CN116004282B - Hydrocracking method for producing jet fuel with high smoke point - Google Patents
Hydrocracking method for producing jet fuel with high smoke point Download PDFInfo
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 93
- 239000000446 fuel Substances 0.000 title claims abstract description 66
- 239000000779 smoke Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002283 diesel fuel Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims description 87
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 230000003197 catalytic effect Effects 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000007670 refining 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 12
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000003921 oil Substances 0.000 description 67
- 239000003350 kerosene Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 20
- 239000001993 wax Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 238000004523 catalytic cracking Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a hydrocracking method for producing high smoke point jet fuel, which comprises the steps of hydrofining wax oil raw oil, mixing reaction effluent with hydrogenated diesel oil, and hydrocracking to obtain the high smoke point jet fuel, wherein the weight fraction of the hydrogenated diesel oil is 5-40% based on the total weight of the wax oil raw oil and the hydrogenated diesel oil, the smoke point of the high smoke point jet fuel is more than 25mm, and the aromatic hydrocarbon content is more than 8% by volume. According to the invention, under the condition of the same mixing proportion of secondary processing oil, jet fuel with higher yield and higher smoke point can be obtained.
Description
Technical Field
The invention relates to the technical field of hydrocarbon raw material treatment, in particular to a hydrocracking method for producing jet fuel with high smoke point.
Background
The most desirable components in jet fuel compositions are monocyclic naphthenes and branched paraffins, which have excellent combustibility, thermal stability and low temperature fluidity. Aromatic content and smoke point are two important indicators of jet fuel: in addition, when the content of the aromatic hydrocarbon is high, the sealing element made of the polymer elastomer is negatively affected, so that the upper limit of the content of the aromatic hydrocarbon is limited by jet fuel standards, but the lower limit of the aromatic hydrocarbon content of the jet fuel is limited recently due to the fact that the lower heat value of the jet fuel with lower aromatic hydrocarbon content affects the service performance of the jet fuel. The smoke point is also called smokeless flame height, which is the maximum height measured in a specially made lamp when the fuel flame does not smoke, expressed in millimeters, and the higher the smoke point, the less prone the fuel to produce soot. In general, two indexes, namely, the aromatic hydrocarbon content and the smoke point, are in a negative correlation, and the smoke point is lower as the aromatic hydrocarbon content is higher.
The oil refining industry produces jet fuel mainly by the following three methods: (1) The deep hydrotreating process with straight run kerosene fraction rich in arene or kerosene fraction obtained through secondary treatment as material can reduce sulfur, nitrogen and arene content obviously, but has great hydrogen consumption and high production cost; (2) Selecting straight-run kerosene fraction of proper crude oil as raw material, under the condition that indexes such as density, combustion performance and the like basically meet the requirements, adopting a non-hydrogenation processing technology or a hydrogenation technology to process so as to remove mercaptan, reduce acid value and improve color and stability, and obtaining qualified jet fuel, wherein the method has low production cost and is the most applicable method at present, but the method is limited by the raw material, and only straight-run kerosene obtained by proper crude oil can be suitable; (3) The hydrocracking process of producing jet fuel with vacuum gas oil, coked wax oil, straight run diesel oil, etc. as material has high investment and operation cost, and the process is not limited by the processing capacity of crude oil in oil refinery, and the heavy inferior material is converted into jet fuel with low arene content and smoke point superior to those of the first two kinds of process.
The smoke point of jet fuel produced by the hydrocracking process is closely related to the pressure rating. The higher the hydrocracking unit pressure, the more obvious the raw aromatics saturation, the higher the smoke point of the obtained jet fuel; the aromatic hydrocarbon saturation depth is low under the medium pressure condition, the influence on the jet fuel smoke point is large, and the high-quality product can be obtained only under the specific raw materials, process or catalyst conditions. The properties of the hydrocracking raw materials have a significant influence on aromatic hydrocarbons of jet fuel oil, the paraffin-based raw materials can generally obtain jet fuel fractions with smoke points of about 30mm, but the aromatic hydrocarbon content is often less than 3% by volume, the smoke points of the jet fuel fractions obtained from cycloalkyl raw materials are about 20mm, and the intermediate raw materials have difficulty in reaching aromatic hydrocarbon content of more than 8% by volume although the smoke points can reach about 25 mm.
