CN116064136B - Wax oil hydrocracking and diesel hydrofining combined process and system - Google Patents
Wax oil hydrocracking and diesel hydrofining combined process and system Download PDFInfo
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- CN116064136B CN116064136B CN202111277040.7A CN202111277040A CN116064136B CN 116064136 B CN116064136 B CN 116064136B CN 202111277040 A CN202111277040 A CN 202111277040A CN 116064136 B CN116064136 B CN 116064136B
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 276
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 257
- 239000000463 material Substances 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 239000001257 hydrogen Substances 0.000 claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000007791 liquid phase Substances 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 27
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 62
- 239000002994 raw material Substances 0.000 claims description 44
- 239000012071 phase Substances 0.000 claims description 19
- 238000005194 fractionation Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 98
- 239000002283 diesel fuel Substances 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 14
- 239000002808 molecular sieve Substances 0.000 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 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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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
本发明公开了一种蜡油加氢裂化与柴油加氢精制组合工艺及系统，所述组合工艺包括如下步骤：（1）柴油原料和氢气反应后得到第1料流，第1料流进一步经分馏后得到第1料流轻馏分和第1料流重馏分；（2）蜡油原料和氢气反应完成后得到第2料流；（3）第2料流与第1料流重馏分混合进入第一加氢裂化反应区，反应生成物经分离后得到气体、石脑油和第3料流；（4）第3料流与第1料流轻馏分混合进入第二加氢裂化反应区，反应完成后得到的第4料流循环与液相物料一起进行处理。还提供一种实现上述工艺的系统。所述组合工艺在实现柴油完全转化为高附加值轻石脑油、重石脑油的同时解决了现有两段加氢裂化工艺中重石脑油选择性低、及随着运转周期延长催化剂活性明显降低的技术问题，同时可以得到满足指标性质要求的目的产品。
The present invention discloses a combined process and system for wax oil hydrocracking and diesel hydrofining, wherein the combined process comprises the following steps: (1) a first stream is obtained after a diesel feedstock reacts with hydrogen, and the first stream is further fractionated to obtain a light fraction of the first stream and a heavy fraction of the first stream; (2) a second stream is obtained after the reaction of the wax oil feedstock and hydrogen is completed; (3) the second stream and the heavy fraction of the first stream are mixed and enter a first hydrocracking reaction zone, and the reaction product is separated to obtain gas, naphtha and a third stream; (4) the third stream and the light fraction of the first stream are mixed and enter a second hydrocracking reaction zone, and the fourth stream obtained after the reaction is completed is circulated and processed together with the liquid phase material. A system for implementing the above process is also provided. The combined process solves the technical problems of low heavy naphtha selectivity and significant reduction in catalyst activity with the extension of the operating cycle in the existing two-stage hydrocracking process while achieving complete conversion of diesel into high-value-added light naphtha and heavy naphtha, and can also obtain a target product that meets the index property requirements.
Description
Technical Field
The invention belongs to the field of petroleum refining, and particularly relates to a wax oil hydrocracking and diesel hydrogenation combined treatment process and system.
Background
With the adjustment of energy structures, the demands of people for chemicals such as BTX are increasing increasingly, and the demands for traditional fuel products are decreasing year by year, especially the demands for diesel products are greatly reduced. Related research institutions and refining enterprises are widely developing oil refining chemical process technologies for producing more chemical raw materials and reducing the diesel-gasoline ratio.
Wax oil two-stage hydrocracking process is the latest research and industrial achievement for realizing the maximum production of heavy naphtha in the hydrogenation field. In the conventional wax oil two-stage hydrocracking process, the heavy naphtha and light naphtha and other light products are extracted from the first stage hydrocracking product through a fractionating tower, the fraction with the distillation range larger than that of the heavy naphtha enters a second hydrocracking reactor for reaction, the second stage hydrocracking reactant is circulated to the fractionating tower to extract the heavy naphtha and the light naphtha and other light products, and the fraction with the distillation range larger than that of the heavy naphtha continuously enters the second hydrocracking reactor, so that the maximum heavy naphtha product is realized. However, the heavy naphtha selectivity of the conventional wax oil two-stage hydrocracking process has a limit value, and the heavy naphtha yield is below 70%. The related researches are mainly focused on improving the activity stability of the catalyst, but the problems are difficult to solve by only relying on the iterative upgrading of the performance of the hydrocracking catalyst.
CN1955263a discloses a method for hydrocracking poor quality catalytic cracking diesel oil and wax oil, the idea of the patent is to fully utilize the characteristic that catalytic diesel oil contains heavy aromatic hydrocarbon to increase the aromatic hydrocarbon potential content of hydrocracking heavy naphtha product, thereby reducing the diesel-gasoline ratio of enterprises.
CN101089140A discloses a two-stage hydrocracking process method, which is characterized in that a hydrogenation column pretreatment reactor is filled with a bulk phase catalyst with high hydrogenation saturation activity, the catalyst contains three metal components of Mo, W and Ni, the catalyst exists in a composite oxide form of NixWyOz before vulcanization, z=x+3y, the Mo exists in an oxide form of MoO 3, the ratio of x and y in the composite oxide NixWyOz is 1: 8~8:1, the weight ratio of the composite oxide NixWyOz to the oxide MoO 3 is 1:10-10:1, the total weight content of the composite oxide NixWyOz and the oxide MoO 3 in the bulk phase catalyst is 40% -100%, and the distillation point of the treated raw materials of the two-stage hydrocracking process can be effectively improved, and the product quality is improved.
CN107344112a discloses a hydrocracking catalyst for producing high-quality catalytic reforming raw materials, a preparation method and application thereof, macroporous alumina powder, a modified USY molecular sieve, beta zeolite and active metal components are uniformly mixed, then acid solution is added, and after full rolling, forming is carried out, and then drying and roasting are carried out, thus obtaining the hydrocracking catalyst. The hydrocracking catalyst can improve the selectivity of heavy naphtha and the property of hydrocracking products.
