CN116042270B - Hydrocracking method for producing heavy naphtha and jet fuel - Google Patents
Hydrocracking method for producing heavy naphtha and jet fuel Download PDFInfo
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- CN116042270B CN116042270B CN202111261724.8A CN202111261724A CN116042270B CN 116042270 B CN116042270 B CN 116042270B CN 202111261724 A CN202111261724 A CN 202111261724A CN 116042270 B CN116042270 B CN 116042270B
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 115
- 239000000446 fuel Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000005336 cracking Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005192 partition Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 178
- 239000003054 catalyst Substances 0.000 claims description 101
- 239000003921 oil Substances 0.000 claims description 95
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 26
- 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
- 238000002156 mixing Methods 0.000 claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 239000002283 diesel fuel Substances 0.000 claims description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010734 process oil Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000047 product Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 17
- 238000007670 refining Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000013316 zoning Methods 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of processing raw oil under high-pressure hydrogen conditions, and discloses a hydrocracking method for producing heavy naphtha and jet fuel. The partition type cracking reactor and the partition type cracking method can be used for efficiently converting the raw oil into heavy naphtha or jet fuel in a large proportion.
Description
Technical Field
The invention relates to the field of processing raw oil under high-pressure hydrogen conditions, in particular to a hydrocracking method for producing heavy naphtha and jet fuel.
Background
In recent years, the sustainable development of the economy in China brings about the continuous increase of the demands of aviation transportation fuels and chemical raw materials.
The hydrocracking process can convert heavy fraction oil into light product, heavy naphtha in the light product can be used as catalytic reforming raw material to produce aromatic hydrocarbon or low-sulfur low-alkene high-octane gasoline blending component, and jet fuel fraction can be used as high-quality No. 3 jet fuel.
However, the domestic single-stage once-through hydrocracking device for producing middle distillate (diesel oil and jet fuel) to produce both high-quality tail oil and reformate has the problems of partial diesel oil production, insufficient heavy naphtha yield and jet fuel yield and the like at present, so that the development of the hydrocracking technology capable of maximally producing the reformate and jet fuel and meeting the market demand and simultaneously producing no diesel oil and tail oil has important practical significance.
CN104611019a, CN104611046a, CN105001909a and CN105018137a disclose a low energy hydrocracking process for producing high quality jet fuels. The method mainly produces heavy naphtha and aviation kerosene by a catalyst grading method, and specifically comprises the steps of mixing raw oil and hydrogen, sequentially passing through a hydrofining and hydrocracking reaction zone, controlling the conversion rate of a cracking reaction to be about 70% to obtain a reaction effluent, and separating to obtain a product.
CN10461102a and CN104611026a disclose a low energy hydrocracking process for producing high quality chemical materials. The method is characterized in that the hydrocracking reaction zone is filled with at least two hydrocracking catalysts, the upstream of the hydrocracking reaction zone is filled with 30% -70% of modified Y molecular sieve of catalyst I, the catalyst II contains 15% -50% of modified Y molecular sieve, and the modified Y molecular sieve in the catalyst I is 10% -30% higher than the catalyst II. The loading volume ratio of the hydrocracking catalyst I to the hydrocracking catalyst II is 1:5-5:1.
From the foregoing, there are several problems with the prior art that maximize the production of heavy naphtha and jet fuel in a single-stage, once-through hydrocracking technology.
Firstly, the conversion rate of the existing single-stage once-through hydrocracking technical condition is low, and the yields of heavy naphtha and jet fuel products are insufficient.
Secondly, if a cracking agent with higher activity is adopted in the single-stage one-time hydrocracking technology, the selectivity of heavy naphtha and jet fuel products is poor.
In addition, the prior art has the problems that the prior art has not been disclosed, firstly, under the existing single-stage once-through hydrocracking technology, the cracking reaction temperature is high and the activity of a cracking catalyst is insufficient due to the adoption of a catalyst grading scheme with relatively low activity, so that the running period of the device is shortened; secondly, when more catalysts with high cracking activity are adopted in the catalyst grading scheme, the selectivity of the heavy naphtha and jet fuel products is poor, and the catalyst has high cracking activity and is sensitive to temperature, so that the catalyst is easy to fluctuate in the operation process of the device, and great inconvenience is brought to normal production.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, heavy inferior wax oil raw materials are difficult to convert and the product route is single.
