83 8 | 0.83 4 | 0.84 2 | 0.84 5 | 0.83 9 |
| Sulphur content, μ g/g | 4.1 | 5.6 | 8.0 | 3.5 | 9.3 | 4.3 |
| Cetane number | 48 | 48 | 54 | 52 | 51 | 52 |
| Operating time, Hr | 8000 | 8000 | 8000 | — | — | 8000 |
| A first reaction zone | ||||||
| Hydrofinishing section | ||||||
| Average reaction temperature,. degree.C | 385 | 380 | 368 | — | — | 363 |
| Hydro-upgrading fraction | — | — | — | — | — | 372 |
| Outlet temperature of | 396 | 392 | 390 | — | — | 375 |
| Sulfur content of product liquid, microgram/g | 25 | 400 | 10 | — | — | 25 |
| Second reaction zone | ||||||
| Inlet temperature of low DEG C | 368 | 384 | 323 | — | — | 337 |
| Average reaction temperature,. degree.C | 376 | 396 | 331 | — | — | 344 |
| Outlet temperature | 384 | 408 | 339 | — | — | 351 |
| Diesel oil product | ||||||
| Density, g/cm3 | 0.84 1 | 0.84 3 | 0.83 5 | — | — | 0.83 9 |
| Sulphur content, μ g/g | 6.5 | 20.8 | 7.3 | — | — | 4.5 |
| Cetane number | 48 | 47 | 54 | — | — | 52 |
The embodiment shows that the diesel raw material can realize the purpose of producing high-quality clean diesel products for a long period at lower reaction temperature by the hydrogenation process of the technology.
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 (18)
1. A hydrogenation process for producing ultra-low sulfur diesel oil with low energy consumption and long period is characterized in that: the method comprises the following steps:
(a) fractionating the diesel raw oil to obtain a light fraction and a heavy fraction, wherein the weight ratio of the light fraction to the heavy fraction is 35: 65-55: 45;
(b) carrying out hydrodesulfurization reaction on the heavy fraction diesel raw oil obtained in the step (a) in a first hydrogenation reaction zone under the action of a hydrodesulfurization catalyst, wherein the sulfur content in a liquid stream flowing out of the first hydrogenation reaction zone is not more than 35 microgram/g;
(c) carrying out hydrodesulfurization reaction on the material flow of the first hydrogenation reaction zone obtained in the step (b) and the light fraction diesel raw oil obtained in the step (a) in a second hydrogenation reaction zone under the action of a hydrodesulfurization catalyst to obtain material flow of the second hydrogenation reaction zone;
(d) and (c) separating the material flow of the second hydrogenation reaction zone obtained in the step (c) into a gas phase and a liquid phase, recycling the obtained hydrogen-rich gas directly or after removing hydrogen sulfide, and separating the obtained liquid phase to obtain gas, naphtha and diesel oil products.
2. The process according to claim 1, characterized in that: the sulfur content in the liquid material flow flowing out of the first hydrogenation reaction area is 8-30 mug/g.
3. The process according to claim 1, characterized in that: one of the following schemes is adopted:
1) the heavy fraction firstly passes through an upper part hydrofining catalyst bed layer in a first hydrogenation reaction zone, one part of generated material flow enters a gas-liquid separator to be separated into a gas phase and a liquid phase, the other part of generated material flow and the liquid phase continuously pass through a lower part of hydrofining catalyst bed layer, and the generated material flow, the light fraction and the gas phase are mixed and then continuously hydrofined in a second hydrogenation reaction zone;
2) firstly, carrying out hydrofining and hydro-upgrading on heavy fractions in a first hydrogenation reaction zone through a hydrofining catalyst bed and a hydro-upgrading catalyst bed, mixing the generated material flow and light fractions, and then continuously carrying out hydrofining in a second hydrogenation reaction zone through the hydrofining catalyst bed;
3) the heavy fraction firstly passes through the upper part of a hydrofining catalyst bed layer in the first hydrogenation reaction zone, one part of generated material flow enters a gas-liquid separator to be separated into a gas phase and a liquid phase, the other part of generated material flow and the liquid phase continuously pass through the lower part of the hydrofining catalyst bed layer and the hydrofining catalyst bed layer to be subjected to hydrofining and hydro-upgrading, and the generated material flow, the light fraction and the gas phase are mixed and then continuously pass through the hydrofining catalyst bed layer in the second hydrogenation reaction zone to be subjected to hydrofining.