Disclosure of Invention
The applicant finds in the research process that the heavy naphtha yield of the wax oil two-stage hydrocracking device which aims at producing heavy naphtha in a large amount has a bottleneck and the selectivity of the heavy naphtha is reduced when the heavy naphtha is operated for a long period. After research, the former is found that, because the cracking path of the reactants is uncontrollable in the conventional two-stage hydrocracking process, the distillation ranges in the reactants react almost simultaneously, and the pursuit of the maximum production of heavy naphtha tends to increase the light naphtha yield. Moreover, with longer operating cycles, heavy naphtha selectivity will be due to the low sulfur content in the secondary hydrocracking reaction feedstock, and long term operation will result in "sulfur loss" of the secondary hydrocracking catalyst resulting in reduced activity. Meanwhile, the applicant finds that the hydrocracking reaction has a dynamic inhibition guiding phenomenon in a cracking reaction area in the research process, namely, substances with the distillation ranges of A-B ℃ are introduced in the hydrocracking process of the full-fraction reactant to promote the substances with the distillation ranges of A-B ℃ to preferentially react with light components (< A ℃), and inhibit the substance reactions with the distillation ranges of > B ℃. The applicant is based on this principle to improve the selectivity of the target product by optimizing the hydrocracking reaction path.
Aiming at the defects existing in the prior art, the invention mainly aims to provide a wax oil two-stage hydrocracking and diesel hydrofining combined process and system. The combined process solves the technical problems of low heavy naphtha selectivity and obviously reduced catalyst activity along with the prolonged operation period in the existing two-stage hydrocracking process while realizing the complete conversion of diesel oil into high-added-value light naphtha and heavy naphtha, and can obtain a target product meeting the index property requirement.
The first aspect of the invention provides a wax oil hydrocracking and diesel hydrofining combined process, which comprises the following steps:
(1) Under the condition of hydrogen, the diesel raw material enters a diesel hydrogenation reaction zone for reaction, and a1 st material flow is obtained after the reaction is completed;
(2) The 1 st material flow is further fractionated to obtain a1 st material flow light fraction and a1 st material flow heavy fraction;
(3) Under the condition of hydrogen, feeding a wax oil raw material into a hydrocracking pretreatment reaction zone, and obtaining a 2 nd material flow after the reaction is completed;
(4) Mixing the 2 nd material flow obtained in the step (3) with the 1 st material flow heavy fraction obtained in the step (2) in the presence of hydrogen, and then entering a first hydrocracking reaction zone, wherein a gas-liquid separation is carried out on a reaction product to obtain a gas-phase material and a liquid-phase material, and further fractionation is carried out on the liquid-phase material to obtain gas, naphtha (which can be further separated into light naphtha and heavy naphtha) and a 3 rd material flow;
(5) And (3) mixing the 3 rd material flow obtained in the step (4) with the 1 st material flow light fraction obtained in the step (2), and feeding the mixture into a second hydrocracking reaction zone, wherein the 4 th material flow obtained after the reaction is completed is circulated and treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the 4 th material flow obtained in the step (5) is further fractionated to obtain a4 th material flow light fraction and a4 th material flow heavy fraction, the segmentation temperature of the 4 th material flow light fraction and the 4 th material flow heavy fraction is 100-250 ℃, preferably 120-200 ℃, wherein the 4 th material flow light fraction can be recycled and treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone, and the 4 th material flow heavy fraction can be recycled and treated together with a diesel raw material.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined process, the distillation range of the diesel raw material is generally 160-400 ℃, the sulfur and nitrogen content is not particularly required, the sulfur content is not more than 1.8wt% and the nitrogen content is not more than 500ppm in general, and the aromatic hydrocarbon content is 10-60 wt%, preferably 20-50 wt%. Further, the diesel fuel raw material can be one or a mixture of several of straight-run diesel fuel, catalytic diesel fuel, hydrogenation stable diesel fuel, coking diesel fuel and the like.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the splitting temperature of the 1 st material flow light fraction and the 1 st material flow heavy fraction is 150-360 ℃, preferably 200-340 ℃.
Furthermore, in the wax oil hydrocracking and diesel oil hydrofining combined process, the wax oil raw material is one or more of normal pressure wax oil, reduced pressure wax oil, deep drawing wax oil and boiling bed wax oil, the distillation range of the wax oil raw material is generally 230-600 ℃, and the sulfur and nitrogen content and composition of the wax oil raw material have no special requirements.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the diesel hydrogenation reaction zone comprises at least one hydrogenation reactor, at least one hydrofining catalyst is arranged in the hydrogenation reactor, the hydrofining catalyst generally comprises a hydrogenation active metal component and a carrier, the hydrogenation active metal component can be one or more of metal elements of VI, VII or VIII, particularly can be selected from two or more metals of Co, mo, ni, W as hydrogenation active metal components, and the carrier can be generally inorganic refractory oxides such as alumina, silica and the like. The hydrofinishing catalyst may be selected from commercially available products or prepared as desired as is common in the art. Particularly, the catalyst can be selected from commercial diesel hydrofining catalysts developed by China petrochemical industry Co., ltd, which are used for smoothing the commercial diesel hydrofining catalysts of FHUDS-3, FHUDS-6, FHUDS-7, FHUDS-8 and the like of the institute of petrochemical industry (FRIPP).
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined process, at least one hydrogenation reactor is arranged in the hydrocracking pretreatment reaction zone, and the hydrogenation reactor contains at least one hydrocracking pretreatment catalyst, preferably 2-4 hydrocracking pretreatment catalysts. In general, the hydrocracking pretreatment catalyst comprises a carrier and a hydrogenation metal component supported on the carrier, wherein the hydrogenation metal component can be at least one metal element selected from VI, VII or VIII groups, and preferably two or more metals selected from Co, mo, ni, W are active components. The catalyst can be selected from commercial hydrocracking pretreatment catalysts such as FF-33, FF-46, FF-66, FTX and the like which are developed by China petrochemical industry Co-Ltd and are smoothed by the petrochemical industry institute, and can also be prepared according to the common sense in the field according to the requirement.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, at least one hydrocracking reactor is arranged in the first hydrocracking reaction zone, at least one hydrocracking catalyst is contained in the hydrocracking reactor, the hydrocracking catalyst comprises a hydrogenation component and a carrier, the hydrogenation component can be one or more of metal elements of VI groups, VII groups or VIII groups, preferably two or more of Co, mo, ni, W groups, and the carrier comprises at least one of a Y molecular sieve, a modified Y molecular sieve, alumina and amorphous silicon aluminum. Generally, the content of the hydrogenation component is 10% -40% calculated by oxide based on the weight of the catalyst. The content of the Y molecular sieve in the catalyst is 5% -25%, preferably 8% -16%. The catalyst can be specifically selected from commercial hydrocracking catalysts such as FC-50, FC-14 and the like developed by China petrochemical industry Co., ltd (FRIPP), and can also be prepared according to the common sense in the field as required.