In order to achieve the above object, the present invention provides a hydrocracking process for producing heavy naphtha and jet fuel, the process comprising:
(1) The raw oil and hydrogen are mixed and enter a hydrofining reaction zone for hydrofining reaction to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3~0.98g/cm3, the nitrogen content is 200-2500 mug/g, the final distillation point is 360-560 ℃, and the aromatic hydrocarbon content is 25-85 wt%;
(2) Introducing tail oil obtained from the fractionation unit and part of the refined effluent into an upper reaction zone of a partitioned hydrocracking reactor to perform a first reaction to obtain a first reaction effluent;
(3) The first reaction effluent, the supplementary hydrogen and the remaining refined effluent of the hydrofining reaction zone are mixed and distributed and then enter the lower reaction zone of the partitioned hydrocracking reactor to carry out a second reaction, so as to obtain a second reaction effluent;
(4) Introducing the second reaction effluent into a fractionation unit for separation to obtain a light naphtha fraction, a heavy naphtha fraction, a jet fuel fraction and a tail oil fraction capable of being recycled to step (2),
In the upper reaction zone of the partitioned hydrocracking reactor, the refined effluent introduced into the upper reaction zone of the partitioned hydrocracking reactor accounts for 5 to 30wt% of the total refined effluent obtained in step (1);
The recycled tail oil fraction accounts for 30% -55% of the total weight of the raw oil in the step (1) which is 100%;
controlling the cracking conversion in the upper reaction zone to be 55% -75% based on 100% total weight of recycled tail oil fraction and part of the refined effluent in step (2), wherein the cracking conversion = 100% -the tail oil fraction yield in the first reaction effluent; the jet fuel fraction has a cutting end point of 260-290 ℃;
In the partitioned hydrocracking reactor, the Y-type molecular sieve content of the hydrocracking catalyst in the upper reaction zone is 5 to 25wt% and the Y-type molecular sieve content of the hydrocracking catalyst in the lower reaction zone is 30 to 65wt% based on the weight of the carrier contained in the hydrocracking catalyst.
The method can optimize the reaction process in a zoning reaction mode and improve the selectivity of the heavy naphtha and jet fuel, thereby realizing the high-efficient conversion of the raw materials into the heavy naphtha and jet fuel in a large proportion.
Drawings
FIG. 1 is a schematic illustration of a hydrocracking process for producing heavy naphtha and jet fuel according to a preferred embodiment of the present invention.
Description of the reference numerals
1. Raw oil
2. Hydrofining reaction zone
3. Partitioned hydrocracking reactor
4. Thermal high pressure separator
5. Thermal low pressure separator
6. Cold high pressure separator
7. Cold low pressure separator
8. Fractionating tower
9. Light hydrocarbon
10. Light naphtha fraction
11. Heavy naphtha fraction
12. Jet fuel fraction
13. Tail oil fraction
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, the present invention provides a hydrocracking process for producing heavy naphtha and jet fuel comprising:
(1) The raw oil and hydrogen are mixed and enter a hydrofining reaction zone for hydrofining reaction to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3~0.98g/cm3, the nitrogen content is 200-2500 mug/g, the final distillation point is 360-560 ℃, and the total aromatic hydrocarbon content is 25-85 wt%;
(2) Introducing tail oil obtained from the fractionation unit and part of the refined effluent into an upper reaction zone of a partitioned hydrocracking reactor to perform a first reaction to obtain a first reaction effluent;
(3) The first reaction effluent, the supplementary hydrogen and the remaining refined effluent of the hydrofining reaction zone are mixed and distributed and then enter the lower reaction zone of the partitioned hydrocracking reactor to carry out a second reaction, so as to obtain a second reaction effluent;
(4) Introducing the second reaction effluent into a fractionation unit for separation to obtain a light naphtha fraction, a heavy naphtha fraction, a jet fuel fraction and a tail oil fraction capable of being recycled to step (2),
In the upper reaction zone of the partitioned hydrocracking reactor, the refined effluent introduced into the upper reaction zone of the partitioned hydrocracking reactor accounts for 5 to 30wt% of the total refined effluent obtained in step (1);
The recycled tail oil fraction accounts for 30% -55% of the total weight of the raw oil in the step (1) which is 100%;
controlling the cracking conversion in the upper reaction zone to be 55% -75% based on 100% total weight of recycled tail oil fraction and part of the refined effluent in step (2), wherein the cracking conversion = 100% -the tail oil fraction yield in the first reaction effluent; the jet fuel fraction has a cutting end point of 260-290 ℃;
In the partitioned hydrocracking reactor, the Y-type molecular sieve content of the hydrocracking catalyst in the upper reaction zone is 5 to 25wt% and the Y-type molecular sieve content of the hydrocracking catalyst in the lower reaction zone is 30 to 65wt% based on the weight of the carrier contained in the hydrocracking catalyst.
At least one of desulfurization, denitrification and aromatic saturation reactions can be performed in the hydrofining reaction zone.
Preferably, the feed oil is a straight run feed oil and/or a secondary process oil.
