CN109504435A - Method for increasing yield of aviation kerosene through hydrocracking - Google Patents
Method for increasing yield of aviation kerosene through hydrocracking Download PDFInfo
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- CN109504435A CN109504435A CN201710833124.1A CN201710833124A CN109504435A CN 109504435 A CN109504435 A CN 109504435A CN 201710833124 A CN201710833124 A CN 201710833124A CN 109504435 A CN109504435 A CN 109504435A
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- hydrocracking
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- aviation kerosene
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- oil
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 73
- 239000003350 kerosene Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000002283 diesel fuel Substances 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 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 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 7
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 239000000779 smoke Substances 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 35
- 150000002431 hydrogen Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 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
- 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
- C10G67/14—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 including at least two different refining steps in the absence of hydrogen
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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 method for producing aviation kerosene in a high yield by hydrocracking, which comprises the following steps: the method comprises the following steps that (1) raw oil S1 and hydrogen are subjected to hydrofining through a first reactor and then sequentially enter a high-pressure separator and a low-pressure separator, and naphtha and aviation kerosene fractions are cut from liquid-phase material flow of the low-pressure separator through a fractionating tower; and the gas phase material flow of the S2 high-pressure separator passes through a recycle hydrogen compressor and then is mixed with the bottom material of the fractionating tower to enter a second reactor for hydrocracking reaction, and then the reaction effluent returns to the first reactor. Wherein the first reactor and the second reactor are respectively filled with a hydrotreating catalyst and a hydrocracking catalyst or a combination agent thereof. The method of the invention produces the aviation kerosene with low content of aromatic hydrocarbon and high smoke point under medium pressure, has the characteristics of low investment, low operation cost, simple operation and the like, and can produce naphtha as the ethylene raw material.
Description
Technical Field
The invention belongs to a method for hydrocracking to produce aviation kerosene in high yield, which adopts Y, Beta composite or mixed molecular sieve with good cracking and ring-opening performance as an acid component of a hydrocracking catalyst, and carries out aviation kerosene refining after hydrocracking, thereby reducing aromatic hydrocarbon in aviation kerosene fraction and improving product quality, and meanwhile, a fractionating tower is arranged between the hydrofining and the hydrocracking, thereby avoiding excessive cracking and improving aviation kerosene yield.
Background
The hydrocracking technology is used as an important processing means for integrating heavy oil lightening, inferior oil quality modification and refining, and has the advantages of flexible production scheme, strong raw material adaptability, high target product selectivity, good quality, high tail oil added value and the like. In recent years, the diesel-gasoline ratio is continuously reduced, the demand of diesel oil is slowly increased, and the self-sufficient rate of aviation kerosene, chemical engineering and aromatic hydrocarbon raw materials is seriously insufficient. Therefore, hydrocracking technology is shifting from the medium oil type to the aviation kerosene or chemical feedstock type. Compared with the traditional high-pressure hydrocracking, the medium-pressure hydrocracking has the advantages of low investment, low operation cost and the like. However, when the process is operated at medium pressure, the quality of the middle distillate product is slightly poorer than that of the high-pressure operation, particularly the aviation kerosene fraction has high aromatic hydrocarbon content and low smoke point, and needs to be further hydrotreated or blended with other products. How to solve the problem that the technology urgently needs to solve when a medium-pressure and low-pressure hydrocracking unit produces qualified aviation kerosene products.
CN98121079.1 discloses a medium pressure hydrocracking process capable of producing qualified aviation kerosene products. The raw oil is subjected to hydrocracking reaction, gas-liquid two phases are subjected to high-resolution separation, and a gas-phase product is used as recycle hydrogen and circulated to a hydrocracking unit; and the liquid phase product enters a fractionating tower to separate naphtha, aviation kerosene, diesel oil and tail oil, one part of aviation kerosene fraction enters an aviation kerosene hydrogenation saturation unit to be subjected to aromatic saturation, and gas serving as make-up hydrogen continues to enter a hydrocracking unit.