Further, as a specific embodiment, the second hydrocracking reaction zone is provided with at least one hydrocracking reactor, the hydrocracking reactor contains at least one hydrocracking catalyst, the hydrocracking catalyst comprises a hydrogenation component and a carrier, the hydrogenation component can be one or more of group VI, group VII or group VIII metal elements, preferably two or more of Co, mo, ni, W, and the carrier comprises at least one of a Y molecular sieve, a modified Y molecular sieve, alumina and amorphous silica-alumina. Generally, the content of the hydrogenation component is 10% -40% calculated by oxide based on the weight of the catalyst. The content of the Y molecular sieve in the catalyst is 5% -25%, preferably 8% -16%. The catalyst can be specifically selected from commercial hydrocracking catalysts such as FC-76, FC-52 and the like developed by China petrochemical industry Co., ltd (FRIPP), and can also be prepared according to the common sense in the field as required.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined process, the gas phase material obtained by gas-liquid separation of the reaction product of the first hydrocracking reaction zone is purified and compressed by a recycle hydrogen compressor, and the recycle hydrogen obtained after compression can enter the diesel hydrogenation reaction zone, the hydrocracking pretreatment reaction zone, the first hydrocracking reaction zone and the second hydrocracking reaction zone for use, and the general purification treatment comprises removal of hydrogen sulfide in the gas phase material, and the specific purification treatment process can adopt any one of the existing processes capable of removing hydrogen sulfide.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the reaction conditions of the diesel hydrogenation reaction zone are generally as follows, the reaction pressure is 1.0-9.0 MPa, preferably 3.0-8.5 MPa, the reaction temperature is 260-400 ℃, preferably 300-360 ℃, the volume space velocity is 0.1-10.0 h -1, preferably 0.6-1.5 h -1, and the hydrogen oil volume ratio is 200-2100, preferably 600-2000.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the reaction condition of the hydrocracking pretreatment reaction zone is generally that the reaction pressure is 6.0-20.0 MPa, preferably 8.0-16.5 MPa, the reaction temperature is 250-450 ℃, preferably 320-400 ℃, the volume airspeed is 0.2-12.0 h -1, preferably 0.6-2.0 h -1, and the hydrogen oil volume ratio is 600-2100, preferably 300-2000.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the reaction condition of the first hydrocracking reaction zone is generally that the reaction pressure is 6.0-20.0 MPa, preferably 8.0-19.5 MPa, the reaction temperature is 280-420 ℃, preferably 330-410 ℃, the volume space velocity is 0.1-5.0 h -1, preferably 0.5-1.2 h -1, and the hydrogen oil volume ratio is 500-1800, preferably 600-1600.
Further, in the wax oil hydrocracking and diesel hydrofining combined process, the reaction condition of the second hydrocracking reaction zone is generally that the reaction pressure is 6.0-20.0 MPa, preferably 8.0-19.5 MPa, the reaction temperature is 250-400 ℃, preferably 320-400 ℃, the volume space velocity is 0.4-7.0 h -1, preferably 0.6-3.0 h -1, and the hydrogen oil volume ratio is 200-2000, preferably 600-1600.
The second aspect of the invention provides a wax oil hydrocracking and diesel hydrofining combined treatment system, which comprises:
The diesel hydrogenation reaction zone is used for receiving diesel raw materials and hydrogen, and obtaining a1 st material flow after reaction;
a first fractionation unit for receiving a1 st stream from the diesel hydrogenation reaction zone, after separation, to obtain a1 st stream light fraction and a1 st stream heavy fraction;
The hydrocracking pretreatment reaction zone is used for receiving wax oil raw materials and hydrogen, and obtaining a2 nd material flow after the reaction is completed;
A first hydrocracking reaction zone for receiving hydrogen, a 2 nd stream from the hydrocracking pretreatment reaction zone, and a1 st stream heavy fraction from the first fractionation column, after reaction to obtain a reaction product;
The gas-liquid separation unit is used for receiving a reaction product from the first hydrocracking reaction zone and separating to obtain a gas-phase material and a liquid-phase material;
a second fractionation unit for receiving the gas phase material from the gas-liquid separation unit, and separating to obtain gas, naphtha (which may be further separated into light naphtha and heavy naphtha as needed) and a 3 rd stream;
And the second hydrocracking reaction zone is used for receiving hydrogen and a3 rd stream from the second fractionation unit, a 4 th stream is obtained after the reaction, and the 4 th stream is communicated with the inlet of the second fractionation unit through a pipeline.
Further, the wax oil hydrocracking and diesel hydrofining combined treatment system further comprises a third fractionating unit, wherein the third fractionating unit is used for receiving a 4 th material flow from the second hydrocracking reaction zone, fractionating the 4 th material flow to obtain a 4 th material flow light fraction and a 4 th material flow heavy fraction, the dividing temperature of the 4 th material flow light fraction and the 4 th material flow heavy fraction is 100-250 ℃, preferably 120-200 ℃, the 4 th material flow light fraction is communicated with an inlet of the second fractionating unit through a pipeline and is treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone, and the 4 th material flow heavy fraction is communicated with an inlet of the diesel hydrogenation reaction zone through a pipeline and is treated together with a diesel raw material.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined treatment system, the system further comprises a purification unit, wherein the purification unit is used for receiving the gas phase material from the gas-liquid separation unit, purified hydrogen is obtained after treatment, the purified hydrogen can enter the diesel hydrogenation reaction zone, the hydrocracking pretreatment reaction zone, the first hydrocracking reaction zone and the second hydrocracking reaction zone for use after being compressed by the circulating hydrogen compressor, the general purification unit is used for removing hydrogen sulfide in the gas phase material, and the specific purification unit can adopt any one of the existing hydrogen sulfide removing processes.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined treatment system, the diesel hydrogenation reaction zone comprises at least one hydrogenation reactor, and at least one hydrofining catalyst is arranged in the hydrogenation reactor.