Preferably, the straight-run raw oil is at least one selected from straight-run diesel raw oil, straight-run wax oil raw oil and wide-fraction oil; the secondary processing oil is at least one selected from deasphalted oil, coal tar, coal direct liquefied oil, coal indirect liquefied oil, catalytic cracking light diesel oil, catalytic cracking heavy diesel oil, residual oil diesel oil and residual oil hydrogenated wax oil.
Preferably, the hydrofining reaction zone contains one or more hydrofining reactors.
Preferably, two or more catalyst beds are provided in each of the hydrofining reactors.
According to a preferred embodiment, each of the hydrofining reactors is filled with a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrofining catalyst and a hydrocracking catalyst in this order along the flow direction of the reaction liquid phase.
Preferably, the hydrofining catalyst is a supported catalyst, the carrier is alumina and/or silica-alumina, and the active metal component is at least one of non-noble metal elements of the VIB group and non-noble metal elements of the VIII group.
Preferably, in the hydrofining catalyst, the non-noble metal element of the VIII group is nickel and/or cobalt, and the non-noble metal element of the VIB group is molybdenum and/or tungsten.
Preferably, the content of the non-noble metal element of the VIII group in terms of oxide is 1 to 15wt percent, the content of the non-noble metal element of the VIB group in terms of oxide is 5 to 40wt percent, and the balance is a carrier based on the total weight of the hydrofining catalyst.
Preferably, the conditions of the hydrofining reaction at least satisfy: the hydrogen partial pressure is 3.0 MPa-20.0 MPa, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.5h -1~6h-1, and the hydrogen-oil volume ratio is 300-2000.
According to a preferred embodiment, the reactor top of the partition type hydrocracking reactor is provided with a feed inlet, the side wall of the reactor is provided with one or more than two feed inlets, and the upper part, the middle part and the lower part of the reactor are respectively provided with a tail oil reaction zone, an intensified mixing zone and a lower refined oil reaction zone.
Preferably, a diffuser and/or distributor is arranged after the feed inlet of the reactor roof of the partitioned hydrocracking reactor.
Preferably, on the reactor side wall of the partitioned hydrocracking reactor, a feed inlet extends into the reactor interior so that material can be introduced from the reactor cross section into the reaction zone. The side wall of the partitioned hydrocracking reactor is provided with a feed inlet which is uniformly or unevenly distributed on the cross section of the reactor.
Preferably, the enhanced mixing zone contains a gas-liquid phase mixing chamber, a supplemental hydrogen mixing chamber, and a distributor.
Preferably, in the zone hydrocracking reactor, one or at least two catalyst beds are provided in each of the upper and lower reaction zones independently.
Preferably, cold hydrogen is arranged between the catalyst beds.
The upper and lower reaction zones of the present invention may be charged with one or more hydrocracking catalysts.
According to a preferred embodiment, the zone hydrocracking reactor is packed in its upper reaction zone with a carbon residue removal catalyst and a hydrocracking catalyst selected from at least one of the following catalysts having the following characteristics:
The catalyst contains active metal components, heat-resistant inorganic oxide serving as a carrier and an acidic component;
The heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide; the acidic component contains a Y-type molecular sieve and optionally amorphous silicon aluminum;
The active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 15-35 wt%, the content of the VIII group metal element calculated by oxide is 2-8 wt%, and the rest is a carrier;
The content of the amorphous silicon-aluminum is 0 to 15 weight percent based on the total weight of the carrier.
Preferably, in the upper reaction zone of the partitioned hydrocracking reactor, the carbon removal catalyst comprises from 5% to 15% by volume of the total catalyst in the upper reaction zone.
The present invention is not particularly limited in the specific kind of carbon residue removal catalyst, and a person skilled in the art may perform the carbon residue removal catalyst commonly used in the art, and the following description of the present invention exemplarily provides a carbon residue removal catalyst, which should not be construed as limiting the present invention.
According to another preferred embodiment, the hydrocracking catalyst packed in the lower reaction zone of the partitioned hydrocracking reactor is selected from at least one of the catalysts having the following characteristics:
The catalyst contains active metal components, heat-resistant inorganic oxide serving as a carrier and a Y-type molecular sieve;
The heat-resistant inorganic oxide is selected from at least one of macroporous silica and macroporous alumina;
The active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; the total weight of the catalyst is taken as a reference, the content of the VIB group metal element calculated by oxide is 15-38wt%, the content of the VIII group metal element calculated by oxide is 2-8wt%, and the rest is a carrier.
Preferably, the hydrofining catalyst and the hydrocracking catalyst of the present invention are oxidation state catalysts or sulfided state catalysts.
Preferably, in step (4), the initial cut point of the tail oil fraction is 260 ℃ to 290 ℃.