The catalytic cracking diesel oil is rich in aromatic hydrocarbon, wherein the aromatic hydrocarbon is mainly polycyclic aromatic hydrocarbon. Because of the high density, low cetane number and high nitrogen content of catalytic cracking diesel, it is often necessary to convert the diesel into diesel blending components by diesel hydro-upgrading. At present, poor-quality catalytic cracking diesel oil is subjected to selective hydrogenation to retain a monocyclic aromatic hydrocarbon structure, and is further converted into a product rich in alkylbenzenes through means of hydrocracking or catalytic cracking and the like, so that the octane number can be improved or the yield of aromatic hydrocarbon materials can be increased.
CN102399586B discloses a medium pressure hydrocracking process for producing jet fuel. The method improves the product quality by recycling the hydrocracking kerosene fraction under the medium pressure grade, but the kerosene fraction has lower yield, high energy consumption and strict requirements on raw materials, and the jet fuel with the smoke point larger than 25mm is obtained by processing relatively high-quality raw materials.
CN106520197B discloses a hydrocracking method for producing aviation kerosene from inferior raw oil. The method is characterized in that the inferior raw material is subjected to hydrofining and hydrocracking reaction, the obtained kerosene fraction is further separated by a kerosene fractionating tower to obtain light and heavy kerosene fractions, and the heavy kerosene fraction is recycled and refined, so that dicyclo-cycloalkane and part of heavy aromatic hydrocarbon can be converted to improve the quality of jet fuel products. Although the method can improve the smoke point of jet fuel, after the conversion of heavy fraction, the yield of jet fuel fraction is reduced, the yields of gaseous hydrocarbon and light naphtha are increased, and the energy consumption and the chemical hydrogen consumption are improved.
CN109705900a discloses a method for producing aviation kerosene and chemical raw materials in maximum from diesel oil fraction. The method takes straight-run diesel oil or coked diesel oil as raw materials, and fractions such as naphtha, aviation kerosene, diesel oil and the like are obtained after hydrofining and hydrocracking reaction, and the diesel oil fraction is recycled to a cracking reaction zone to further increase the aviation kerosene fraction. The method takes the diesel oil fraction as the raw material, and the obtained aviation kerosene fraction has high smoke point and low aromatic hydrocarbon content.
CN109266390a discloses a method for hydrocracking and producing aviation kerosene. The method adopts two steps of processes, the raw materials are separated and fractionated after hydrofining, and the obtained diesel oil and tail oil fraction enter a hydrocracking reaction zone, so that the purposes of increasing the yield of aviation kerosene and improving the quality of aviation kerosene products are realized. The method adopts a two-stage full-circulation process, can improve the yield of the aviation kerosene fraction and improve the smoke point, but has limited aromatic hydrocarbon content due to the fact that diesel oil and tail oil which are rich in paraffin are all converted.
Disclosure of Invention
The invention aims to solve the contradiction problem between the smoke point and the aromatic hydrocarbon content of jet fuel fraction when jet fuel is produced by the conventional hydrocracking technology, and provides a method for simultaneously obtaining jet fuel with high aromatic hydrocarbon content and high smoke point.
The invention provides a hydrocracking method for producing high smoke point jet fuel, which comprises the steps of mixing wax oil raw oil and hydrogen, then enabling the mixture to enter a hydrofining reactor to contact with a hydrofining catalyst for reaction, enabling reaction effluent of the hydrofining reactor to enter a hydrocracking reactor to contact with the hydrocracking catalyst for reaction after being mixed with hydrogenated diesel oil, and separating reaction effluent of the hydrocracking reactor to at least obtain high smoke point jet fuel; the density of the hydrogenated diesel oil is 0.85-0.94 g/cm 3, the distillation range is 165-350 ℃, the mass fraction of the cyclic hydrocarbon in the hydrogenated diesel oil is 80-95% based on the mass of the hydrogenated diesel oil, the mass fraction of the total aromatic hydrocarbon is at least 60%, and the content of the monocyclic aromatic hydrocarbon is more than 50% of the total aromatic hydrocarbon; taking the total weight of wax oil raw oil and hydrogenated diesel oil as a reference, the weight fraction of the hydrogenated diesel oil is 5-40%; the smoke point of the jet fuel with high smoke point is more than 25mm, and the aromatic hydrocarbon content is more than 8 volume percent.