Furthermore, in the wax oil hydrocracking and diesel oil hydrofining combined treatment system, the hydrocracking pretreatment reaction zone is provided with at least one hydrogenation reactor, and the hydrogenation reactor contains at least one hydrocracking pretreatment catalyst.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined treatment system, the first hydrocracking reaction zone is provided with at least one hydrocracking reactor, and the hydrocracking reactor contains at least one hydrocracking catalyst.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined treatment system, the second hydrocracking reaction zone is provided with at least one hydrocracking reactor, and the hydrocracking reactor contains at least one hydrocracking catalyst.
Furthermore, in the wax oil hydrocracking and diesel hydrofining combined treatment system, the gas-liquid separation unit generally comprises a hot high-pressure separator, a hot low-pressure separator, a cold high-pressure separator and a cold low-pressure separator, and the connection modes between the separators and the fractionating tower are all the same as the existing connection modes in the prior art, so that the person skilled in the art can freely select the connection modes according to actual needs.
Compared with the prior art, the wax oil hydrocracking and diesel hydrofining combined process and system provided by the invention have the following characteristics:
1. The applicant finds that in the research, the hydrocracking reaction has a dynamic inhibition guiding phenomenon, and heavy refined diesel oil obtained after the diesel oil raw material is hydrofined is introduced into the first hydrocracking reaction zone by utilizing the phenomenon, so that heavy diesel oil components in wax oil raw materials mainly reacted in the first hydrocracking reaction zone are promoted to be efficiently converted into light diesel oil, heavy naphtha and light naphtha, and the reaction of converting tail oil fractions in the wax oil raw materials into heavy components is inhibited, thereby improving the heavy naphtha yield in the first hydrocracking reaction zone. The heavy diesel oil fraction in the conventional two-stage hydrocracking reactor is relatively high in polarity and is preferentially adsorbed on a catalyst to be converted into a light diesel oil component, and the generated light diesel oil fraction does not enter a product distillation range, so that the light diesel oil fraction can circularly enter a two-stage hydrocracking zone, excessive cracking is easy to occur to increase light naphtha and gas products, and the yield of the heavy naphtha and the yield of liquefied products are further reduced. The light refined diesel oil obtained by hydrofining the diesel oil raw material is introduced into the second hydrocracking reaction zone, so that the light diesel oil components in the second hydrocracking reaction zone are promoted to be efficiently converted into heavy naphtha and light naphtha, and the yield of the heavy naphtha is further improved.
2. Along with the extension of the operation period, the sulfur content in the raw material (first hydrocracking reaction product) entering the second hydrocracking reaction zone is extremely low, so that the hydrocracking catalyst in the second hydrocracking reaction zone faces the problem of sulfur loss, the problem of sulfur loss can lead to gradual reduction of catalyst activity in the hydrocracking reaction process of the second hydrocracking reaction zone and further reduction of conversion rate, and the light refined diesel oil (1 st material flow light fraction) obtained after diesel oil refining is introduced into the second hydrocracking reaction zone, so that the sulfur content is about 10-100 ppm, thereby playing the role of supplementing sulfur to the hydrocracking catalyst and not affecting the product properties of secondary hydrocracking.
3. According to the invention, the high economical hydroconversion of diesel oil is realized by setting a reasonable reaction path, the reaction temperature of a diesel oil hydrogenation reaction zone is reduced firstly, so that when a reaction product (particularly, a4 th material flow heavy fraction) obtained in a second hydrocracking reaction zone is recycled to the diesel oil hydrogenation reaction zone for treatment, more favorable thermodynamic conditions can be provided for reactions such as aromatic hydrocarbon saturation and the like which are rich in the reaction product, the circulating oil which is difficult to treat in the conventional two-stage hydrocracking process is fully saturated, and the diesel oil raw material is converted into high-added-value products such as light naphtha and heavy naphtha by the method, so that the diesel oil ratio is reduced to zero in a real sense.
Drawings
FIG. 1 is a schematic diagram of a combined process flow of wax oil hydrocracking and diesel hydrofining in the present invention.
The main drawings are as follows:
In FIG. 1, 1-diesel feed, 2-diesel hydrogenation reaction zone, 3-1 st stream, 4-wax oil feed, 5-hydrocracking pretreatment reaction zone, 6-2 nd stream, 7-gas-liquid separator, 8-gas phase feed, 9-recycle hydrogen, 10-new hydrogen, 11-liquid phase feed, 12-first hydrocracking reaction zone, 13-first hydrocracking reaction product, 14-second fractionation column, 15-gas, 16-naphtha, 17-3 rd stream, 18-second hydrocracking reaction zone, 19-4 th stream, 20-third fractionation column, 21-4 th stream light fraction, 22-4 th stream heavy fraction, 23-first fractionation column, 24-1 st stream light fraction, 25-1 st stream heavy fraction.
FIG. 2 is a schematic diagram of a conventional wax oil hydrocracking and diesel hydrofining combined process flow in the prior art.
Detailed Description
The technical scheme and technical effects of the invention are further described below with reference to the accompanying drawings and the detailed description.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or other components.
Spatially relative terms, such as "below," "beneath," "lower," "above," "upper," and the like, may be used herein for ease of description to describe one element's or feature's relationship to another element's or feature's in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the article in use or operation in addition to the orientation depicted in the figures. For example, if the article in the figures is turned over, elements described as "below" or "beneath" other elements or features would then be oriented "above" the elements or features. Thus, the exemplary term "below" may encompass both a direction of below and a direction of above. The article may have other orientations (rotated 90 degrees or other orientations) and the spatially relative descriptors used herein interpreted accordingly.
The terms "first," "second," and the like herein are used for distinguishing between two different elements or regions and are not intended to limit a particular position or relative relationship. In other words, in some embodiments, the terms "first," "second," etc. may also be interchanged with one another.
In this document, all numerical values of a parameter (e.g., quantity or condition) are to be understood as being modified in all instances by the term "about," whether or not "about" actually occurs before the numerical value.
