CN114437788B - Fischer-Tropsch synthetic oil processing technology - Google Patents
Fischer-Tropsch synthetic oil processing technology Download PDFInfo
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- CN114437788B CN114437788B CN202011116112.5A CN202011116112A CN114437788B CN 114437788 B CN114437788 B CN 114437788B CN 202011116112 A CN202011116112 A CN 202011116112A CN 114437788 B CN114437788 B CN 114437788B
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- 238000005516 engineering process Methods 0.000 title claims abstract description 7
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 143
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000002283 diesel fuel Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 238000005194 fractionation Methods 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 94
- 239000002808 molecular sieve Substances 0.000 claims description 21
- 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 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000005336 cracking Methods 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000011959 amorphous silica alumina Substances 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 abstract description 9
- 238000009833 condensation Methods 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000001993 wax Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
Landscapes
- 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 Fischer-Tropsch synthetic oil processing technology, which comprises the following steps: (1) The Fischer-Tropsch synthesis oil enters a hydrogenation pretreatment reactor for reaction; (2) Feeding the material flow obtained in the step (1) into a hydrocracking reactor, wherein a hydrocracking reaction zone and a hydrocracking product fractionation zone are arranged in the hydrocracking reactor, at least two hydrocracking catalyst beds are arranged in the hydrocracking reaction zone, and the material flow obtained after the hydrofining reaction in the step (1) enters the hydrocracking reactor from the bed layers of the hydrocracking catalyst to carry out hydrocracking reaction; (3) And (3) obtaining hydrocracking unconverted oil at the bottom of the hydrocracking reactor in the step (2), obtaining diesel oil at the side line of a fractionation zone of a hydrocracking product, and obtaining hydrogen and naphtha after fractionating the top material flow of the hydrocracking reactor. The method improves the condensation point of the full-fraction boiling support synthetic oil for producing diesel oil by hydrocracking and improves the selectivity of the diesel oil.
Description
Technical Field
The invention relates to a Fischer-Tropsch synthetic oil processing technology, in particular to a technology for producing diesel oil by hydrocracking Fischer-Tropsch synthetic oil.
Background
The petroleum resources of China are deficient, the external dependence of crude oil exceeds 70%, the coal resources of China are relatively rich, and besides the coal resources are used for power generation, heating and the like, in recent years, the coal chemical industry is rapidly developed in China.
Among them, the Fischer-Tropsch synthesis process has been widely developed in China because of the capability of converting coal into Fischer-Tropsch synthetic oil. The Fischer-Tropsch synthesis oil hydrocarbon structure composition is a very good hydrocarbon resource with paraffin as the main component. High cetane number, low sulfur content diesel components and/or high grade lubricating oils can be produced by hydrocracking or hydroisomerization.
Chinese patent CN200510068181.2 discloses a method for producing high cetane number diesel oil by hydrotreating fischer-tropsch synthetic oil. The Fischer-Tropsch synthesis oil full fraction, hydrogen and a hydrofining catalyst are contacted, a hydrofining reaction stream and a hydrocracking reaction stream are mixed and separated to obtain a middle distillate oil product, naphtha and tail oil, and the tail oil is mixed with the hydrogen and then is circulated to an isomerism cracking reactor to be contacted with the hydroisomerization cracking catalyst. The method can reduce the influence of the water content generated in the reaction process of the Fischer-Tropsch synthesis oil on the hydrocracking catalyst through the reverse hydrogenation process design, but the intermediate of the diesel fraction generated in the reaction process in the cracking reactor cannot timely leave the reactor, so that the reaction is excessive, the selectivity of the diesel is poor, and in addition, the low-temperature fluidity of the diesel fraction originally existing in the raw material of the Fischer-Tropsch synthesis oil is poor because the diesel fraction is not subjected to the pour point depressing treatment of the hydrocracking reactor.
Chinese patent CN201610365749.5 discloses a processing method of boiling synthetic oil: (1) Mixing Fischer-Tropsch synthesis produced oil and hydrogen to enter a hydrocracking reactor, and reacting under the action of a hydrocracking catalyst, wherein the average pore diameter of the hydrocracking catalyst is in a decreasing trend along the flow direction of a material flow; (2) Separating the hydrogenation effluent in the step (1) into a gas phase and a liquid phase, recycling the gas phase, and feeding the liquid phase into a fractionating tower; (3) Fractionating in a fractionating tower to obtain naphtha, aviation kerosene, diesel oil and tail oil; the tail oil is recycled to the hydrocracking reactor. The method can greatly improve the light oil yield and reduce the freezing point of aviation kerosene and the freezing point of diesel oil by the gradient design of the average pore diameter of the hydrocracking catalyst along the cracking reactor, but the selectivity of the diesel oil is poor.