In the invention, the distillation range of the wax oil raw oil is 300-600 ℃, the density is 0.88-0.97 g/cm 3, and the wax oil raw oil is one or more of normal pressure wax oil, reduced pressure wax oil, hydrogenation wax oil, coking wax oil and deasphalted oil.
In one embodiment of the invention, in the hydrogenated diesel, the content of the monocyclic aromatic hydrocarbon accounts for more than 60% of the total aromatic hydrocarbon content; the sulfur content of the hydrogenated diesel oil is 1-2000 mug/g, and the nitrogen content is 1-200 mug/g.
In one embodiment of the invention, the hydrogenated diesel oil refers to one or more of hydrogenated catalytic diesel oil, residual oil hydrogenated diesel oil and coal tar hydrogenated diesel oil; the hydrogenated catalytic diesel is hydrogenated diesel fraction from a catalytic diesel hydrogenation device or hydrogenated diesel fraction from a hydrogenation unit of an LTAG process. The preferred hydrogenated diesel fuel of the invention is hydrogenated catalytic diesel fuel.
In the hydrofining reactor, the wax oil raw oil is mainly subjected to hydrodesulfurization, hydrodenitrogenation, aromatic hydrocarbon saturation and other reactions, and in order to ensure the activity and stability of the hydrocracking catalyst containing the molecular sieve at the downstream, the organic nitrogen content is less than 20 mug/g based on the liquid effluent of the hydrofining reactor.
In one embodiment of the present invention, the reaction conditions of the hydrofinishing reactor are: the hydrogen partial pressure is 10.0-18.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 400-2000 Nm 3/m3, and the liquid hourly space velocity is 0.2-3.0 h -1.
In one embodiment of the invention, the hydrofining catalyst is a supported catalyst, the carrier is alumina and/or silica-alumina, and the active metal component is at least one selected from group VIB metals and/or at least one selected from group VIII metals; the group VIII metal is selected from nickel and/or cobalt, the group VIB metal is selected from molybdenum and/or tungsten, the content of the group VIII metal is 1-10% by weight based on the total weight of the hydrofining catalyst, the content of the group VIB metal is 10-45% by weight based on oxide, and preferably, the active metal component is selected from two or three of nickel, molybdenum and tungsten metals.
The mixture of the reaction effluent of the hydrofining reactor and the hydrogenated diesel oil enters a hydrocracking reactor, and in a preferred case, the reaction mixture contacted with the hydrocracking catalyst has an aromatic hydrocarbon content of at least 25 percent and an organic nitrogen content of less than 20 mug/g.
Since the catalytic cracking diesel oil is rich in aromatic hydrocarbon, the aromatic hydrocarbon content is generally more than 70 wt%, wherein polycyclic aromatic hydrocarbon accounts for more than 60% of the total aromatic hydrocarbon, and the nitrogen content is 500-2000 mug/g. If the catalytic cracking diesel oil directly enters the hydrofining reactor, the aromatic hydrocarbon saturation degree of the catalytic cracking diesel oil is higher due to the existence of higher hydrogen partial pressure, so that most of aromatic hydrocarbon is completely saturated, and the total aromatic hydrocarbon content of liquid phase products of the hydrofining reactor is less than 30w percent.
The pressure grade of the conventional catalytic cracking diesel hydrogenation device and the LTAG process hydrogenation unit is 4-10 MPa, and the device belongs to a medium pressure range. In the pressure range, the catalytic cracking diesel is the hydrogenation catalytic diesel which is rich in monocyclic aromatic hydrocarbon and is obtained through selective hydrogenation, the total aromatic hydrocarbon content is more than 60 percent by weight, the monocyclic aromatic hydrocarbon content is more than 50 percent by weight, preferably more than 60 percent by weight of the total aromatic hydrocarbon content, the monocyclic aromatic hydrocarbon contains a large amount of tetrahydronaphthalene structural hydrocarbons which are obtained through partial saturation of bicyclic aromatic hydrocarbon, and the structural molecules can obtain alkylbenzene products through ring opening of saturated rings under the hydrocracking process condition.