The properties of the raw oil used in the examples and comparative examples of the present invention are shown in Table 1.
TABLE 1 Properties of raw oil
The wax oil hydrocracking and diesel hydrofining combined process comprises the following steps of allowing a diesel raw material 1 to enter a diesel hydrogenation reaction zone 2 for reaction in the presence of new hydrogen 10, obtaining a1 st material flow 3 after the reaction is completed, fractionating the 1 st material flow 3 through a first fractionating tower 23 to obtain a1 st material flow light fraction 24 and a1 st material flow heavy fraction 25, allowing the wax oil raw material 4 and the new hydrogen 10 to enter a hydrocracking pretreatment reaction zone 5, mixing the obtained pretreatment reaction product 6 with the 1 st material flow heavy fraction 25, allowing the obtained pretreatment reaction product to enter a first hydrocracking reaction zone 12, allowing the obtained pretreatment reaction product to react in the presence of hydrogen, allowing a reaction product 13 obtained after the reaction is completed to enter a gas-liquid separator 7 for separation, obtaining a gas phase material 8 and a liquid phase material 11, compressing the gas phase material 8 through a circulating hydrogen compressor, obtaining circulating hydrogen 9, and allowing the circulating hydrogen 9 to be further circulated back into the diesel hydrogenation reaction zone, the hydrocracking pretreatment reaction zone, the first hydrocracking reaction zone and the second hydrocracking reaction zone for use, allowing the liquid phase material 11 to enter a second fractionating tower 14, and obtaining gas 15, 16 and 17, and obtaining gas flows after separation. The 3 rd stream 17 and the 1 st stream light fraction 24 are mixed and enter a second hydrocracking reaction zone 18 for reaction, a 4 th stream 19 (second-stage hydrocracking product) is obtained after the reaction, the 4 th stream 19 is preferably further fractionated in a third fractionating tower 20 to obtain a 4 th stream light fraction 21 and a 4 th stream heavy fraction 22, the 4 th stream light fraction 21 can be recycled and mixed with a liquid phase material 11 obtained by separating a reaction product of the first hydrocracking reaction zone and enter the second fractionating tower 14 for treatment, and the 4 th stream heavy fraction 22 can be recycled to the diesel hydrogenation reaction zone 2 for treatment together with the diesel raw material 1.
In the embodiment and the comparative example, the diesel hydrogenation reaction zone, the hydrocracking pretreatment reaction zone, the first hydrocracking reaction zone and the second hydrocracking reaction zone are all provided with a hydrogenation reactor which is respectively named as a diesel hydrogenation reactor, a hydrocracking pretreatment reactor, a first hydrocracking reactor and a second hydrocracking reactor.
Example 1
The diesel oil and wax oil in Table 1 are used as raw materials, a technological process shown in FIG. 1 is adopted, a FHUDS-6 diesel oil hydrofining catalyst is filled in a diesel oil hydrogenation reactor, an FF-56 pretreatment catalyst is filled in a hydrocracking pretreatment reactor, an FC-14 hydrocracking catalyst is filled in a first hydrocracking reactor, and an FC-76 hydrocracking catalyst is filled in a second hydrocracking reactor. The split temperature of the 1 st stream light fraction and the 1 st stream heavy fraction was 340 ℃, and the split temperature of the 4 th stream light fraction and the 4 th stream heavy fraction was 120 ℃. The reaction conditions of the diesel hydrogenation reactor are that the reaction pressure is 5.0 MPa, the reaction temperature is 360 ℃, the volume space velocity is 0.8h -1, the hydrogen oil volume ratio is 800, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 14.0 MPa, the reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the hydrogen oil volume ratio is 1000, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the hydrogen oil volume ratio is 1200, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 340 ℃, the volume space velocity is 2.2h -1, the hydrogen oil volume ratio is 1600, and the reaction results are shown in Table 2.
Example 2
The diesel oil and wax oil in Table 1 are used as raw materials, a technological process shown in FIG. 1 is adopted, a FHUDS-8 diesel oil hydrofining catalyst is filled in a diesel oil hydrogenation reactor, an FF-66 pretreatment catalyst is filled in a hydrocracking pretreatment reactor, FC-14 and FC-76 hydrocracking catalysts are sequentially filled in a first hydrocracking reactor according to the flow direction of liquid phase materials, the mass ratio of the FC-14 to the FC-76 hydrocracking catalysts is 50:50, FC-76 and FC-52 hydrocracking catalysts are sequentially filled in a second hydrocracking reactor according to the flow direction of liquid phase materials, and the mass ratio of the FC-76 to the FC-52 hydrocracking catalysts is 20:80. The split temperature of the 1 st stream light fraction and the 1 st stream heavy fraction was 260 ℃, and the split temperature of the 4 th stream light fraction and the 4 th stream heavy fraction was 170 ℃. The reaction conditions of the diesel hydrogenation reactor are that the reaction pressure is 8.0MPa, the reaction temperature is 340 ℃, the volume space velocity is 1.5h -1, the hydrogen oil volume ratio is 500, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 12.0MPa, the reaction temperature is 360 ℃, the volume space velocity is 2.0h -1, the hydrogen oil volume ratio is 1600, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 12.0MPa, the average reaction temperature is 340 ℃, the volume space velocity is 0.5h -1, the hydrogen oil volume ratio is 1600, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 12.0MPa, the average reaction temperature is 320 ℃, the volume space velocity is 1.0h -1, the hydrogen oil volume ratio is 1000, and the reaction results are shown in Table 2.