Chinese patent CN201610617631.7 discloses a process for producing diesel oil and lubricating oil products by hydrocracking of fischer-tropsch synthetic oil, which comprises contacting fischer-tropsch oil with a first hydrocracking catalyst at a hydrogen partial pressure of 6-8MPa, a temperature of 300-390 ℃, a volume space velocity of 0.8-1.2h-1, and a hydrogen oil volume ratio of (600-800): 1, and then the product is cut to obtain a fraction at 350-500 ℃, and then the fraction at 350-500 ℃ is contacted with a second hydrocracking catalyst, wherein the volume space velocity is 0.8-1.2h < -1 >, the hydrogen partial pressure is 6-8MPa, the temperature is 300-390 ℃, and the hydrogen oil volume ratio is (600-800): 1 to obtain the diesel oil with the temperature of 150-370 ℃ and the lubricating oil component with the temperature of more than 370 ℃. The method also has the problem of poor selectivity of diesel oil.
How to improve the processing efficiency of the full-fraction boiling support synthetic oil and give consideration to the diesel oil condensation point and the diesel oil selectivity in the processing process of the full-fraction boiling support synthetic oil are problems which need to be solved by scientific researchers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Fischer-Tropsch synthetic oil processing technology, which can improve the condensation point of the full-fraction boiling-Torr synthetic oil for hydrocracking to produce diesel oil and improve the selectivity of the diesel oil.
A fischer-tropsch synthesis oil processing process, comprising the steps of:
(1) The Fischer-Tropsch synthetic oil enters a hydrogenation pretreatment reactor to carry out hydrofining reaction under the action of a hydrofining catalyst;
(2) Feeding the material flow after the hydrofining reaction in the step (1) into a hydrocracking reactor, wherein a hydrocracking reaction zone and a hydrocracking product fractionation zone are arranged in the hydrocracking reactor, at least two hydrocracking catalyst beds are arranged in the hydrocracking reaction zone, and feeding the material flow after the hydrofining reaction in the step (1) into the hydrocracking reactor from the bed layers of the hydrocracking catalyst to carry out hydrocracking reaction;
(3) And (2) obtaining hydrocracking unconverted oil at the bottom of the hydrocracking reactor, wherein part or all of the hydrocracking unconverted oil can be returned to the hydrocracking reactor, diesel oil is obtained from the side line of the fractionating zone of the hydrocracking product, hydrogen and naphtha are obtained from the top material flow of the hydrocracking reactor after fractionation, the hydrogen is recycled, and optionally, the naphtha part is recycled to the fractionating zone of the hydrocracking reactor.
The properties of the Fischer-Tropsch oil in step (1) of the process of the invention are as follows: the distillate with the distillation range of 130-750 ℃ and the distillation range of 130-380 ℃ accounts for not less than 20 percent, preferably 25-60 percent, and more preferably 30-50 percent of the mass of the Fischer-Tropsch synthetic oil; the mass content of the linear alkane is 85% -98%, preferably 88% -98%, further preferably 92% -98%, the mass content of the alkene is 1% -15%, preferably 3% -12%, further preferably 5% -10%, and the mass content of the oxygen is 0.1% -5%, preferably 0.5% -3%.
In the method of the invention, the hydrofining reaction conditions in the step (1) are as follows: the reaction pressure is 1.0-5.0MPa, the reaction temperature is 180-320 ℃, and the liquid hourly space velocity calculated by the Fischer-Tropsch synthetic oil in the step (1) is 1.0-10.0h -1 Hydrogen oil volume ratio 50: 1-500: 1.
in the method, the hydrofining catalyst in the step (1) takes VIB group and/or VIII group metals as active components and alumina or silicon-containing alumina as a carrier. The group VIB metal is typically Mo and/or W and the group VIII metal is typically Co and/or Ni. Based on the weight of the catalyst, the content of the metal of the VIB group is 8-28 wt% based on the oxide, and the content of the metal of the VIII group is 2-15 wt% based on the oxide.
