WO2017161981A1 - System and method for producing low-condensation-point middle distillate using fischer-tropsch synthesized whole distillate - Google Patents
System and method for producing low-condensation-point middle distillate using fischer-tropsch synthesized whole distillate Download PDFInfo
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- WO2017161981A1 WO2017161981A1 PCT/CN2017/073864 CN2017073864W WO2017161981A1 WO 2017161981 A1 WO2017161981 A1 WO 2017161981A1 CN 2017073864 W CN2017073864 W CN 2017073864W WO 2017161981 A1 WO2017161981 A1 WO 2017161981A1
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- the invention relates to the technical field of deep processing of Fischer-Tropsch synthetic oil, in particular to a system and a method for producing a low-condensation middle distillate oil from a Fischer-Tropsch synthesis whole distillate.
- the main product of low temperature Fischer-Tropsch synthesis is a complex mixture of C4 ⁇ C70 hydrocarbons and a small amount of oxygen compounds. It has the characteristics of sulfur-free, nitrogen-free, metal-free and low aromatics.
- the traditional hydrocracking adopts the upper feeding mode, the bed temperature gradient and the pressure drop are both large, the upper part of the reactor is easy to coke, the equipment investment and operating cost are high, and the isomerization rate is insufficient, the diesel set point is high, and the chemical is high. High hydrogen consumption.
- Fischer-Tropsch synthetic oil is quite different from petroleum. Unsaturated olefins and acids are mainly concentrated in light components. Hydrogenation of light components will release a large amount of heat and cause coking, while the temperature rise is obvious and the temperature is not easy to control.
- the object of the present invention is to provide a system and a method for producing a low-condensation middle distillate oil from a Fischer-Tropsch synthesis whole distillate.
- both the hydrocracking and the hydroisomerization are carried out by using a lower feed mode to make the hydrogen concentration along the reaction.
- the axial distribution is more reasonable, the reactor temperature gradient is the smallest, and the problem of large pressure drop in the upper part of the catalyst bed is overcome.
- the Fischer-Tropsch synthesis whole distillate designed by the present invention produces a low-condensation middle distillate system characterized in that it comprises a first hydrogenation reactor, a second hydrogenation reactor, a gas-liquid separator, and fractionation.
- the first hydrogenation reactor comprises an upper catalyst bed and a lower catalyst bed
- the Fischer-Tropsch heavy oil delivery pipeline is connected to the central input end of the first hydrogenation reactor
- the Fischer-Tropsch light oil delivery pipeline is connected to the bottom input end of the first hydrogenation reactor
- the bottom input end of the first hydrogenation reactor is located first Below the catalyst bed under the hydrogenation reactor
- the central input end of the first hydrogenation reactor is located first Between the catalyst bed and the lower catalyst bed of the hydrogenation reactor, the first hydrogen gas transmission pipeline is connected with the Fischer-Tropsch heavy oil transportation pipeline, and the second hydrogen gas transmission pipeline is connected with the Fischer-Tropsch light oil transportation pipeline, the first hydrogenation reactor
- the output pipe is connected to the bottom input end of the second hydrogenation reactor, and the top output end of the second hydrogenation reactor is connected to the input end of the gas-liquid separator, and the liquid phase output end of the
- a method for producing a low-condensation middle distillate using the above system characterized in that it comprises the following steps:
- Step 1 Hydrogen saturation in the second hydrogen delivery conduit is dissolved in Fischer-Tropsch light oil in the Fischer light oil delivery pipeline to form a hydrogen-saturated Fischer-Tropsch light oil, the hydrogen-saturated Fischer-Tropsch light oil from the first hydrogenation reactor
- the bottom input end is input to the first hydrogenation reactor, and the hydrogen in the first hydrogen delivery pipeline is saturated and dissolved in the Fischer-Tropsch heavy oil in the Fischer-Tropsch heavy oil delivery pipeline to form a hydrogen-saturated Fischer-Tropsch heavy oil, and the hydrogen-saturated Fischer-Tropsch heavy oil is
- the central input end of a hydrogenation reactor is input to the first hydrogenation reactor, and the hydrogen-saturated Fischer-Tropsch light oil and the hydrogen-saturated Fischer-Tropsch heavy oil are respectively subjected to a hydrocracking reaction under the action of a hydrotreating catalyst and a hydrocracking catalyst to form an intermediate Distillate, middle distillate is fed to the second hydrogenation reactor through the bottom input of the second hydrogenation reactor;
- Step 2 The middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed, respectively, to form a low condensation intermediate Distillate oil
- Step 3 The low-condensation middle distillate enters the gas-liquid separator for gas-liquid separation treatment, and the separated liquid phase enters the fractionation column to fractionate to obtain the naphtha product and the target product low-condensed diesel oil.