The inventor of the present invention found through intensive research that based on the carbon number distribution of the hydrocarbon structure of the hydrogenation catalytic diesel, the dicyclic aromatic hydrocarbon of the naphthalene structure is mainly concentrated in C11-C15, namely, the naphthalene ring has single or multiple substituents with 1-5 carbon numbers, after the structure is converted by the method of the present invention, the alkylbenzene with 11-15 carbon numbers can be obtained, the distillate range is mainly concentrated in 185-260 ℃ and belongs to the jet fuel distillate section, therefore, the aromatic hydrocarbon content of the distillate section can be greatly improved, and meanwhile, the smoke point of the distillate section is limited and negative influence can be generated.
In one embodiment of the invention, the reaction conditions of the hydrocracking reactor are: the hydrogen partial pressure is 10.0-18.0 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.4-4.0 h -1.
After the catalytic diesel is partially hydrogenated under the medium pressure condition, the nitrogen content is generally 1-200 mug/g, and when the nitrogen content after the hydrogenated catalytic diesel is mixed with the effluent of the hydrofining section is more than 20 mug/g, the upper part of the hydrocracking catalyst is filled with a partial hydrofining catalyst so as to reduce the nitrogen content of the mixed hydrocarbon contacting the hydrocracking catalyst to be within 20 mug/g in order to avoid the influence on the cracking activity of the hydrocracking catalyst.
In one embodiment of the present invention, the hydrocracking reactor is packed with a hydrocracking catalyst, a post-refining catalyst; in the hydrocracking reactor, the volume ratio of the hydrocracking catalyst to the post-refining catalyst is 1:30-1:1.
In one embodiment of the present invention, the hydrocracking reactor is filled with a hydrofining catalyst, a hydrocracking catalyst, a post-refining catalyst; in the hydrocracking reactor, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1:20-1:5, and the volume ratio of the hydrocracking catalyst to the post-refining catalyst is 1:30-1:1.
In one embodiment of the invention, the total volume ratio of hydrofinishing reactor to catalyst in hydrocracking reactor is from 4:1 to 1:4.
In one embodiment of the invention, the hydrocracking catalyst is formed by a carrier and a VIII group metal and/or VIB group metal catalyst supported on the carrier, wherein the carrier comprises alumina and a molecular sieve; the molecular sieve is one or more of a Y-type molecular sieve and a beta-type molecular sieve; the group VIII metal is selected from nickel and/or cobalt, and the group VIB metal is selected from molybdenum and/or tungsten; based on the whole hydrocracking catalyst, the alumina accounts for 30-72 wt%, the molecular sieve accounts for 1-30 wt%, the VIB group metal accounts for 15-35 wt% and the VIII group metal accounts for 2-8 wt% in terms of oxide.
In one embodiment of the invention, the post-refining catalyst is a supported catalyst, the support is alumina and/or silica-alumina, and the active metal component is at least one metal selected from group VIB metals and/or at least one metal selected from group VIII metals; the VIII metal is selected from nickel and/or cobalt, the VIB metal is selected from molybdenum and/or tungsten, the total weight of the refined catalyst is calculated by oxide, the content of the VIII metal is 1-10 wt%, and the content of the VIB metal is 10-45 wt%.
And (3) separating and fractionating the mixture after the hydrocracking reaction to obtain dry gas, liquefied gas, naphtha, high smoke point jet fuel, diesel oil and tail oil fraction. In the invention, the initial boiling point of the jet fuel with high smoke point is 140-165 ℃, the final boiling point is 230-270 ℃, and the aromatic hydrocarbon content is not more than 25 volume percent.
Compared with hydrorefined wax oil, the hydrocatalyzed diesel has smaller molecular size and lower monocyclic aromatic hydrocarbon hydrogenation saturation rate, so that the alkylbenzene structure can be reserved in a larger proportion in the hydrocracking reaction, the generation of the bicycloalkane structure is reduced, and the production of the jet fuel with high aromatic hydrocarbon and high smoke point is facilitated.
The invention has the advantages that the catalytic diesel oil which is partially saturated under the medium pressure condition is mixed with the hydrogenated wax oil which is deeply saturated under the high pressure condition to be used as the mixed raw material of the hydrocracking section, so that the aromatic hydrocarbon in the raw material is reserved to a large extent while the low nitrogen content is met, and the aromatic hydrocarbon is transferred into jet fuel fraction, thereby obtaining the high-quality jet fuel with high smoke point and high aromatic hydrocarbon content. Compared with jet fuel obtained by hydrofining and hydrocracking the conventional wax oil fraction and catalytic diesel mixed raw material, the jet fuel has the characteristics of higher aromatic hydrocarbon and equivalent smoke point under the condition of the same catalytic diesel blending proportion.