Preferably, the tail oil fraction is thrown outwards in the mass proportion of 1-5 wt% (namely the total tail oil fraction obtained in the step (4)) and the rest part is recycled to the upper reaction zone of the partitioned hydrocracking reactor for reaction.
In order to regulate the temperature sensitivity of the cracking catalyst in the upper reaction zone of the zone cracking reactor and reduce the influence of fluctuation of the operation of the device, a bypass or a secondary line and a special regulating valve group are preferably arranged on the main effluent line of the refining reaction zone to introduce partial materials into the upper reaction zone of the zone cracking reactor.
The process provided below in connection with fig. 1 provides a hydrocracking process for producing heavy naphtha and jet fuel according to a preferred embodiment of the present invention.
In fig. 1, raw oil 1 is mixed with hydrogen and then enters a hydrofining reaction zone 2 for hydrofining reaction to obtain a refined effluent; introducing the tail oil fraction 13 obtained from the fractionating tower 8 and part of the refined effluent into an upper reaction zone of the partitioned hydrocracking reactor 3 to perform a first reaction to obtain a first reaction effluent; the first reaction effluent is mixed and distributed with supplementary hydrogen and the rest refined effluent introduced from the side of the partitioned hydrocracking reactor, and then enters a lower reaction zone of the partitioned hydrocracking reactor for a second reaction to obtain a second reaction effluent; and introducing the second reaction effluent into a hot high-pressure separator 4 for gas-liquid separation, further separating the obtained liquid phase by a hot low-pressure separator 5, then sending the liquid phase into a fractionating tower 8 for fractional cutting, sending the obtained gas phase into a cold high-pressure separator 6 for gas-liquid separation, separating the obtained liquid phase by a cold low-pressure separator 7, then sending the liquid phase into the fractionating tower 8 for fractional cutting, and respectively obtaining light hydrocarbon 9, light naphtha fraction 10, heavy naphtha fraction 11, jet fuel fraction 12 and recyclable tail oil fraction 13 by the fractionating tower.
The invention will be described in detail below by way of examples. In the following examples of the method of the present invention,
The yield of the heavy naphtha fraction is defined as: the weight percentage of the heavy naphtha fraction (65-155 ℃) and the mixed raw materials cut by the whole fraction product through the fractionating tower.
The yield of jet fuel fractions is defined as: the total fraction product is obtained by cutting jet fuel fraction (155-T1 ℃) and mixed raw materials by a fractionating tower; t1 is the final cutting point of jet fuel, and is controlled to be 260-290 ℃.
The yield of the tail oil fraction is defined as: the weight percentage of the tail oil fraction and the mixed raw materials cut by the whole fraction product through the fractionating tower, and the initial distillation point of the tail oil fraction cutting is controlled to be 260-290 ℃.
The properties of the raw materials used in the examples are shown in Table 1.
The hydrofining catalyst used in the examples was the same as that used in the examples and was sold under the trade name RN-410B, which was produced by Chang Ling division of China petrochemical Co., ltd. The hydrodecarbonization catalysts used are the same, and the trade mark is RCS-201, which is produced by Chang Ling division of China petrochemical Co.
TABLE 1
Example 1, example 2, example 3
In example 1, example 2 and example 3, the following hydrocracking catalysts were used:
In example 1, the upper reaction zone of the cracking reactor was charged with 10% by volume of the carbon residue removing agent and 90% by volume of the hydrocracking catalyst 1, based on 100% by volume of the catalyst charged in the upper reaction zone. The lower reaction zone of the cracking reactor is filled with catalyst A.
Composition of hydrocracking catalyst 1: based on oxide, W is 28.3 weight percent, ni is 4.5 weight percent, and the rest is a carrier; the content of the Y-type molecular sieve is 25wt percent, the content of amorphous silicon aluminum is 10wt percent and the balance is aluminum oxide based on the carrier.
Composition of hydrocracking catalyst a: based on oxide, W is 31.5 wt%, ni is 4.7 wt%, and the rest is a carrier; the Y-type molecular sieve content was 45 wt% based on the carrier.
In example 2, the upper reaction zone of the cracking reactor was charged with 10% by volume of the carbon residue removing agent and 90% by volume of the hydrocracking catalyst 2, based on 100% by volume of the catalyst charged in the upper reaction zone, and the lower reaction zone of the cracking reactor was charged with catalyst B.
Composition of hydrocracking catalyst 2: based on oxide, W is 26.7 wt%, ni is 4.8 wt%, and the rest is a carrier; the content of the Y-type molecular sieve is 22 weight percent based on the carrier, and the balance is alumina.