- both the hydrocracking and the hydroisomerization adopt the lower feeding mode, so that the hydrogen concentration is more rationally distributed along the axial direction of the reactor, the reactor temperature gradient is the smallest, and the problem of large pressure drop in the upper part of the catalyst bed is overcome. .
- Fischer-Tropsch synthesis products are mainly saturated linear hydrocarbons with high saturation and low chemical hydrogen consumption.
- the Fischer-Tropsch light oil and the Fischer-Tropsch heavy oil are separately fed as described in the present invention, so that the temperature of the refined reaction bed can be kept stable, and the temperature of the Fischer-Tropsch heavy oil feed is lowered, and the energy is lowered. Consumption.
- Figure 1 is a schematic view of the structure of the present invention
- 1 - first hydrogenation reactor 1 - first hydrogenation reactor, 2 - second hydrogenation reactor, 3 - gas liquid separator, 4 - fractionation tower, 5 - Fischer heavy oil pipeline, 6 - Fischer light oil pipeline, 7 - First hydrogen delivery pipe, 8 - second hydrogen delivery pipe, 9 - naphtha product output port, 10 - low condensation diesel output port.
- a Fischer-Tropsch full-distillate oil production system as shown in Figure 1 comprises a first hydrogenation reactor 1, a second hydrogenation reactor 2, a gas-liquid separator 3, a fractionation column 4, and Fischer-Tropsch a heavy oil delivery conduit 5, a Fischer light oil delivery conduit 6, a first hydrogen delivery conduit 7 and a second hydrogen delivery conduit 8, wherein the first hydrogenation reactor 1 comprises an upper catalyst bed and a lower catalyst bed,
- the Fischer heavy oil delivery pipe 5 is connected to the central input end of the first hydrogenation reactor 1
- the Fischer-Tropical light oil delivery pipe 6 is connected to the bottom input end of the first hydrogenation reactor 1, the first hydrogenation reactor 1
- the bottom input end is located below the catalyst bed under the first hydrogenation reactor 1, and the central input end of the first hydrogenation reactor 1 is located between the catalyst bed and the lower catalyst bed on the first hydrogenation reactor 1.
- the first hydrogen delivery conduit 7 is in communication with the Fischer-Tropsch heavy oil delivery conduit 5
- the second hydrogen delivery conduit 8 is in communication with the Fischer-Tropsch light oil delivery conduit 6
- the output conduit of the first hydrogenation reactor 1 is coupled to the second hydrogenation reactor 2 Bottom input, the top output of the second hydrogenation reactor 2 is connected
- the liquid phase output end of the gas-liquid separator 3 is connected to the input end of the fractionation column 4
- the fractionation column 4 has a naphtha product output port 9 and a low-condensation diesel output port 10
- a fractionation tower The circulating oil output of 4 is connected to the bottom input of the second hydrogenation reactor 2.
- the upper catalyst bed of the first hydrogenation reactor 1 is filled with a hydrocracking catalyst, and the lower catalyst bed of the first hydrogenation reactor 1 is filled with a hydrotreating catalyst.
- the hydrogenation active metal in the hydrorefining catalyst is Ni and Mo
- the content of the oxygen compound is in the range of 1% to 40% by mass
- the catalyst carrier is a porous refractory oxide such as alumina, oxidized. Silicon or composite oxide.
- the hydrotreating catalyst has a specific surface area in the range of 200 to 600 m 2 /g
- the hydrorefining catalyst has a pore volume in the range of 0.3 to 0.6 ml/g.
- the content of the amorphous silicon aluminum in the hydrocracking catalyst is 40% to 80% by mass, and the hydrogenation active metals in the hydrocracking catalyst are Ni and W, in the hydrocracking catalyst.
- the total content of oxygenates is 10% to 30% by mass.
- the molecular sieve in the hydrocracking catalyst is one or more of Y-type molecular sieve, ⁇ molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular sieve.
- the hydrocracking catalyst has a molecular sieve content of 1% to 20% by mass, the hydrocracking catalyst has a specific surface area of 200 to 500 m 2 /g, and the hydrocracking catalyst has a pore volume of 0.3 to 0.7. Ml/g.