According to the method, in the step (2), two hydrocracking catalyst beds are arranged in a hydrocracking reaction zone in the hydrocracking reactor, fischer-Tropsch synthesis oil enters the hydrocracking reactor from the middle of the hydrocracking catalyst beds, a liquid phase material flow enters a lower-filled hydrocracking catalyst bed for reaction, and a gas phase material flow enters an upper-filled hydrocracking catalyst bed for reaction.
The hydrocracking reaction operating conditions in step (2) of the process of the present invention are as follows: the reaction pressure is 1MPa to 5MPa, preferably 1MPa to 4MPa, more preferably 1.5MPa to 3.5MPa, and particularly can be 2MPa, 2.5MPa or 3MPa; the reaction temperature is 260-380 ℃, preferably 280-360 ℃; the liquid hourly space velocity is 0.2h -1 -4h -1 Preferably 0.5h -1 -1-3.0h -1 The hydrogen-oil ratio is 50: 1-500: 1, a step of; the liquid hourly space velocity is based on the total volume of the hydrocracking catalyst loaded in the hydrocracking reactor.
In the method of the present invention, the reaction temperature of the hydrocracking catalyst bed filled in the upper part of the hydrocracking reaction zone in the step (2) is 5 ℃ to 60 ℃, preferably 10 ℃ to 50 ℃ and more preferably 15 ℃ to 30 ℃ lower than the reaction temperature of the catalyst bed filled in the lower part of the hydrocracking reaction zone.
The hydrocracking catalyst in step (2) of the process of the present invention may be prepared using commercially available products or according to the prior art. The hydrocracking catalyst generally comprises a cracking component and a metal component, wherein the cracking component can use one or more molecular sieves in Y, beita, SAPO, ZSM and other types of molecular sieves, the metal component is VIB group and/or VIII group metal, and the hydrocracking catalyst can comprise components such as alumina, amorphous silicon-aluminum and the like besides the metal component and the cracking component.
In the process of the present invention, the lower-packed hydrocracking catalyst and the upper-packed hydrocracking catalyst in step (2) may be the same or different, preferably different, and more preferably the weight content of the acidic component of the lower-packed hydrocracking catalyst is 1 to 15%, preferably 4 to 12% higher than that of the upper-packed hydrocracking catalyst, and the differences include the same components but different contents, for example, the lower-packed hydrocracking catalyst and the upper-packed hydrocracking catalyst each employ a beita molecular sieve or a y+beita molecular sieve as the acidic component.
According to the method disclosed by the invention, in the step (2), the hydrocracking catalyst filled in the lower part of the hydrocracking reaction zone takes a beita molecular sieve or a Y+beita molecular sieve as an acidic component, and the hydrocracking catalyst filled in the upper part of the hydrocracking reaction zone takes the beita, SAPO-11 and/or SAPO-34 molecular sieves as the acidic components.
In one or more embodiments of the invention, the hydrocracking catalyst in the lower portion of the hydrocracking reactor comprises MoO by weight 3 Or WO 3 15-30%, 2-10% of NiO, 0-15% of modified Y-type molecular sieve, and preferably 0-20% of modified beita-type molecular sieve; 50-80% of amorphous silicon aluminum and/or aluminum oxide. Preferably contains MoO 3 Or WO 3 18-25%, 3-8% of NiO and 8-18% of modified beita molecular sieve; 55-75% of amorphous silicon aluminum and/or aluminum oxide;
in one or more embodiments of the invention, the hydrocracking catalyst in the upper portion of the hydrocracking reactor comprises MoO by weight 3 Or WO 3 15-30%, niO 2-10%, modified beita molecular sieve 0-15%; 0 to 8 percent of SAPO-11, 0 to 8 percent of SAPO-34 and 55 to 80 percent of amorphous silicon aluminum and/or aluminum oxide. Preferably comprisesMoO 3 Or WO 3 18-28%, 3-8% of NiO, 0-10% of modified beita molecular sieve, 0-6% of SAPO-11 and 0-6% of SAPO-34; 60 to 75 percent of amorphous silicon aluminum and/or aluminum oxide.
According to the method, the recycle ratio of the hydrocracked unconverted oil in the step (3) is full cycle-1: 10, preferably 1:1 to 1:5 (recycle to reactor to external swing mass ratio).