Compared with the prior art, the jet fuel fraction with higher yield can be obtained under the condition of the same blending proportion of secondary processing oil, and the jet fuel fraction is the jet fuel with high smoke point, the smoke point is more than 25mm, and the aromatic hydrocarbon content is more than 8% by volume.
Drawings
FIG. 1 is a schematic illustration of one embodiment of a hydrocracking process for producing high smoke point jet fuel provided by the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, without thereby limiting the invention.
FIG. 1 is a schematic illustration of one embodiment of a hydrocracking process for producing high smoke point jet fuel provided by the present invention. As shown in fig. 1, the wax oil fraction from line 1 and the hydrogen-rich gas from line 22 are mixed and fed into the hydrofining reactor 2 to contact the hydrofining catalyst, and mainly undergo desulfurization, denitrification and aromatic saturation reactions. After the reaction effluent of the hydrofining reactor 2 is mixed with the hydrogenated catalytic diesel oil from the pipeline 3, the mixture enters the hydrocracking reactor 5 through the pipeline 4 and is sequentially contacted with the hydrofining catalyst, the hydrocracking catalyst and the post-refining catalyst, the obtained gas-liquid mixture flows through the pipeline 6 to enter the high-pressure separator 7, the acidic water is discharged through the pipeline 8, the hydrogen-rich gas enters the recycle hydrogen compressor 9 to be boosted, and the boosted stripping gas is mixed with new hydrogen from the pipeline 21 to be used as make-up hydrogen and cold hydrogen. The high-fraction liquid phase enters a low-pressure separator 11 through a pipeline 10, low-fraction gas is discharged through a pipeline 12, acid water is discharged through a pipeline 13, and the low-fraction liquid phase enters a fractionating tower 15 through a pipeline 14 for separation. Light naphtha obtained by separation is extracted through a pipeline 16; the heavy naphtha fraction obtained by separation is withdrawn through a line 17; the separated jet fuel fraction is withdrawn via line 18; the separated diesel fraction is withdrawn through a pipeline 19; the separated tail oil fraction exits the apparatus via line 20.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
In examples and comparative examples, the smoke point of jet fuel was obtained by GB/T382 method for measuring smoke point of kerosene and jet fuel; the aromatic hydrocarbon content of jet fuel is obtained by GB/T11132 method for determination of hydrocarbons in liquid Petroleum products (fluorescence indicator adsorption method).
In the examples, the product of the hydrofining catalyst A is RN-410, the product of the hydrofining catalyst B is RS-2100, the product of the hydrocracking catalyst C is RHC-220, the product of the hydrocracking catalyst D is RHC-133, and the above catalysts are produced by the division of catalyst Chang Ling of China petrochemical Co.
The raw oil E and the raw oil F used in the examples are hydrogenation catalytic diesel, and are from a catalytic cracking diesel hydrogenation device, the raw oil G is catalytic diesel, and the raw oil H and the raw oil I are decompression wax oil, and the properties are shown in Table 1. It can be seen from table 1 that the total aromatic hydrocarbon content of the hydrocatalytic diesel raw materials E and F reaches more than 70%, wherein the monocyclic aromatic hydrocarbon accounts for more than 70% of the total aromatic hydrocarbon content. The total aromatic hydrocarbon content of the raw oil G is 82.5%, and the monocyclic aromatic hydrocarbon content is 33.4%, so that the catalyst is conventional catalytic diesel. The raw oil H and the raw oil I are conventional depressurized wax oil, and the raw oil I is inferior compared with the raw oil H.
Example 1
The raw oil H and hydrogen are mixed and enter a hydrofining reactor to contact and react with a hydrofining catalyst A, the reaction effluent is mixed with raw oil E, the mixture enters a hydrocracking reactor to contact and react with a hydrocracking catalyst C and a post-refining catalyst A in sequence, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 2, and the hydrocracking reactor feed composition, product yield and properties are shown in Table 3.