4. The process according to claim 1, characterized in that: the proportion of the hydrogen sulfide added value of the first hydrogenation reaction zone in the total hydrogen sulfide added value is 45-70%.
5. The process according to claim 1, characterized in that: the diesel raw oil is one or more of straight-run diesel, catalytic diesel, coking diesel, thermal cracking diesel, visbreaking diesel, synthetic diesel, coal tar diesel fraction, coal direct liquefaction diesel and shale oil diesel.
6. The process according to claim 1, characterized in that: the amount of sulfur in heavy fraction obtained by fractionating the diesel raw material accounts for 45-70% of the total sulfur in the diesel raw material.
7. The process according to claim 1, characterized in that: the first hydrogenation reaction zone is a reactor or a plurality of reactors, and a catalyst bed layer or a plurality of catalyst bed layers are arranged in the reactor.
8. The process according to claim 1, characterized in that: the operating conditions of the first hydrogenation reaction zone are as follows: the reaction pressure is 3.0-13.0 MPa, and the volume space velocity of the heavy fraction diesel oil raw material oil is 0.2h-1~10.0h-1The average reaction temperature is 220-440 ℃, and the volume ratio of hydrogen to oil is 200: 1-1500: 1.
9. The process according to claim 8, characterized in that: the operating conditions were: the reaction pressure is 4.0-12.0 MPa, and the volume space velocity of the heavy fraction raw oil is 0.3h-1~8.0h-1The average reaction temperature is 230-433 ℃, and the volume ratio of hydrogen to oil is 300: 1-1200: 1.
10. The process according to claim 3, characterized in that: the hydro-upgrading catalyst carrier used in the first hydrogenation reaction zone contains alumina and a molecular sieve; based on the weight of the catalyst, the content of the VIB group metal is 10-35 wt% calculated by oxide, the content of the VIII group metal is 3-15 wt% calculated by oxide, the content of the molecular sieve is 5-40 wt%, and the content of the alumina is 10-80 wt%; its specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g.
11. The process according to claim 3, characterized in that: the first hydrogenation reaction zone hydrogenation modification process conditions are as follows: the reaction pressure is 3.0MPa to 13.0MPa, the reaction temperature is 300 ℃ to 433 ℃, and the liquid hourly volume space velocity is 0.2h-1～15.0h-1The volume ratio of the hydrogen to the oil is 100: 1-2000: 1.
12. The process according to claim 1, characterized in that: the second hydrogenation reaction zone is a reactor or a plurality of reactors, and a catalyst bed layer or a plurality of catalyst bed layers are arranged in the reactor.
13. The process according to claim 1, characterized in that: the operating conditions of the second hydrogenation reaction zone are as follows: the reaction pressure is 3.0-13.0 MPa, and the total volume airspeed of the light fraction and heavy fraction diesel oil raw oil is 0.2h-1~20.0h-1The average reaction temperature is 190-437 ℃, and the volume ratio of the total hydrogen to the oil is 150: 1-1200: 1.
14. The process according to claim 13, characterized in that: the operation conditions are that the reaction pressure is 4.0MPa to 12.0MPa, and the total volume airspeed of the diesel raw oil is 0.3h-1~16.0h-1The average reaction temperature is 200-430 ℃, and the volume ratio of the total hydrogen to the oil is 200: 1-1000: 1.
15. The process according to claim 1, characterized in that: the average reaction temperature of the first hydrogenation reaction zone is 3-40 ℃ higher than that of the second hydrogenation reaction zone.
16. The process according to claim 1, characterized in that: the hydrogenation active component in the hydrodesulfurization catalyst at least contains Co, and the weight content of the Co is 5-70% by weight calculated by oxide.
17. The process according to claim 1, characterized in that: controlling the volume ratio of the Mo-Ni type hydrogenation catalyst to the Co-containing type hydrogenation catalyst in the first hydrogenation reaction zone to be 5: 95-20: 80, and using the Co-containing type hydrogenation catalyst in the second hydrogenation reaction zone.
18. The process according to claim 3, characterized in that: the volume proportion of the extracted partial material flow in terms of gas phase accounts for 10-50 v% of the raw material gas phase at the inlet of the reaction zone.
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| CN102041071A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Hydrogenation technology for diesel |
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Effective date of registration: 20231023 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. |