The synthetic oil with boiling support has wide range of fractions and is a mixed hydrocarbon containing naphtha, diesel oil and wax oil fractions. In the prior art, the process of producing diesel oil fraction by hydrocracking the boiling bracket synthetic oil can be divided into a process of producing diesel oil fraction by full fraction hydrocracking or a process of producing diesel oil by hydrocracking light fraction and heavy fraction firstly by fractionation. When the full-fraction boiling-support synthetic oil hydrocracking process is adopted, the diesel oil and the wax oil fraction of the boiling-support synthetic oil are subjected to hydrocracking reaction together, on one hand, part of the wax oil is cracked and converted into diesel oil fraction, and on the other hand, the diesel oil fraction formed by the wax oil conversion and the original diesel oil fraction in the boiling-support synthetic oil raw material are subjected to cracking reaction, so that the selectivity of the diesel oil is reduced; when the process of producing diesel oil by first fractionating light fraction, heavy fraction and hydrocracking heavy fraction is adopted, the diesel oil fraction originally contained in the lower boiling bracket raw material of the process is not subjected to hydrocracking treatment, the congealing point is higher, the congealing point of the mixed diesel oil obtained by blending the diesel oil fraction contained in the final boiling bracket synthetic oil raw material with hydrocracking diesel oil is higher, and in the process of producing diesel oil by hydrocracking heavy fraction, more secondary cracking occurs, and the produced diesel oil is further cracked, so that the selectivity of the diesel oil fraction is reduced.
The process adopts a mode that full-fraction Fischer-Tropsch synthetic oil is fed from the middle part of a reactor, diesel oil fraction and wax oil fraction in the full-fraction Fischer-Tropsch synthetic oil are processed in the upper part and the lower part of the reactor respectively, the upper part of the catalyst bed is used for processing diesel oil obtained by hydrocracking the diesel oil fraction and the wax oil fraction in the Fischer-Tropsch synthetic oil raw material, so that the diesel oil is further isomerized and reduced in condensation, the lower part of the catalyst bed is used for processing the wax oil fraction in the Fischer-Tropsch synthetic oil raw material to partially convert the diesel oil fraction, and meanwhile, a proper catalyst system and operation conditions are respectively designed for the targets of diesel oil fraction isomerization and wax oil fraction hydrocracking, so that the original diesel oil fraction isomerization and condensation point reduction requirements in the full-fraction Fischer-Tropsch synthetic oil are ensured; on the other hand, the transitional cracking of the diesel oil fraction in the full-fraction boiling support synthetic oil and the cracked diesel oil fraction obtained by hydrocracking wax oil is reduced, and the diesel oil selectivity is ensured.
Detailed Description
The invention relates to a Fischer-Tropsch synthetic oil hydrocracking method, which comprises the following specific processes: the Fischer-Tropsch synthesis oil raw material and hydrogen are mixed and enter a hydrogenation pretreatment reactor, reaction generated oil enters a hydrocracking reactor from the middle part and reacts with hydrogen entering from the lower part of the reactor in a reverse contact way in the reactor at the lower part of the cracking reactor, diesel oil and naphtha generated by the reaction continue to flow upwards to react in the reaction zone at the upper part of the reactor, the reaction product enters a fractionation zone upwards, the naphtha and the hydrogen continue to flow upwards through a fractionated diesel oil product extraction device and enter a reflux tank to separate the hydrogen and the naphtha, the hydrogen oil flows out from the top of the reflux tank for recycling after separation, and part of the naphtha flows back to the hydrocracking reactor and the other part of the naphtha is discharged out of the device. And part of unconverted oil in the reaction zone at the lower part of the hydrocracking reactor flows out of the device, and the other part of unconverted oil is recycled and mixed with oil generated by the pretreatment reactor and enters the hydrocracking reactor for continuous reaction.
The operation and effect of the process of the present invention will be further discussed below with reference to examples, which are not to be construed as limiting the process of the present invention. Diesel fraction selectivity = diesel fraction yield/(100-tail fraction yield) ×100% in the following examples and comparative examples
Example 1
Table 1 shows the properties of the raw oil, table 2 shows the composition of the catalyst, and table 3 shows the operating conditions and the reaction effect.
TABLE 1
| Density, g/cm 3 | 0.8042 |
| Distillation range, DEG C | |
| IBP | 165 |
| 10％ | 308 |
| 30％ | 362 |
| 50％ | 462 |
| 70％ | 552 |
| 90％ | 575 |
| FBP | 705 |
| Olefin content, wt% | 6％ |
| Oxygen content, wt% | 1％ |
TABLE 2
TABLE 3 Table 3
Example 2
Table 4 shows the properties of the raw oil, table 5 shows the composition of the catalyst, and Table 6 shows the operating conditions and the reaction effect.