Composition of hydrocracking catalyst B: based on oxide, W is 28.5 weight percent, ni is 4.1 weight percent, and the rest is a carrier; the content of the Y-type molecular sieve is 35% by weight based on the carrier, and the balance is alumina.
In example 3, the upper reaction zone of the cracking reactor was charged with 10% by volume of the carbon residue removing agent and 90% by volume of the hydrocracking catalyst 3, based on 100% by volume of the catalyst charged in the upper reaction zone, and the lower reaction zone of the cracking reactor was charged with the catalyst C.
Composition of hydrocracking catalyst 3: based on oxide, W is 29.5 wt%, ni is 4.7 wt%, and the rest is a carrier; the content of the Y-type molecular sieve is 20 weight percent based on the carrier, the mass fraction of amorphous silicon aluminum is 5 percent, and the balance is aluminum oxide.
Composition of hydrocracking catalyst C: based on oxide, W is 31.5 wt%, ni is 4.8 wt%, and the rest is a carrier; the content of the Y-type molecular sieve is 40% by weight based on the carrier, and the balance is alumina.
Raw materials 1, 2 and 3 shown in table 1 are respectively mixed with hydrogen and then sequentially pass through a hydrofining reaction zone, a small amount of effluent of the refining reaction zone is mixed with circulating tail oil and then enters an upper reaction zone of a partition type cracking reactor for reaction, the other effluent of the refining reaction zone enters an intensified mixing chamber of the partition type hydrocracking reactor from the side of the reactor, and after being uniformly mixed with circulating hydrogen and the upper reaction effluent, the mixture enters a lower reaction zone of the partition type cracking reactor for reaction through a distributor, the obtained reaction products are separated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel and tail oil fraction, and the technological condition parameters and product distribution data of the reaction are listed in table 2.
TABLE 2
As can be seen from the data in Table 2, in examples 1 to 3, the yields of heavy naphtha, which were obtained by the reaction in the zone cracking reactor, were 41.0%, 41.8% and 39.7%, respectively, and the yields of jet fuel, which were obtained by the reaction in the zone cracking reactor, were 46.6%, 45.6% and 45.3%, respectively, using the straight run feedstock or the blended feedstock as claimed in the present invention. It is apparent from this that the partition type cracking reactor and hydrocracking method of the present invention can be used to obtain a heavy naphtha fraction and a jet fuel fraction in a large ratio with high efficiency.
Example 4, example 5, comparative example 1
In example 4 and comparative example 1, the same hydrocracking catalyst as in example 1 was used.
In example 5, the upper portion of the cracking reactor was charged with 8% by volume of the carbon residue removing agent and 92% by volume of the hydrocracking catalyst 4, based on 100% by volume of the catalyst charged in the upper reaction zone, and the lower portion of the cracking reactor was charged with catalyst D.
Composition of hydrocracking catalyst 4: based on oxide, W is 30.5 wt%, ni is 4.7 wt%, and the rest is a carrier; the mass fraction of the Y-type molecular sieve is 23% by weight based on the carrier, the mass fraction of the amorphous silicon aluminum is 15%, and the balance is aluminum oxide.
Composition of hydrocracking catalyst D: based on oxide, W is 32.5 wt%, ni is 4.8 wt%, and the rest is a carrier; the mass fraction of the Y-type molecular sieve is 50% by weight based on the carrier, and the balance is alumina.
In example 4, example 5 and comparative example 1, raw materials 1, 4 and 5 were respectively mixed with hydrogen and then sequentially passed through a hydrofinishing reaction zone, a small amount of effluent from the refining reaction zone was mixed with circulating tail oil and then entered into an upper reaction zone of a zone-type cracking reactor for reaction, the other effluent from the refining reaction zone was entered into an intensified mixing chamber of the zone-type hydrocracking reactor from the side of the reactor, and after being uniformly mixed with circulating hydrogen and the upper reaction effluent, entered into a lower reaction zone of the zone-type cracking reactor through a distributor for reaction, and the obtained reaction products were separated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel and tail oil fraction, and the process condition parameters and product distribution data of the reaction are shown in table 3.
TABLE 3 Table 3
As can be seen from the data in Table 3, the yields of the heavy naphtha products of the reactions conducted in the zone cracking reactors using the straight run feedstock or the blended feedstock as claimed in the present invention in examples 4 and 5 were 38.5% and 37.3%, respectively, and the yields of the jet fuel products were 48.8% and 50.5%, respectively. It is apparent from this that the partition type cracking reactor and hydrocracking method of the present invention can be used to obtain a heavy naphtha fraction and a jet fuel fraction in a large ratio with high efficiency.