CN200410068935.X discloses a medium-pressure hydrocracking method for producing jet fuel, wherein raw oil and hydrogen are mixed and firstly subjected to hydrotreating, a gas-phase material flow of a hydrotreating effluent subjected to thermal high-pressure separation directly enters a second hydrotreating reactor for aromatic saturation, and a liquid-phase material flow of a thermal high-pressure separator is subjected to pressure reduction and then sequentially enters a thermal low-pressure separator, a cold low-pressure separator and a fractionating tower; the effluent of the second hydrotreating reactor is subjected to cold high-pressure separation to obtain a liquid phase material flow and a gas phase material flow, wherein the gas phase material flow is recycled, and the liquid phase material flow enters a cold low-pressure separator and a fractionating tower in sequence after being subjected to pressure reduction; and separating the liquid phase material flow in the fractionating tower to obtain naphtha fraction, jet fuel fraction, diesel oil fraction and tail oil.
Heavy wax oil and catalytic diesel oil are not suitable for being used as raw materials for producing aviation kerosene by medium-pressure hydrocracking due to high aromatic hydrocarbon content. After hydrorefining and hydrocracking light wax oil, straight-run diesel oil or their mixed material, the aviation kerosene fraction is further treated and aromatic hydrocarbon is saturated, so that the aviation kerosene standard requirements can be met. The hydrocracking and productive aviation kerosene technology starts from two aspects of catalyst and process, the active component of the hydrocracking catalyst selects an acidic carrier with cracking and ring-opening functions, and the hydrocracking degree can be controlled on the process to produce aviation kerosene to the maximum extent while the selectivity of the catalyst is improved. According to the invention, a fractionating tower is arranged between a first reactor and a second reactor, the tail oil fraction after naphtha and aviation kerosene fraction are fractionated is subjected to hydrocracking, the hydrocracked product enters the first reactor again for aromatic saturation, and then enters the fractionating tower for fractionating the naphtha and aviation kerosene fraction. Wherein the hydrocracking catalyst has Y, Beta composite or mixed molecular sieve with good cracking and ring-opening performance as an acidic component. The yield of the aviation kerosene is improved from the process and the catalyst, and the aviation kerosene quality is improved.
Disclosure of Invention
The invention aims to realize that light wax oil and straight-run diesel oil are used as raw materials in a medium-pressure range by reasonably adjusting a process flow on the basis of the prior art, so that aviation kerosene can be produced to the maximum extent, and meanwhile, naphtha and tail oil can be used as ethylene raw materials.
Therefore, the invention provides a method for hydrocracking aviation kerosene with high yield, which comprises the following steps:
the method comprises the following steps that (1) raw oil and hydrogen of S1 are subjected to hydrofining (desulfurization and denitrification and aromatic saturation) through a first reactor and then sequentially enter a high-pressure separator and a low-pressure separator, and liquid-phase material flow of the low-pressure separator is subjected to fractionation by a fractionating tower to obtain naphtha fraction and aviation kerosene fraction;
the gas phase material flow of the S2 high-pressure separator passes through a recycle hydrogen compressor and then is mixed with the bottom material of the fractionating tower to enter a second reactor for hydrocracking reaction, and then the reaction effluent returns to the first reactor;
the catalyst filled in the first reactor and the second reactor is respectively selected from at least one of hydrotreating catalyst and hydrocracking catalyst;
the hydrotreating catalyst comprises 1-10 wt% of NiO and 15-30 wt% of MoO31-5 wt% of F, 1-3 wt% of B and the balance of a carrier, wherein the carrier is alumina or amorphous silicon-aluminum;
the hydrocracking catalyst comprises 1-10 wt% of NiO and 10-25 wt% of WO3And the balance of the carrier, wherein the carrier consists of 20-60 wt% of a composite molecular sieve, 40-80 wt% of alumina and 0-50 wt% of amorphous silicon-aluminum, and the composite molecular sieve is formed by compounding or mixing a Beta molecular sieve and a Y molecular sieve.
The first reactor is used as raw material pretreatment for desulfurization and denitrification and simultaneously for aviation kerosene aromatic hydrocarbon hydrogenation saturation, and the fractionating tower is arranged between the first reactor and the second reactor to cut the aviation kerosene fraction in the raw material while cutting the hydrocracking product, so that excessive cracking is avoided.
The method for hydrocracking and producing aviation kerosene in a high yield manner, disclosed by the invention, is characterized in that the reaction pressure of the first reactor and the reaction pressure of the second reactor are preferably 5-14 MPa.
The hydrocracking method for producing aviation kerosene in a high yield, provided by the invention, has the distillation range of the raw oil preferably ranging from 200 ℃ to 500 ℃.