TABLE 4 Table 4
TABLE 5 example 2 catalyst
TABLE 6
Example 3
Table 7 shows the properties of the raw oil, table 8 shows the composition of the catalyst, and Table 9 shows the operating conditions and the reaction effect.
TABLE 7
TABLE 8
TABLE 9
Example 4
Table 10 shows the properties of the raw oil, table 11 shows the composition of the catalyst, and Table 12 shows the operating conditions and the reaction effect. Table 10
TABLE 11
Table 12
Example 5
Table 13 shows the properties of the raw oil, table 14 shows the composition of the catalyst, and table 15 shows the operating conditions and the reaction effect. TABLE 13
| Density, g/cm 3 | 0.7855 |
| Distillation range, DEG C | |
| IBP | 148 |
| 10％ | 268 |
| 30％ | 344 |
| 50％ | 375 |
| 70％ | 470 |
| 90％ | 540 |
| FBP | 600 |
| Olefin content, wt% | 10％ |
| Oxygen content, wt% | 1％ |
TABLE 14
TABLE 15
Example 6
Table 16 shows the properties of the raw oil, table 17 shows the composition of the catalyst, and Table 18 shows the operating conditions and the reaction effect.
Table 16
| Density, g/cm 3 | 0.7855 |
| Distillation range, DEG C | |
| IBP | 148 |
| 10％ | 268 |
| 30％ | 344 |
| 50％ | 375 |
| 70％ | 470 |
| 90％ | 540 |
| FBP | 600 |
| Olefin content, wt% | 10％ |
| Oxygen content, wt% | 1％ |
TABLE 17
TABLE 18
| Pretreatment reactor | Hydrocracking reactor upper part | Hydrocracking reactor lower part | |
| Reaction temperature, DEG C | 240 | 326 | 345 |
| Reaction pressure, MPa | 2.0 | 4.5 | 4.5 |
| Hydrogen to oil volume ratio | 200 | 310 | 200 |
| Volume space velocity, h -1 | 1.0 | 2.0 | 2.5 |
| Tail oil circulation ratio | 1:2 | ||
| Temperature of the top of the tower, DEG C | 230 | ||
| Overhead pressure, MPa | 4.3 | ||
| Reflux ratio | 3.0 | ||
| Conversion X%, percent | 63.9 |
Example 7
Table 19 shows the properties of the raw oil, table 20 shows the composition of the catalyst, and Table 21 shows the operating conditions and the reaction effect.
TABLE 19
| Density, g/cm 3 | 0.8042 |
| Distillation range, DEG C | |
| IBP | 165 |
| 10％ | 308 |
| 30％ | 362 |
| 50％ | 462 |
| 70％ | 552 |
| 90％ | 575 |
| FBP | 705 |
| Olefin content, wt% | 6％ |
| Oxygen content, wt% | 1％ |
Table 20
Table 21
Example 8
Table 22 shows the properties of the raw oil, table 23 shows the composition of the catalyst, and table 24 shows the operating conditions and the reaction effect.
Table 22
| Density, g/cm 3 | 0.8042 |
| Distillation range, DEG C | |
| IBP | 165 |
| 10％ | 308 |
| 30％ | 362 |
| 50％ | 462 |
| 70％ | 552 |
| 90％ | 575 |
| FBP | 705 |
| Olefin content, wt% | 6％ |
| Oxygen content, wt% | 1％ |
Table 23
Table 24
Table 25 shows the product distributions and quality of examples 1 to 8
Table 25
Continuous meter 25
| Example 5 | Example 6 | Example 7 | Example 8 | |
| Product yield | ||||
| Diesel oil fraction, wt% | 56.1 | 56.0 | 55.2 | 54.3 |
| Condensation point, DEG C | -19 | -22 | -24 | -19 |
| Tail oil fraction, wt% | 33.5 | 36.1 | 37.5 | 38.8 |
| Diesel fraction selectivity,% | 84.3 | 87.6 | 88.3 | 88.7 |
Comparative example 1
By adopting a conventional process flow, fischer-Tropsch synthesis raw oil and hydrogen flow into a refining and cracking reaction, and the generated oil enters a fractionating tower to cut out each component for reaction, wherein table 26 is the raw oil property, 27 is the catalyst composition, and 28 is the operation condition and the reaction effect.