As can be seen from the data in table 3, with the partition type hydrocracking reactor provided by the present invention, comparative example 1 also obtained a higher jet fuel fraction yield of 50.3% with poor feedstock 6; however, the nitrogen mass fraction of the adopted raw oil is too high, so that the selectivity of the conversion of the circulating tail oil into the heavy naphtha is unfavorable, and the yield of the heavy naphtha is reduced by about 32.5%; on the other hand, too high mass fraction of raw material nitrogen increases the reaction severity, which is unfavorable for long-period operation of the device.
Example 6, comparative example 2, comparative example 3
In example 6, comparative example 2 and comparative example 3, the same hydrocracking catalyst loading scheme as in example 2 was used.
In example 6, comparative example 2 and comparative example 3, raw material 2 was mixed with hydrogen and then sequentially passed through a hydrofinishing reaction zone, a small amount of effluent from the refining reaction zone was mixed with circulating tail oil and then entered into an upper reaction zone of a partition type cracking reactor for reaction, the remaining effluent from the refining reaction zone was entered into an intensified mixing chamber of the partition type hydrocracking reactor from the side of the reactor, and after being uniformly mixed with circulating hydrogen and the upper reaction effluent, entered into a lower reaction zone of the partition type cracking reactor through a distributor for reaction, and the obtained reaction product was separated to obtain light naphtha fraction, heavy naphtha fraction, jet fuel and tail oil fraction, and the technological condition parameters and product distribution data of the reaction are shown in table 4.
TABLE 4 Table 4
As can be seen from the data in Table 4, in example 6, under the working condition of processing the straight-run diesel oil with higher mass ratio, the yields of the heavy naphtha fraction and the jet fuel fraction are 40.9% and 46.8%, respectively, by using the partition type hydrocracking reactor and the hydrocracking method of the present invention, it is shown that the heavy naphtha fraction and the jet fuel fraction can be obtained in a high efficiency and large proportion.
As can be seen from the data in table 4, the yields of the heavy naphtha fraction and the jet fuel fraction were 42.5% and 40.6% and 42.3% respectively, under the working conditions of processing the raw materials of the straight-run diesel with higher mass ratios, by using the jet fuel cutting schemes of the products other than the partition type hydrocracking reactor and the hydrocracking method of the present invention, in comparative example 2 and comparative example 3.
It should be noted that, in comparative example 2, the cutting scheme for reducing the cut end point of the jet fuel was adopted, the jet fuel yield was only 42.3%, the jet fuel yield was insufficient, and the jet fuel freezing point was-58.6 ℃ and still had a higher deep drawn space, thus indicating that the adoption of the cutting scheme for reducing the cut end point of the jet fuel was disadvantageous for realizing the maximization of the jet fuel yield.
In comparative example 3, the jet fuel yield was increased to 47.7% by using a cleavage protocol that increased the cleavage endpoint of the jet fuel, but the increase in cleavage endpoint of the jet fuel resulted in a corresponding increase in the freeze point of the jet fuel of-45.0 ℃ to disqualify the freeze point of the jet fuel (No. 47.0 ℃).
Example 7, comparative example 4, comparative example 5
In example 7, comparative example 4 and comparative example 5, the same hydrocracking catalyst loading scheme as in example 1 was used.
In the embodiment 7, the comparative example 4 and the comparative example 5, the raw material 1 and hydrogen are mixed and then sequentially pass through a hydrofining reaction zone, a small amount of effluent of the refining reaction zone and circulating tail oil are mixed and then enter an upper reaction zone of a partition type cracking reactor for reaction, the other effluent of the refining reaction zone enters an enhanced mixing chamber of the partition type hydrocracking reactor from the side of the reactor, and after being uniformly mixed with circulating hydrogen and the upper reaction effluent, the mixture enters a lower reaction zone of the partition type cracking reactor for reaction through a distributor, and the obtained reaction products are separated and then light naphtha fraction, heavy naphtha fraction, jet fuel fraction and tail oil fraction are obtained; in the reaction process, the conversion depth of the fresh material passing through once or the circulating tail oil quantity are controlled to be different, and the technological condition parameters and the product distribution data of the main reactions of different circulating tail oil quantities are shown in Table 5.
TABLE 5
As can be seen from the data in Table 5, in example 7, the partitioned hydrocracking reactor and the hydrocracking method provided by the invention are adopted, the circulating tail oil amount is controlled to be 35%, and the yields of the heavy naphtha and the jet fuel are 38.3% and 49.4%, respectively.