Example 3
The diesel oil and wax oil in the table 1 are taken as raw materials, a process flow shown in figure 1 is adopted, a hydrofining reactor is filled with FHUDS-7 diesel oil hydrofining catalyst, a hydrocracking pretreatment reactor is sequentially filled with FF-66 and FTX pretreatment catalyst according to the flow direction of liquid phase materials, and the mass ratio of the FF-66 to the FTX pretreatment catalyst is 70:30. The first hydrocracking reactor is filled with self-made hydrocracking catalyst, the pore volume is 0.36mL/g, the loading amounts of Ni metal oxide and W metal oxide are respectively 3.0wt%, 23.0wt% (the total metal loading amount is 26.0%), the Y molecular sieve content is 16wt%, the second hydrocracking reactor is filled with self-made hydrocracking catalyst, the pore volume is 0.30mL/g, the loading amounts of Ni metal oxide and W metal oxide are respectively 3.0wt%, 19.0wt% (the total metal loading amount is 22.0%), and the Y molecular sieve content is 10wt%. The split temperature of the 1 st stream light fraction and the 1 st stream heavy fraction was 200 ℃, and the split temperature of the 4 th stream light fraction and the 4 th stream heavy fraction was 200 ℃. The reaction conditions of the diesel hydrogenation reactor are that the reaction pressure is 3.6MPa, the reaction temperature is 320 ℃, the volume space velocity is 0.6h -1, the hydrogen oil volume ratio is 1500, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 16.5MPa, the reaction temperature is 380 ℃, the volume space velocity is 1.0h -1, the hydrogen oil volume ratio is 1000, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 15.5MPa, the average reaction temperature is 365 ℃, the volume space velocity is 0.9h -1, the hydrogen oil volume ratio is 1300, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 15.5MPa, the average reaction temperature is 355 ℃, the volume space velocity is 3.0h -1, the hydrogen oil volume ratio is 1500, and the reaction results are shown in Table 2.
Example 4
The diesel oil and wax oil in table 1 are taken as raw materials, a process flow shown in fig. 1 is adopted, wherein the 4 th material flow is completely circulated to a second fractionating tower for treatment, a FHUDS-6 diesel oil hydrofining catalyst is filled in a diesel oil hydrogenation reactor, an FF-56 pretreatment catalyst is filled in a hydrocracking pretreatment reactor, an FC-14 hydrocracking catalyst is filled in a first hydrocracking reactor, and an FC-76 hydrocracking catalyst is filled in a second hydrocracking reactor. The split temperature of the 1 st stream light fraction and the 1 st stream heavy fraction was 340 ℃. The reaction conditions of the diesel hydrogenation reaction zone are that the reaction pressure is 5.0 MPa, the reaction temperature is 360 ℃, the volume space velocity is 0.8h -1, the hydrogen oil volume ratio is 800, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 14.0MPa, the reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the hydrogen oil volume ratio is 1000, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the hydrogen oil volume ratio is 1200, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 340 ℃, the volume space velocity is 2.2h -1, the hydrogen oil volume ratio is 1600, and the reaction results are shown in Table 2.
As shown in figure 2, the wax oil hydrocracking and diesel hydrofining combined process in the conventional process comprises the following steps that a wax oil raw material 1 and new hydrogen 15 enter a hydrocracking pretreatment reaction zone 2, a pretreatment reaction product 3 obtained after the reaction enters a first hydrocracking reaction zone 4 and reacts in the presence of the new hydrogen 15, a reaction product 16 obtained after the reaction is completed enters a wax oil-gas-liquid separator 5 to be separated to obtain a gas phase material 13 and a liquid phase material 6, the gas phase material 13 is treated and compressed by a recycle hydrogen compressor 14 to obtain recycle hydrogen, and the recycle hydrogen can be further recycled to the hydrocracking pretreatment reaction zone 2, the first hydrocracking reaction zone 4 and the second hydrocracking reaction zone 11 for use, and the liquid phase material 6 enters a wax oil fractionating tower 7 to be separated to obtain a first gas 8, a first naphtha 9 (comprising light naphtha and heavy naphtha) and unconverted oil 10. The unconverted oil 10 enters a second hydrocracking reaction zone 11 for reaction, and a second-stage hydrocracking product 12 obtained after the reaction enters a wax oil fractionating tower 7 for treatment.
The diesel raw material 27 and new hydrogen 15 enter a diesel hydrofining reactor 17 to react, a reaction product 18 obtained by the reaction enters a diesel oil-gas-liquid separator 19 to be separated to obtain a gas phase material flow 25 and a liquid phase material flow 20, wherein the gas phase material flow 25 is treated and compressed by a circulating hydrogen compressor 26 to obtain circulating hydrogen, the circulating hydrogen can be further circulated to the diesel hydrofining reactor for use, and the liquid phase material flow 20 enters a diesel fractionating tower 21 to be separated to obtain a second gas product 22, second naphtha 23 and refined diesel 24.
Comparative example 1
The process flow described in fig. 2 was used with diesel and wax oils as raw materials in table 1. The diesel hydrofining reactor is filled with FHUDS-6 diesel hydrofining catalyst, the hydrocracking pretreatment reactor is filled with FF-56 pretreatment catalyst, the first hydrocracking reactor is filled with FC-14 hydrocracking catalyst, and the second hydrocracking reactor is filled with FC-76 hydrocracking catalyst. The reaction conditions of the diesel hydrofining reactor are that the reaction pressure is 5.0 MPa, the reaction temperature is 360 ℃, the volume space velocity is 0.8h -1, the volume ratio of hydrogen to oil is 800, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 14.0 MPa, the reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the volume ratio of hydrogen to oil is 1000, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 380 ℃, the volume space velocity is 1.2h -1, the volume ratio of hydrogen to oil is 1200, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 16.0MPa, the average reaction temperature is 340 ℃, the volume space velocity is 2.2h -1, the volume ratio of hydrogen to oil is 1600, and the reaction results are shown in table 3.
Comparative example 2
The process flow described in fig. 2 was used with diesel and wax oils as raw materials in table 1. The diesel hydrofining reactor is filled with FHUDS-8 diesel hydrofining catalyst, the hydrocracking pretreatment reactor is filled with FF-66 pretreatment catalyst, the first hydrocracking reactor is sequentially filled with FC-14 and FC-76 hydrocracking catalyst according to the flow direction of liquid phase material, the mass ratio of the FC-14 to the FC-76 hydrocracking catalyst is 50:50, the second hydrocracking reactor is sequentially filled with FC-76 to the FC-52 hydrocracking catalyst according to the flow direction of liquid phase material, and the mass ratio of the FC-76 to the FC-52 hydrocracking catalyst is 20:80. The reaction conditions of the diesel hydrofining reactor are that the reaction pressure is 8.0 MPa, the reaction temperature is 340 ℃, the volume space velocity is 1.5h -1, the volume ratio of hydrogen to oil is 500, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 12.0MPa, the reaction temperature is 360 ℃, the volume space velocity is 2.0h -1, the volume ratio of hydrogen to oil is 1600, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 12.0MPa, the average reaction temperature is 340 ℃, the volume space velocity is 0.5h -1, the volume ratio of hydrogen to oil is 1600, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 12.0MPa, the average reaction temperature is 320 ℃, the volume space velocity is 1.0h -1, the volume ratio of hydrogen to oil is 1000, and the reaction results are shown in table 3.