- the second hydrogenation reactor 2 comprises two catalyst reaction beds, and the first catalyst reaction bed layer and the second catalyst reaction bed layer are respectively from bottom to top, and the first catalyst reaction bed layer is loaded and added.
- the hydrogen cracking catalyst, the second catalyst reaction bed is loaded with a hydroisomerization catalyst.
- the cracking performance of the hydroisomerization catalyst is relatively weak, and the isomerization of linear hydrocarbons is the main reaction, and the freezing point can be significantly reduced.
- the hydrotreating catalyst, the hydrocracking catalyst and the hydroisomerization catalyst may be selected from existing matched commercial catalysts.
- the first hydrogenation reactor 1 comprises a refining and cracking treatment process
- the second hydrogenation reactor 2 comprises a cracking and heterogeneous treatment process
- a method for producing a low-condensation middle distillate using the above system comprising the steps of:
- Step 1 Hydrogen saturation in the second hydrogen delivery conduit 8 is dissolved in Fischer-Tropsch light oil (temperature ⁇ 350 ° C) in the Fischer-Tropsch light oil delivery pipe 6, forming a hydrogen-saturated Fischer-Tropsch light oil, which is lightly charged.
- the oil is supplied to the first hydrogenation reactor 1 from the bottom input end of the first hydrogenation reactor 1, and the hydrogen in the first hydrogen delivery conduit 7 is saturated and dissolved in the Fischer-Tropsch heavy oil in the Fischer-Tropsch heavy oil delivery conduit 5 to form a hydrogen saturation.
- Fischer heavy oil (temperature ⁇ 350 ° C), the hydrogen-saturated Fischer-Tropsch heavy oil is input into the first hydrogenation reactor 1 from the central input end of the first hydrogenation reactor 1, and the hydrogen-saturated Fischer-Tropsch light oil and the hydrogen-saturated Fischer-Tropsch heavy oil are respectively
- the hydrocracking reaction and hydrocracking catalyst are subjected to hydrocracking reaction to form a middle distillate oil, and the middle distillate oil is fed into the second hydrogenation reactor 2 through the bottom input end of the second hydrogenation reactor 2;
- Step 2 The middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor 2 through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed to form a low-condensation reaction.
- Middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor 2 through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed to form a low-condensation reaction.
- Step 3 The low-condensation middle distillate enters the gas-liquid separator 3 for gas-liquid separation treatment, and the separated liquid phase enters the fractionation column 4 to fractionate and obtain the naphtha product and the target product low-condensed diesel oil, and the separated gas phase is very Less, it can be used as fuel gas.
- Step 4 the circulating oil in the fractionation column 4 is returned to the bottom input end of the second hydrogenation reactor 2, and the circulating oil generates hydrogen in the second hydrogenation reactor 2 to generate hydrogen, and the hydrogen used in the hydroisomerization reaction is insufficient.
- the part is supplemented.
- the present invention may optionally be filled with a hydrogenation protecting agent at the bottom input end and the middle input end of the first hydrogenation reactor 1, or may be refined after the top output end of the second hydrogenation reactor 2 is charged.
- the low-condensation herein means diesel oil undergoing hydrocracking, especially hydroisomerization and decondensation, and the freezing point can be called low-condensation as long as it is lower than 0# diesel according to actual needs.
- Table 1 shows the experimental conditions and experimental results used in the examples.
- the hydrotreating catalyst, the hydrocracking catalyst, and the hydroisomerization catalyst are all prepared by a laboratory conventional method in accordance with the above-described methods and conditions of the present invention.
- Table 1 shows the experimental conditions and results of the process.
- Table 1 shows that the yield of the low-condensation diesel produced by the present invention is good and the product properties are good.
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Abstract
A system and method for producing low-condensation-point middle distillate using Fischer-Tropsch synthesized whole distillate. In the system, a Fischer-Tropsch heavy oil transport pipe (5) is connected to a middle input end of a first hydrogenation reactor (1); a Fischer-Tropsch light oil transport pipe (6) is connected to a bottom input end of the first hydrogenation reactor (1); a first hydrogen transport pipe (7) is in communication with the Fischer-Tropsch heavy oil transport pipe (5); a second hydrogen transport pipe (8) is in communication with the Fischer-Tropsch light oil transport pipe (6); an output pipe of the first hydrogenation reactor (1) is connected to a bottom input end of a second hydrogenation reactor (2); a top output end of the second hydrogenation reactor (2) is connected to an input end of a gas-liquid separator (3); a liquid-phase output end of the gas-liquid separator (3) is connected to an input end of a fractionating column (4); the fractionating column (4) has a naphtha product output port (9) and a low-condensation-point diesel output port (10). In the method, a lower feeding approach is used in all the hydrogenation reactors, thereby achieving more appropriate distribution of hydrogen concentration along the axial directions of the reactors and minimum temperature gradient in the reactors, and overcoming the defect of large pressure drop in the upper part of a catalyst bed layer.