Comparative example 1
The mixed oil of the raw oil E and the raw oil H sequentially enters a hydrofining and hydrocracking reactor together with hydrogen to contact and react with a hydrofining catalyst A, a hydrocracking catalyst C and a post-refining catalyst A in sequence, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Comparative example 2
The mixed oil of the raw oil G and the raw oil H sequentially enters a hydrofining and hydrocracking reactor together with hydrogen, and then contacts and reacts with a hydrofining catalyst A and a hydrocracking catalyst C, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Comparative example 3
Raw oil H and hydrogen are mixed and then sequentially enter a hydrofining and hydrocracking reactor to be in contact reaction with a hydrofining catalyst A and a hydrocracking catalyst C, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 2, and the product yields and properties are shown in Table 3.
Example 2
The raw oil H and hydrogen are mixed and enter a hydrofining reactor to contact and react with a hydrofining catalyst A, the reaction effluent is mixed with raw oil F, the mixture enters a hydrocracking reactor to contact and react with the hydrofining catalyst A, a hydrocracking catalyst D and a post-refining catalyst A in sequence, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 4, and the hydrocracking reactor feed composition, product yield and properties are shown in Table 5.
Example 3
The raw oil I and hydrogen are mixed and then enter a hydrofining reactor to contact and react with a hydrofining catalyst B, the reaction effluent is mixed with raw oil F and enters a hydrocracking reactor to contact and react with the hydrofining catalyst B, a hydrocracking catalyst D and a post-refining catalyst B in sequence, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 4, and the hydrocracking reactor feed composition, product yield and properties are shown in Table 5.
Example 4
The raw oil I and hydrogen are mixed and then enter a hydrofining reactor to contact and react with a hydrofining catalyst B, the reaction effluent is mixed with raw oil F and enters a hydrocracking reactor to contact and react with the hydrofining catalyst B, a hydrocracking catalyst D and a post-refining catalyst B in sequence, and the reaction effluent is separated and fractionated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel fraction, diesel fraction and tail oil fraction. The reaction conditions are shown in Table 4, and the hydrocracking reactor feed composition, product yield and properties are shown in Table 5.
It can be seen from examples and comparative examples that by adopting the method provided by the invention, jet fuel with high smoke point and high aromatic hydrocarbon content can be directly obtained under the conventional process flow by blending hydrogenation catalytic diesel oil at the inlet of a hydrocracking reactor. Compared with the hydrocracking technology for processing straight-run wax oil under the same condition, the hydrocracking technology has higher aromatic hydrocarbon content and smoke point, and compared with the mixed raw material of the straight-run wax oil and catalytic diesel oil, the hydrocracking technology sequentially passes through the hydrofining reactor and the hydrocracking reactor, has higher smoke point and higher aromatic hydrocarbon content of jet fuel products, and can meet the requirements of special jet fuel which simultaneously requires lower limit of smoke point and lower limit of aromatic hydrocarbon content.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
Claims (14)
1. A hydrocracking method for producing high smoke point jet fuel, wax oil raw oil and hydrogen are mixed and then enter a hydrofining reactor to contact with a hydrofining catalyst for reaction, reaction effluent of the hydrofining reactor is mixed with hydrogenated diesel oil and then enters a hydrocracking reactor to contact with the hydrocracking catalyst for reaction, aromatic hydrocarbon content is at least 25%, organic nitrogen content is less than 20 mug/g in the reaction mixture of the contact hydrocracking catalyst, and the reaction effluent of the hydrocracking reactor is separated to obtain the high smoke point jet fuel; the density of the hydrogenated diesel oil is 0.85-0.94 g/cm 3, the distillation range is 165-350 ℃, the mass fraction of the cyclic hydrocarbon in the hydrogenated diesel oil is 80-95% based on the mass of the hydrogenated diesel oil, the mass fraction of the total aromatic hydrocarbon is at least 60%, and the content of the monocyclic aromatic hydrocarbon is more than 50% of the total aromatic hydrocarbon; taking the total weight of wax oil raw oil and hydrogenated diesel oil as a reference, the weight fraction of the hydrogenated diesel oil is 5-40%;
the initial boiling point of the jet fuel with high smoke point is 140-165 ℃, the final boiling point is 230-270 ℃, the smoke point of the jet fuel with high smoke point is more than 25mm, the aromatic hydrocarbon content is more than 8% by volume and not more than 25% by volume.
2. The method according to claim 1, wherein the wax oil raw oil has a distillation range of 300-600 ℃ and a density of 0.88-0.97 g/cm 3, and is one or more selected from normal pressure wax oil, reduced pressure wax oil, hydrogenated wax oil, coker wax oil and deasphalted oil.