The hydrocracking method for producing aviation kerosene in high yield is characterized in that the raw oil is at least one selected from light wax oil, straight-run diesel oil and coker diesel oil, and the content of coker diesel oil in the raw oil is preferably below 15 wt%.
The hydrocracking method for increasing the yield of aviation kerosene, provided by the invention, is characterized in that the reaction conditions of the first reactor are preferably as follows:the reaction temperature is 260-420 ℃, and the volume space velocity is 0.5-3.0 h-1Hydrogen to oil volume ratio of 500 to 2000Nm3/m3(ii) a The reaction conditions of the second reactor are as follows: the reaction temperature is 260-420 ℃, and the volume space velocity is 0.3-3.0 h-1Hydrogen to oil volume ratio of 500 to 2000Nm3/m3。
The method for hydrocracking aviation kerosene with high yield, provided by the invention, is characterized in that the first reactor is preferably filled with a hydrotreating catalyst, or the upper layer is filled with a hydrotreating catalyst, and the lower layer is preferably filled with a hydrocracking catalyst.
The method for hydrocracking aviation kerosene with high yield, provided by the invention, is characterized in that the second reactor is preferably filled with a hydrocracking catalyst, or the upper layer of the second reactor is filled with a hydrocracking catalyst, and the lower layer of the second reactor is filled with a hydrotreating catalyst.
The method for hydrocracking and producing aviation kerosene in high yield, disclosed by the invention, is preferably that the specific surface area of the hydrotreating catalyst is 120-300 m2(iv) per gram, total pore volume is 0.25-0.50 ml/gram.
The method for hydrocracking and producing aviation kerosene in high yield, disclosed by the invention, is preferably that the specific surface of the hydrocracking catalyst is 200-450 m2The total pore volume is 0.30-0.65 ml/g, the infrared acid amount is 0.20-0.55 mmol/g, and the ratio of B acid to L acid is 0.1-1.0.
In the method, the product after hydrocracking in the second reactor enters the first reactor, and pre-refining and post-refining are concentrated in the first reactor, so that the long-period quality of the aviation kerosene product is ensured, and the equipment and operation cost is saved. In addition, the Beta and Y composite or mixed molecular sieve with good cracking and ring-opening performances is used as the acidic component of the hydrocracking catalyst, and the aviation kerosene refining is carried out after hydrocracking, so that the aromatic hydrocarbon in aviation kerosene fractions is reduced, the product quality is improved, and meanwhile, the fractionating tower is arranged between the hydrofining and the hydrocracking, so that the yield of aviation kerosene is improved by avoiding excessive cracking.
In conclusion, the method for producing the aviation kerosene with low aromatic hydrocarbon content and high smoke point under the medium pressure has the characteristics of low investment, low operation cost, simple operation and the like, and can produce naphtha as the ethylene raw material.
Drawings
FIG. 1 is a schematic diagram of a medium-pressure hydrocracking method for high-yield aviation kerosene, provided by the present invention, in which many necessary devices such as a heating furnace, a pump, etc. are omitted; wherein,
1. a first reactor; 2. a high pressure separator; 3. a low pressure separator; 4. a fractionating column; 5. a second reactor; 6. bottom materials; 7. a reaction effluent; 8. a gas phase product; 9. raw oil; 10. (ii) fresh hydrogen; 11. a liquid phase stream; 12. a naphtha fraction; 13. aviation kerosene fraction;
raw oil 9, new hydrogen 10 and reaction effluent 7 of a second reactor are mixed, the mixture enters a high-pressure separator 2 after desulfurization and denitrification and aromatic saturation in a first reactor 1, liquid phase material flow 11 of the high-pressure separator passes through a low-pressure separator 3 and then is cut into naphtha fraction 12 and aviation kerosene fraction 13 in a fractionating tower 4, a gas phase product 8 of the high-pressure separator 2 is compressed by a recycle hydrogen compressor and then is mixed with a bottom material 6 of the fractionating tower, the mixture enters a second reactor 5 for hydrocracking reaction, and the reaction effluent 7 is mixed with the raw oil 9 and the new hydrogen 10 and then returns to the first reactor 1.