Comparative example 3
The process flow described in fig. 2 was used with diesel and wax oils as raw materials in table 1. The diesel hydrofining reactor is filled with FHUDS-7 diesel hydrofining catalyst, the hydrocracking pretreatment reactor is sequentially filled with FF-66 and FTX pretreatment catalyst according to the flow direction of liquid phase materials, and the mass ratio of the FF-66 to the FTX pretreatment catalyst is 70:30. The first hydrocracking reactor is filled with self-made hydrocracking catalyst, pore volume is 0.36mL/g, the loading amounts of Ni metal oxide and W metal oxide are 3.0 percent and 23.0 percent respectively (the total metal loading amount is 25.0 percent), the Y molecular sieve content is 16 percent, the second hydrocracking reactor is filled with self-made hydrocracking catalyst, pore volume is 0.30mL/g, the loading amounts of Ni metal oxide and W metal oxide are 3.0 percent and 19.0 percent respectively (the total metal loading amount is 22.0 percent), and the Y molecular sieve content is 10 percent. The reaction conditions of the diesel hydrofining reactor are that the reaction pressure is 3.6 MPa, the reaction temperature is 320 ℃, the volume space velocity is 0.6h -1, the volume ratio of hydrogen to oil is 1500, the reaction conditions of the hydrocracking pretreatment reactor are that the reaction pressure is 16.5MPa, the reaction temperature is 380 ℃, the volume space velocity is 1.0h -1, the volume ratio of hydrogen to oil is 1000, the reaction conditions of the first hydrocracking reactor are that the reaction pressure is 15.5MPa, the average reaction temperature is 365 ℃, the volume space velocity is 0.9 h -1, the volume ratio of hydrogen to oil is 13400, the reaction conditions of the second hydrocracking reactor are that the reaction pressure is 15.5MPa, the average reaction temperature is 355 ℃, the volume space velocity is 3.0h -1, the volume ratio of hydrogen to oil is 1500, and the reaction results are shown in Table 3.
Table 2 example reaction results
TABLE 3 comparative reaction results
In the comparative examples, the light naphtha yield, the heavy naphtha yield and the diesel yield were calculated from the total of the two sets of plant products and the raw materials.
The experimental results of the examples and the comparative examples show that the activity of the wax oil two-stage hydrocracking catalyst under the wax oil hydrocracking and diesel hydrofining combined process flow of the method is stable, and the yield and the deactivation rate of the heavy naphtha are superior to those of the conventional wax oil two-stage hydrocracking catalyst. The diesel-gasoline ratio is reduced to zero, and the property of heavy naphtha is obviously improved, so that obvious economic benefits are brought to refineries.
Claims (27)
1. A wax oil hydrocracking and diesel hydrofining combined process, which comprises the following steps:
(1) Under the condition of hydrogen, the diesel raw material enters a diesel hydrogenation reaction zone for reaction, and a1 st material flow is obtained after the reaction is completed;
(2) Fractionating the 1 st material flow to obtain a1 st material flow light fraction and a1 st material flow heavy fraction, wherein the dividing temperature of the 1 st material flow light fraction and the 1 st material flow heavy fraction is 150-360 ℃;
(3) Under the condition of hydrogen, feeding a wax oil raw material into a hydrocracking pretreatment reaction zone, and obtaining a 2 nd material flow after the reaction is completed;
(4) Mixing the 2 nd material flow obtained in the step (3) with the 1 st material flow heavy fraction obtained in the step (2) in the presence of hydrogen, and then entering a first hydrocracking reaction zone, carrying out gas-liquid separation on a reaction product to obtain a gas phase material and a liquid phase material, and further fractionating the liquid phase material to obtain gas, naphtha and the 3 rd material flow;
(5) And (3) mixing the 3 rd material flow obtained in the step (4) with the 1 st material flow light fraction obtained in the step (2), and feeding the mixture into a second hydrocracking reaction zone, wherein the 4 th material flow obtained after the reaction is completed is circulated and treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone.
2. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the 4 th material flow obtained in the step (5) is fractionated to obtain a 4 th material flow light fraction and a 4 th material flow heavy fraction, and the dividing temperature of the 4 th material flow light fraction and the 4 th material flow heavy fraction is 100-250 ℃.
3. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the 4 th material flow obtained in the step (5) is fractionated to obtain a 4 th material flow light fraction and a 4 th material flow heavy fraction, and the dividing temperature of the 4 th material flow light fraction and the 4 th material flow heavy fraction is 120-200 ℃.
4. A combined wax oil hydrocracking and diesel hydrofining process according to claim 2 or 3, wherein the 4 th stream light fraction is recycled and treated with the liquid phase material separated from the reaction product of the first hydrocracking reaction zone, and the 4 th stream heavy fraction is recycled and treated with the diesel feedstock.
5. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the distillation range of the diesel raw material is 160-400 ℃ and the aromatic hydrocarbon content is 10-60 wt%.
6. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the distillation range of the diesel raw material is 160-400 ℃ and the aromatic hydrocarbon content is 20-50 wt%.
7. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the diesel raw material is one or a mixture of several of straight-run diesel, catalytic diesel and coker diesel.
8. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the diesel feedstock is selected from the group consisting of hydrogenated stable diesel.
9. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the split temperature of the 1 st stream light fraction and the 1 st stream heavy fraction is 200-340 ℃.
10. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the wax oil raw material is one or more of normal pressure wax oil, reduced pressure wax oil and boiling bed wax oil.
11. The combined wax oil hydrocracking and diesel hydrofining process according to claim 1, wherein the wax oil raw material is deep drawn wax oil.
12. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the diesel hydrogenation reaction zone is that the reaction pressure is 1.0-9.0 MPa, the reaction temperature is 260-400 ℃, the volume space velocity is 0.1-10.0 h -1, and the hydrogen-oil volume ratio is 200-2100.
13. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the diesel hydrogenation reaction zone is that the reaction pressure is 3.0-8.5 MPa, the reaction temperature is 300-360 ℃, the volume space velocity is 0.6-1.5 h -1, and the hydrogen-oil volume ratio is 600-2000.
14. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the hydrocracking pretreatment reaction zone is that the reaction pressure is 6.0-20.0 MPa, the reaction temperature is 250-450 ℃, the volume space velocity is 0.2-12.0 h -1, and the hydrogen oil volume ratio is 300-2000.
15. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the hydrocracking pretreatment reaction zone is that the reaction pressure is 8.0-16.5 MPa, the reaction temperature is 320-400 ℃, the volume space velocity is 0.6-2.0 h -1, and the hydrogen oil volume ratio is 300-2000.
16. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the first hydrocracking reaction zone is that the reaction pressure is 6.0-20.0 MPa, the reaction temperature is 280-420 ℃, the volume space velocity is 0.1-5.0 h -1, and the hydrogen-oil volume ratio is 500-1800.
17. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the first hydrocracking reaction zone is that the reaction pressure is 8.0-19.5 MPa, the reaction temperature is 330-410 ℃, the volume space velocity is 0.5-1.2 h -1, and the hydrogen oil volume ratio is 600-1600.
18. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the second hydrocracking reaction zone is that the reaction pressure is 6.0-20.0 MPa, the reaction temperature is 250-400 ℃, the volume space velocity is 0.4-7.0 h -1, and the hydrogen oil volume ratio is 200-2000.
19. The wax oil hydrocracking and diesel hydrofining combined process according to claim 1, wherein the reaction condition of the second hydrocracking reaction zone is that the reaction pressure is 8.0-19.5 MPa, the reaction temperature is 320-400 ℃, the volume space velocity is 0.6-3.0 h -1, and the hydrogen oil volume ratio is 600-1600.
20. A combined wax oil hydrocracking and diesel hydrofining treatment system, the combined treatment system comprising:
The diesel hydrogenation reaction zone is used for receiving diesel raw materials and hydrogen, and obtaining a1 st material flow after reaction;
a first fractionation unit for receiving a1 st stream from the diesel hydrogenation reaction zone, after separation, to obtain a1 st stream light fraction and a1 st stream heavy fraction;
The hydrocracking pretreatment reaction zone is used for receiving wax oil raw materials and hydrogen, and obtaining a2 nd material flow after the reaction is completed;
A first hydrocracking reaction zone for receiving hydrogen, a 2 nd stream from the hydrocracking pretreatment reaction zone, and a1 st stream heavy fraction from the first fractionation column, after reaction to obtain a reaction product;
The gas-liquid separation unit is used for receiving a reaction product from the first hydrocracking reaction zone and separating to obtain a gas-phase material and a liquid-phase material;
The second fractionating unit is used for receiving the liquid phase material from the gas-liquid separating unit and separating to obtain gas, naphtha and a3 rd material flow;
A second hydrocracking reaction zone for receiving hydrogen, a 1 st stream light fraction from the first fractionation unit and a 3 rd stream from the second fractionation unit, after reaction, a 4 th stream is obtained, the 4 th stream being in line communication with the second fractionation unit inlet.
21. The combined wax oil hydrocracking and diesel hydrofining treatment system according to claim 20, wherein the combined wax oil hydrocracking and diesel hydrofining treatment system comprises a third fractionating unit for receiving a 4 th stream from the second hydrocracking reaction zone, fractionating the 4 th stream to obtain a 4 th stream light fraction and a 4 th stream heavy fraction, wherein the dividing temperature of the 4 th stream light fraction and the 4 th stream heavy fraction is 100-250 ℃, the 4 th stream light fraction is communicated with an inlet of the second fractionating unit through a pipeline and is treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone, and the 4 th stream heavy fraction is communicated with an inlet of the diesel hydrogenation reaction zone through a pipeline and is treated together with a diesel raw material.
22. The combined wax oil hydrocracking and diesel hydrofining treatment system according to claim 20, wherein the combined wax oil hydrocracking and diesel hydrofining treatment system comprises a third fractionating unit for receiving a 4 th stream from the second hydrocracking reaction zone, fractionating the 4 th stream to obtain a 4 th stream light fraction and a 4 th stream heavy fraction, wherein the dividing temperature of the 4 th stream light fraction and the 4 th stream heavy fraction is 120-200 ℃, the 4 th stream light fraction is communicated with an inlet of the second fractionating unit through a pipeline and is treated together with a liquid phase material obtained by separating a reaction product of the first hydrocracking reaction zone, and the 4 th stream heavy fraction is communicated with an inlet of the diesel hydrogenation reaction zone through a pipeline and is treated together with a diesel raw material.
23. The combined wax oil hydrocracking and diesel hydrofining treatment system according to claim 20, further comprising a purifying unit for receiving the gas phase material from the gas-liquid separation unit, and obtaining purified hydrogen after treatment, wherein the purified hydrogen is compressed by the recycle hydrogen compressor and then enters the diesel hydrogenation reaction zone, the hydrocracking pretreatment reaction zone, the first hydrocracking reaction zone and the second hydrocracking reaction zone for use.
24. The combined wax oil hydrocracking and diesel hydrofining processing system of claim 20, wherein the diesel hydrogenation reaction zone comprises at least one hydrogenation reactor, the hydrogenation reactor being charged with at least one hydrofining catalyst.
25. The combined wax oil hydrocracking and diesel hydrofining treatment system according to claim 20, wherein the hydrocracking pretreatment reaction zone is provided with at least one hydrogenation reactor, and the hydrogenation reactor contains at least one hydrocracking pretreatment catalyst.
26. The combined wax oil hydrocracking and diesel hydrofining processing system of claim 20, wherein the first hydrocracking reaction zone is provided with at least one hydrocracking reactor, and the hydrocracking reactor contains at least one hydrocracking catalyst.
27. The combined wax oil hydrocracking and diesel hydrofining processing system of claim 20, wherein the second hydrocracking reaction zone is provided with at least one hydrocracking reactor, and the hydrocracking reactor contains at least one hydrocracking catalyst.
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