3. The method according to claim 1, wherein the content of monocyclic aromatic hydrocarbon in the hydrogenated diesel oil is more than 60% of the total aromatic hydrocarbon content; the sulfur content of the hydrogenated diesel oil is 1-2000 mug/g, and the nitrogen content is 1-200 mug/g.
4. The method according to claim 1 or 3, wherein the hydrogenated diesel is one or more of hydrogenated catalytic diesel, residual oil hydrogenated diesel and coal tar hydrogenated diesel; the hydrogenated catalytic diesel is hydrogenated diesel fraction from a catalytic diesel hydrogenation device or hydrogenated diesel fraction from a hydrogenation unit of an LTAG process.
5. The process of claim 1, wherein the reaction conditions of the hydrofinishing reactor are: the hydrogen partial pressure is 10.0-18.0 MPa, the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 400-2000 Nm 3/m3, and the liquid hourly space velocity is 0.2-3.0 h -1.
6. The process according to claim 1, wherein the hydrofinishing catalyst is a supported catalyst, the support is alumina and/or silica-alumina, the active metal component is at least one group VIB metal and/or at least one group VIII metal; the group VIII metal is selected from nickel and/or cobalt and the group VIB metal is selected from molybdenum and/or tungsten.
7. The process according to claim 6, wherein the group VIII metal is present in an amount of 1 to 10 wt.% and the group VIB metal is present in an amount of 10 to 45 wt.% on an oxide basis based on the total weight of the hydrofinishing catalyst.
8. The method of claim 6, wherein the active metal component is selected from two or three of nickel, molybdenum and tungsten metals.
9. The process of claim 1, wherein the reaction conditions of the hydrocracking reactor are: the hydrogen partial pressure is 10.0-18.0 MPa, the reaction temperature is 300-420 ℃, and the liquid hourly space velocity is 0.4-4.0 h -1.
10. The method according to claim 1, wherein the hydrocracking reactor is filled with a hydrocracking catalyst, a post-refining catalyst; in the hydrocracking reactor, the volume ratio of the hydrocracking catalyst to the post-refining catalyst is 1:30-1:1.
11. The method according to claim 1, wherein the hydrocracking reactor is filled with a hydrofining catalyst, a hydrocracking catalyst, a post-refining catalyst; in the hydrocracking reactor, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1:20-1:5, and the volume ratio of the hydrocracking catalyst to the post-refining catalyst is 1:30-1:1.
12. The process of claim 1 wherein the total volume ratio of hydrofinishing reactor to catalyst in hydrocracking reactor is from 4:1 to 1:4.
13. The process of claim 1 wherein the hydrocracking catalyst is a catalyst comprising a support comprising alumina, molecular sieves, and a group VIII metal and a group VIB metal supported on a support; the molecular sieve is one or two of a Y-type molecular sieve and a beta-type molecular sieve; the group VIII metal is selected from nickel and/or cobalt, and the group VIB metal is selected from molybdenum and/or tungsten; based on the whole hydrocracking catalyst, the alumina accounts for 30-72 wt%, the molecular sieve accounts for 1-30 wt%, the VIB group metal accounts for 15-35 wt% and the VIII group metal accounts for 2-8 wt% in terms of oxide.
14. The process according to claim 10 or 11, characterized in that the post-purification catalyst is a supported catalyst, the support is alumina and/or silica-alumina, the active metal component is at least one metal selected from group VIB metals and at least one metal selected from group VIII metals; the VIII metal is selected from nickel and/or cobalt, the VIB metal is selected from molybdenum and/or tungsten, the total weight of the refined catalyst is calculated by oxide, the content of the VIII metal is 1-10 wt%, and the content of the VIB metal is 10-45 wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
| CN111117701A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Hydrogenation method for maximum production of heavy naphtha and jet fuel components |
| CN112143522A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydrogenation method and system for production chemical material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN103013559A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Hydrocracking method for selective increasing of aviation kerosene yield |
| CN111117701A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Hydrogenation method for maximum production of heavy naphtha and jet fuel components |
| CN112143522A (en) * | 2019-06-26 | 2020-12-29 | 中国石油化工股份有限公司 | Hydrogenation method and system for production chemical material |
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