The comparison example 4 and the comparison example 5 respectively control the circulating tail oil quantity to be 13wt% and 65wt%, the corresponding heavy naphtha yield to be 41.3% and 33.6%, and the jet fuel yield to be 42.3% and 52.8%, and it is to be noted that in the comparison example 4, in order to control the lower circulating tail oil quantity, the fresh raw materials are required to adopt a higher one-pass conversion depth, so that the reaction condition is harsh, the long-period operation of the device is affected, and the excessive one-pass conversion rate of the fresh raw materials also can bring about the rapid increase of the byproduct yield of light naphtha oil and the like, so that the yields of the main products heavy naphtha and jet fuel are reduced and the ineffective hydrogen consumption is high; in contrast, in comparative example 5, although higher jet fuel yields were obtained with higher recycle ratios, the increase in recycle tail oil correspondingly increased the energy consumption and operating costs of the plant and reduced the selectivity to heavy naphtha, and therefore the process was not economically justified.
Example 8, comparative example 6 and comparative example 7
In example 8, comparative example 6 and comparative example 7, the same hydrocracking catalyst loading scheme as in example 4 was used.
In example 8, comparative example 6 and comparative example 7, the raw material 4 was mixed with hydrogen and then sequentially passed through a hydrofining reaction zone, a small amount of effluent from the refining reaction zone was mixed with circulating tail oil and then introduced into the upper reaction zone of the partitioned hydrocracking reactor to react, the remaining effluent from the refining reaction zone was introduced into the enhanced mixing chamber of the partitioned hydrocracking reactor from the side of the reactor, and after being uniformly mixed with circulating hydrogen and the upper reaction effluent, introduced into the lower reaction zone of the partitioned hydrocracking reactor through a distributor to react, the obtained reaction product was separated to obtain a light naphtha fraction, a heavy naphtha fraction, a jet fuel and a tail oil fraction, and the mass ratio of refined oil removed from the upper reaction zone of the partitioned hydrocracking reactor was controlled to be different in the reaction process, and the obtained process condition parameters and product distribution data are shown in table 6.
TABLE 6
As can be seen from the data in table 6, example 8 uses the partitioned hydrocracking reactor and hydrocracking process of the present invention, and the yields of the heavy naphtha fraction and the jet fuel fraction are 38.7% and 47.8%, respectively, thus indicating that the partitioned hydrocracking reactor and the hydrocracking process of the present invention can produce heavy naphtha and jet fuel in a high efficiency and large scale.
As can be seen from the data in table 6, the refined oil quality ratio and cracking conversion in the upper reaction zone of the de-zoned cracking reactor of comparative example 6 and comparative example 7 were not within the scope of the present invention, and were 2.0% and 38.0%, respectively, the corresponding heavy naphtha fraction yields were 43.2% and 33.3%, respectively, and the jet fuel fraction yields were 39.2% and 48.5%, respectively; in the comparative example 6, the refined oil quality ratio in the upper reaction zone of the partition reactor is lower, which brings about the reduction of the selectivity of heavy naphtha and jet fuel which are main products in the upper reaction zone, and meanwhile, the problems of low cracking reaction operation temperature, mismatching with the lower reaction zone operation temperature, weak capability of resisting the fluctuation of the operation of the device and the like exist; the comparative example 7 shows that the ratio of the quality of refined oil in the upper reaction zone of the partition type hydrocracking reactor is too high, and the too high ratio of refined oil not only brings about the reduction of the selectivity of converting the cycle tail oil into heavy naphtha.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A hydrocracking process for producing heavy naphtha and jet fuel, the process comprising:
(1) The raw oil and hydrogen are mixed and enter a hydrofining reaction zone to carry out hydrofining reaction, so as to obtain refined effluent, wherein the density of the raw oil is 0.84g/cm 3~0.98g/cm3, the nitrogen content is 200-2500 mug/g, the final distillation point is 360-560 ℃, and the aromatic hydrocarbon content is 25-85 wt%;
(2) Introducing tail oil obtained from the fractionation unit and part of the refined effluent into an upper reaction zone of a partitioned hydrocracking reactor to perform a first reaction to obtain a first reaction effluent;
(3) The first reaction effluent, the supplementary hydrogen and the remaining refined effluent of the hydrofining reaction zone are mixed and distributed and then enter the lower reaction zone of the partitioned hydrocracking reactor to carry out a second reaction, so as to obtain a second reaction effluent;
(4) Introducing the second reaction effluent into a fractionation unit for separation to obtain a light naphtha fraction, a heavy naphtha fraction, a jet fuel fraction and a tail oil fraction capable of being recycled to step (2),
In the upper reaction zone of the partitioned hydrocracking reactor, the refined effluent introduced into the upper reaction zone of the partitioned hydrocracking reactor accounts for 5-30 wt% of the total refined effluent obtained in step (1);
The recycled tail oil fraction accounts for 30% -55% of the total weight of the raw oil in the step (1) which is 100%;
Controlling the cracking conversion rate in the upper reaction zone to be 55% -75% based on the total weight of the recycled tail oil fraction and part of the refined effluent in the step (2) being 100%, wherein the cracking conversion rate=100% -the yield of the tail oil fraction in the first reaction effluent; the final cutting point of the jet fuel fraction is 260-290 ℃;
In the partitioned hydrocracking reactor, the weight of a carrier contained in the hydrocracking catalyst is taken as a reference, the Y-type molecular sieve content of the hydrocracking catalyst in the upper reaction zone is 5-25 wt%, and the Y-type molecular sieve content of the hydrocracking catalyst in the lower reaction zone is 35-65 wt%;
The reactor top of the partition type hydrocracking reactor is provided with a feed inlet, the side wall of the reactor is provided with one or more than two feed inlets, and the upper part, the middle part and the lower part of the reactor are respectively provided with a tail oil reaction zone, a reinforced mixing zone and a lower refined oil reaction zone;
a diffuser and/or a distributor are arranged behind a feed inlet of the reactor top of the partitioned hydrocracking reactor;
On the side wall of the reactor of the partitioned hydrocracking reactor, a feed inlet extends into the reactor so that materials can be introduced into a reaction zone from the cross section of the reactor;
The intensified mixing region comprises a gas-liquid phase mixing chamber, a supplementary hydrogen mixing chamber and a distributor.