FIG. 2 is a schematic diagram of a conventional process for medium-pressure hydrocracking of high-yield aviation kerosene, wherein many necessary devices such as a heating furnace, a pump and the like are omitted. Wherein,
2-1, raw oil; 2-2, a first reactor; 2-3, a second reactor; 2-4, a high pressure separator; 2-5, a low pressure separator; 2-6, a fractionating tower; 2-7, a third reactor; 2-8 of naphtha fraction; 2-9, aviation kerosene fraction; 2-10, circulating hydrogen; 2-11, new hydrogen; 2-12, bottom effluent; 2-13, aviation kerosene product.
Detailed Description
The invention will be further described with reference to specific examples, but it should be understood that the invention is not limited thereto.
Example 1
A mixed raw material (namely raw oil 9) of straight-run diesel oil from an atmospheric and vacuum distillation unit, vacuum wax oil and coker wax oil from a coker passes through a first reactor and a second reactor, wherein the first reactor is filled with a hydrofining catalyst A1, and the second reactor is filled with a hydrocracking catalyst B1. The feedstock properties, catalyst properties, specific operating conditions, product distribution and product results are all shown in table 1. The yield of aviation kerosene can reach 60.6%, and the smoke point is 27.9 mm.
Referring to fig. 1, raw oil 9, new hydrogen 10 and reaction effluent 7 of a second reactor are mixed, the mixture enters a high-pressure separator 2 after desulfurization and denitrification and aromatic saturation in a first reactor 1, liquid-phase material flow 11 of the high-pressure separator passes through a low-pressure separator 3, naphtha fraction 12 and aviation kerosene fraction 13 are cut out from a fractionating tower 4, a gas-phase product 8 of the high-pressure separator 2 is compressed by a recycle hydrogen compressor, mixed with a bottom material 6 of the fractionating tower and then enters a second reactor 5 for hydrocracking reaction, and the reaction effluent 7 is mixed with the raw oil 9 and the new hydrogen 10 and then returns to the first reactor 1.
TABLE 1 example 1 feed oil, catalyst Properties, operating conditions and product distribution
In the table, CB/CL is the acid amount ratio of the B acid to the L acid (the same applies hereinafter).
Example 2
The straight-run diesel oil from an atmospheric and vacuum distillation unit passes through a first reactor and a second reactor, wherein the first reactor is filled with a hydrofining catalyst A2, and the second reactor is filled with a hydrocracking catalyst B2. The feedstock properties, catalyst properties, specific operating conditions, product distribution and product results are all shown in table 2. The yield of aviation kerosene can reach 66.2%, and the smoke point is 28.3 mm.
The specific process flow is the same as in example 1.
TABLE 2 example 2 feed oil, catalyst Properties, operating conditions and product distribution
Example 3
The mixed raw material of straight-run diesel oil and vacuum wax oil from an atmospheric and vacuum distillation unit passes through a first reactor and a second reactor, wherein the first reactor is filled with a hydrofining catalyst A3, and the second reactor is filled with a hydrocracking catalyst B3. The feedstock properties, catalyst properties, specific operating conditions, product distribution and product results are all shown in table 3. The yield of aviation kerosene can reach 62.9%, and the smoke point is 27.3 mm.
The specific process flow is the same as in example 1.
TABLE 3 example 3 feed oil, catalyst Properties, operating conditions and product distribution
Comparative example 1
The mixed raw material of straight-run diesel oil and vacuum wax oil from an atmospheric and vacuum device is hydrofined by a first reactor and then enters a second reactor for hydrocracking, and the aviation kerosene fraction after fractionation is refined in a third reactor. The first reactor was filled with hydrofinishing catalyst A3, the second reactor with hydrocracking catalyst B3, and the third reactor with post-refining catalyst C. The feedstock properties, catalyst properties, specific operating conditions, product distribution and product results are all shown in table 4. The yield of aviation kerosene can reach 56.3%, and the smoke point is 26.2 mm.