Table 26
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Table 27
| Density, g/cm 3 | Pretreatment catalyst | Hydrocracking reactor |
| Active metal, wt% | ||
| WO3 | 22 | 22 |
| NiO | 4 | 6 |
| Beita molecular sieve, wt% | - | 15 |
| Alumina, wt% | 74 | |
| Alumina + amorphous silica alumina, wt% | - | 57 |
Table 28
Comparative example 2
By adopting a conventional process flow, fischer-Tropsch synthesis raw oil and hydrogen flow into a refining and cracking reaction, and the generated oil enters a fractionating tower to cut out each component for reaction, wherein table 29 shows the raw oil property, 30 shows the catalyst composition, and 31 shows the operation condition and the reaction effect.
Table 29
| Density, g/cm 3 | 0.8042 |
| Distillation range, DEG C | |
| IBP | 165 |
| 10％ | 308 |
| 30％ | 362 |
| 50％ | 462 |
| 70％ | 552 |
| 90％ | 575 |
| FBP | 705 |
| Olefin content, wt% | 6％ |
| Oxygen content, wt% | 1％ |
Table 30
| Density, g/cm3 | Pretreatment catalyst | Hydrocracking reactor |
| Active metal, wt% | ||
| WO3 | 24 | 22 |
| NiO | 4 | 6 |
| Beita molecular sieve, wt% | - | 15 |
| Alumina, wt% | 72 | |
| Alumina + amorphous silica alumina, wt% | - | 57 |
Table 31
| Pretreatment reactor | Hydrocracking reactor | |
| Reaction temperature, DEG C | 300 | 343 |
| Reaction pressure, MPa | 9.0 | 9.0 |
| Hydrogen to oil volume ratio | 300 | 400 |
| Volume space velocity, h-1 | 8.0 | 1.5 |
| Conversion, percent | 58.8 |
Table 32 shows the distribution of the products of comparative examples 1 to 2
Table 32
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Claims (15)
1. A Fischer-Tropsch synthetic oil processing technology is characterized in that: the process comprises the following steps:
(1) The Fischer-Tropsch synthetic oil enters a hydrogenation pretreatment reactor to carry out hydrofining reaction under the action of a hydrofining catalyst;
(2) Feeding the material flow after the hydrofining reaction in the step (1) into a hydrocracking reactor, wherein a hydrocracking reaction zone and a hydrocracking product fractionation zone are arranged in the hydrocracking reactor, at least two hydrocracking catalyst beds are arranged in the hydrocracking reaction zone, and feeding the material flow after the hydrofining reaction in the step (1) into the hydrocracking reactor from the bed layers of the hydrocracking catalyst to carry out hydrocracking reaction; the Fischer-Tropsch synthesis oil enters a hydrocracking reactor from the middle of a hydrocracking catalyst bed layer, a liquid phase material flow enters a lower hydrocracking catalyst bed layer filled in the lower part for reaction, and a gas phase material flow enters an upper hydrocracking catalyst bed layer filled in the upper part for reaction;
the reaction temperature of the hydrocracking catalyst bed layer filled in the upper part of the hydrocracking reaction zone in the step (2) is 5-60 ℃ lower than that of the catalyst bed layer filled in the lower part of the hydrocracking reaction zone; the weight content of the acidic component of the hydrocracking catalyst filled in the lower part is 1-15% higher than that of the hydrocracking catalyst filled in the upper part;
(3) And (2) obtaining hydrocracking unconverted oil at the bottom of the hydrocracking reactor, wherein part or all of the hydrocracking unconverted oil returns to the hydrocracking reactor, diesel oil is obtained from the side line of the fractionating zone of the hydrocracking product, hydrogen and naphtha are obtained from the top of the hydrocracking reactor after the top of the hydrocracking reactor is fractionated, the hydrogen is recycled, and optionally, the naphtha part is recycled to the fractionating zone of the hydrocracking reactor.
2. The process according to claim 1, characterized in that: the properties of the Fischer-Tropsch oil in step (1) are as follows: the distillate with the distillation range of 130-750 ℃ and the mass ratio of 130-380 ℃ in the Fischer-Tropsch synthetic oil is not lower than 20%.
3. The process according to claim 1, characterized in that: the properties of the Fischer-Tropsch oil in step (1) are as follows: the mass content of the linear alkane is 85% -98%, the mass content of the alkene is 1% -15%, and the mass content of the oxygen is 0.1% -5%.