2. The method of claim 1, wherein the feedstock is a straight run feedstock and/or a secondary process oil.
3. The method of claim 2, wherein the straight run feedstock is selected from at least one of straight run diesel feedstock, straight run wax oil feedstock, and wide cut oil; the secondary processing oil is at least one selected from deasphalted oil, coal tar, coal direct liquefied oil, coal indirect liquefied oil, catalytic cracking light diesel oil, catalytic cracking heavy diesel oil, residual oil diesel oil and residual oil hydrogenated wax oil.
4. The process of any of claims 1-3, wherein the hydrofinishing reaction zone contains one or more hydrofinishing reactors.
5. The process of claim 4, wherein two or more catalyst beds are disposed in each of the hydrofinishing reactors.
6. The process according to claim 4, wherein each of the hydrorefining reactors is filled with a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrorefining catalyst and a hydrocracking catalyst in this order in the direction of the flow of the reaction liquid phase.
7. The method according to claim 6, wherein 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 non-noble metal elements and group VIII non-noble metal elements.
8. The process according to claim 7, wherein in the hydrofinishing catalyst the group VIII non-noble metal element is nickel and/or cobalt and the group VIB non-noble metal element is molybdenum and/or tungsten.
9. The method according to claim 7 or 8, wherein the content of the group VIII non-noble metal element in terms of oxide is 1wt% to 15wt%, the content of the group VIB non-noble metal element in terms of oxide is 5wt% to 40wt%, and the balance is a carrier, based on the total weight of the hydrofining catalyst.
10. A process according to any one of claims 1 to 3, wherein the hydrofinishing reaction conditions are at least: the hydrogen partial pressure is 3.0-20.0 MPa, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.5h -1~6h-1, and the hydrogen-oil volume ratio is 300-2000.
11. A process according to any one of claims 1 to 3, wherein in the partitioned hydrocracking reactor, one or at least two catalyst beds are provided independently in each of the upper and lower reaction zones.
12. The process of claim 11, wherein the partitioned hydrocracking reactor is packed with a carbon residue removal catalyst and a hydrocracking catalyst in an upper reaction zone, the hydrocracking catalyst being selected from at least one of the following catalysts:
The catalyst contains active metal components, heat-resistant inorganic oxide serving as a carrier and an acidic component;
The heat-resistant inorganic oxide is selected from at least one of silicon oxide and aluminum oxide; the acidic component contains a Y-type molecular sieve and optionally amorphous silicon aluminum;
The active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; based on the total weight of the catalyst, the content of the VIB group metal element calculated by oxide is 15-38wt%, the content of the VIII group metal element calculated by oxide is 2-8wt%, and the rest is a carrier;
the content of the amorphous silicon-aluminum is 0 to 15 weight percent based on the total weight of the carrier.
13. The process of claim 11, wherein the hydrocracking catalyst packed in the lower reaction zone of the partitioned hydrocracking reactor is selected from at least one of the following catalysts having the following characteristics:
The catalyst contains active metal components, heat-resistant inorganic oxide serving as a carrier and a Y-type molecular sieve;
The heat-resistant inorganic oxide is selected from at least one of macroporous silica and macroporous alumina;
the active metal component is at least two metal elements selected from a group VIB metal element and a group VIII metal element; the total weight of the catalyst is taken as a reference, the content of the metal element of the VIB group is 15-35 wt% based on the oxide, the content of the metal element of the VIII group is 2-8 wt% based on the oxide, and the rest is the carrier.
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