Referring to figure 2, raw oil 2-1, new hydrogen 2-11, bottom effluent 2-12 and recycle hydrogen 2-10 are mixed, enter a second reactor 2-3 for hydrocracking reaction after being desulfurized and denitrified by a first reactor 2-2 and aromatic hydrocarbon saturation, then enter a fractionating tower 2-6 through a high-pressure separator 2-4 and a low-pressure separator 2-5, and are cut into naphtha fraction 2-8 and aviation kerosene fraction 2-9, and the bottom effluent 2-12 returns to be mixed with the raw oil 2-1, the new hydrogen 2-11 and the recycle hydrogen 2-10 and enters the first reactor 2-2. And after the gas-phase product of the high-pressure separator 2-4 is compressed by a recycle hydrogen compressor, returning a part of recycle hydrogen 2-10 to the first reactor 2-2, mixing the other part of recycle hydrogen 2-10 with the aviation kerosene fraction 2-9, entering a third reactor 2-7 for aromatic saturation, and obtaining aviation kerosene products 2-13 after passing through a high-pressure separator and a low-pressure separator.
TABLE 4 comparative example 1 feedstock, catalyst Properties, operating conditions and product distribution
As can be seen from the comparison between the example 3 and the comparative example 1, compared with the prior art, the method has the characteristics of low investment, high aviation kerosene yield, good quality and the like.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (9)
1. The hydrocracking method for producing aviation kerosene in high yield is characterized by comprising the following steps:
hydrofining raw oil S1 and hydrogen in a first reactor, sequentially entering a high-pressure separator and a low-pressure separator, and cutting naphtha fraction and aviation kerosene fraction from liquid-phase material flow of the low-pressure separator through a fractionating tower;
the gas phase material flow of the S2 high-pressure separator passes through a recycle hydrogen compressor and then is mixed with the bottom material of the fractionating tower to enter a second reactor for hydrocracking reaction, and then the reaction effluent returns to the first reactor;
the catalyst filled in the first reactor and the second reactor is respectively selected from at least one of hydrotreating catalyst and hydrocracking catalyst;
the hydrotreating catalyst comprises 1-10 wt% of NiO and 15-30 wt% of MoO31-5 wt% of F, 1-3 wt% of B and the balance of a carrier, wherein the carrier is alumina or amorphous silicon-aluminum;
the hydrocracking catalyst comprises 1-10 wt% of NiO and 10-25 wt% of WO3And the balance of the carrier, wherein the carrier consists of 20-60 wt% of a composite molecular sieve, 40-80 wt% of alumina and 0-50 wt% of amorphous silicon-aluminum, and the composite molecular sieve is formed by compounding or mixing a Beta molecular sieve and a Y molecular sieve.
2. The method for hydrocracking aviation kerosene of claim 1, wherein the reaction pressure of the first reactor and the second reactor is 5-14 MPa.
3. The method for hydrocracking aviation kerosene of claim 1, wherein the distillation range of said feedstock oil is 200 to 500 ℃.
4. The method for hydrocracking aviation kerosene of claim 1, wherein said feedstock is at least one selected from the group consisting of light wax oil, straight-run diesel oil and coker diesel oil, and the content of coker diesel oil in said feedstock is 15 wt% or less.
5. The method for hydrocracking high-yield aviation kerosene according to claim 1, wherein the reaction conditions of said first reactor are: the reaction temperature is 260-420 ℃, and the volume space velocity is 0.5-3.0 h-1Hydrogen to oil volume ratio of 500 to 2000Nm3/m3(ii) a The reaction conditions of the second reactor are as follows: the reaction temperature is 260-420 ℃, and the volume space velocity is 0.3-3.0 h-1Hydrogen to oil volume ratio of 500 to 2000Nm3/m3。
6. The method for hydrocracking high-yield aviation kerosene according to claim 1, wherein the first reactor is filled with a hydrotreating catalyst, or the upper layer is filled with a hydrotreating catalyst and the lower layer is filled with a hydrocracking catalyst.
7. The method for hydrocracking aviation kerosene of claim 1, wherein the second reactor is filled with a hydrocracking catalyst, or the upper layer is filled with a hydrocracking catalyst and the lower layer is filled with a hydrotreating catalyst.
8. The method for hydrocracking high-yield aviation kerosene according to claim 1, wherein the specific surface area of said hydrotreating catalyst is 120-300 m2(iv) per gram, total pore volume is 0.25-0.50 ml/gram.
9. The method for hydrocracking high-yield aviation kerosene of claim 1, wherein the specific surface area of the hydrocracking catalyst is 200-450 m2The total pore volume is 0.30-0.65 ml/g, the infrared acid amount is 0.20-0.55 mmol/g, and the ratio of B acid to L acid is 0.1-1.0.
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