4. The process according to claim 1, characterized in that: the hydrofining reaction conditions described in step (1) are as follows: the reaction pressure is 1.0-5.0MPa, the reaction temperature is 180-320 ℃, and the liquid hourly space velocity calculated by the Fischer-Tropsch synthetic oil in the step (1) is 1.0-10.0h -1 Hydrogen oil volume ratio 50: 1-500: 1.
5. the process according to claim 1, characterized in that: the hydrofining catalyst in the step (1) takes VIB group and/or VIII group metals as active components and alumina or silicon-containing alumina as a carrier.
6. The process according to claim 5, wherein: the VIB group metal is Mo and/or W, the VIII group metal is Co and/or Ni, the weight of the catalyst is taken as the reference, the VIB group metal content is 8-28 wt% of oxide, and the VIII group metal content is 2-15 wt% of oxide.
7. The process according to claim 1, characterized in that: the hydrocracking reaction in step (2) is operated under the following conditions: the reaction pressure is 1MPa-5 MPa; the reaction temperature is 260-380 ℃; the liquid hourly space velocity is 0.2h -1 -4h -1 The hydrogen oil volume ratio is 50: 1-500: 1, a step of; the liquid hourly space velocity is based on the total volume of the hydrocracking catalyst loaded in the hydrocracking reactor.
8. The process according to claim 1, characterized in that: and (2) the reaction temperature of the hydrocracking catalyst bed layer filled in the upper part of the hydrocracking reaction zone is 10-50 ℃ lower than that of the catalyst bed layer filled in the lower part of the hydrocracking reaction zone.
9. The process according to claim 1, characterized in that: and (2) the reaction temperature of the hydrocracking catalyst bed layer filled in the upper part of the hydrocracking reaction zone is 15-30 ℃ lower than that of the catalyst bed layer filled in the lower part of the hydrocracking reaction zone.
10. The process according to claim 1, characterized in that: the hydrocracking catalyst in the step (2) contains a cracking component and a metal component, wherein the cracking component is one or more of Y, beta, SAPO and ZSM molecular sieves, the metal component is VIB group and/or VIII group metal, and the hydrocracking catalyst comprises alumina and amorphous silica-alumina components besides the metal component and the cracking component.
11. The process according to claim 1, characterized in that: the weight content of the acidic component of the hydrocracking catalyst filled in the lower part is 4-12% higher than that of the hydrocracking catalyst filled in the upper part.
12. The process according to claim 1, characterized in that: the hydrocracking catalyst filled in the lower part of the hydrocracking reaction zone in the step (2) takes a beta molecular sieve or a Y+beta molecular sieve as an acidic component, and the hydrocracking catalyst filled in the upper part of the hydrocracking reaction zone takes beta, SAPO-11 and/or SAPO-34 molecular sieves as acidic components.
13. The process according to claim 12, wherein: the hydrocracking catalyst at the lower part of the hydrocracking reactor in the step (2) contains MoO by weight 3 Or WO 3 15-30%, 2-10% of NiO, 0-15% of modified Y-type molecular sieve and 0-20% of modified beta-type molecular sieve; 50-80% of amorphous silicon aluminum and/or aluminum oxide.
14. The process according to claim 12, wherein: the hydrocracking catalyst at the upper part of the hydrocracking reactor in the step (2) contains MoO by weight 3 Or WO 3 15-30%, niO 2-10%, modified beta molecular sieve 0-15%; 0-8% of SAPO-11, 0-8% of SAPO-34 and 55-80% of amorphous silicon aluminum and/or aluminum oxide.
15. The process according to claim 12, wherein: in the step (3), the cycle ratio of the hydrocracked unconverted oil is full cycle-1: 10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104611056A (en) * | 2015-02-11 | 2015-05-13 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreatment method of low-temperature Fischer-Tropsch synthesis product |
| CN106350110A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Method for producing middle distillate oil from Fischer-Tropsch synthetic oil |
| CN109988623A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible inverted sequence hydrocracking process |
| CN109988606A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible inverted sequence hydrocracking process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611056A (en) * | 2015-02-11 | 2015-05-13 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreatment method of low-temperature Fischer-Tropsch synthesis product |
| CN106350110A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Method for producing middle distillate oil from Fischer-Tropsch synthetic oil |
| CN109988623A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible inverted sequence hydrocracking process |
| CN109988606A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of flexible inverted sequence hydrocracking process |
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