Description
本发明涉及费托合成油深度加工技术领域，具体地指一种费托合成全馏分油生产低凝中间馏分油***及方法。The invention relates to the technical field of deep processing of Fischer-Tropsch synthetic oil, in particular to a system and a method for producing a low-condensation middle distillate oil from a Fischer-Tropsch synthesis whole distillate.
低温费托合成主要产品是含C4～C70的烃类及少量的含氧化合物的复杂混合物，具有无硫、无氮、无金属、低芳烃等特点。The main product of low temperature Fischer-Tropsch synthesis is a complex mixture of C4～C70 hydrocarbons and a small amount of oxygen compounds. It has the characteristics of sulfur-free, nitrogen-free, metal-free and low aromatics.
传统加氢裂化采用上进料方式，床层温度梯度和压降均较大，反应器上部易结焦，设备投资和运行成本较高，此外异构化率不足，所产柴油凝点高，化学氢耗高。The traditional hydrocracking adopts the upper feeding mode, the bed temperature gradient and the pressure drop are both large, the upper part of the reactor is easy to coke, the equipment investment and operating cost are high, and the isomerization rate is insufficient, the diesel set point is high, and the chemical is high. High hydrogen consumption.
费托合成油与石油有较大不同，其中不饱和烯烃、酸等主要集中于轻组分，轻组分加氢精制会放出大量的热并造成结焦，同时温升明显，温度不易控制。Fischer-Tropsch synthetic oil is quite different from petroleum. Unsaturated olefins and acids are mainly concentrated in light components. Hydrogenation of light components will release a large amount of heat and cause coking, while the temperature rise is obvious and the temperature is not easy to control.
发明内容Summary of the invention
本发明的目的就是要提供一种费托合成全馏分油生产低凝中间馏分油***及方法，该***及方法中加氢裂化和加氢异构都采用下进料方式，使氢浓度沿反应器轴向分布更合理，反应器温度梯度最小，同时克服了催化剂床层上部压降大的问题。The object of the present invention is to provide a system and a method for producing a low-condensation middle distillate oil from a Fischer-Tropsch synthesis whole distillate. In the system and method, both the hydrocracking and the hydroisomerization are carried out by using a lower feed mode to make the hydrogen concentration along the reaction. The axial distribution is more reasonable, the reactor temperature gradient is the smallest, and the problem of large pressure drop in the upper part of the catalyst bed is overcome.
为实现此目的，本发明所设计的费托合成全馏分油生产低凝中间馏分油***，其特征在于：它包括第一加氢反应器、第二加氢反应器、气液分离器、分馏塔、费托重油输送管道、费托轻油输送管道、第一氢气输送管道和第二氢气输送管道，其中，所述第一加氢反应器包含上催化剂床层和下催化剂床层，所述费托重油输送管道连接第一加氢反应器的中部输入端，费托轻油输送管道连接第一加氢反应器的底部输入端，所述第一加氢反应器的底部输入端位于第一加氢反应器下催化剂床层的下方，所述第一加氢反应器的中部输入端位于第一
加氢反应器上催化剂床层和下催化剂床层之间，第一氢气输送管道与费托重油输送管道连通，第二氢气输送管道与费托轻油输送管道连通，第一加氢反应器的输出管道连接第二加氢反应器的底部输入端，第二加氢反应器的顶部输出端连接气液分离器的输入端，气液分离器的液相输出端连接分馏塔的输入端，所述分馏塔具有石脑油产品输出口和低凝柴油输出口，分馏塔的循环油输出端连接第二加氢反应器的底部输入端。To achieve this object, the Fischer-Tropsch synthesis whole distillate designed by the present invention produces a low-condensation middle distillate system characterized in that it comprises a first hydrogenation reactor, a second hydrogenation reactor, a gas-liquid separator, and fractionation. a tower, a Fischer heavy oil delivery pipeline, a Fischer-Tropsch light oil transportation pipeline, a first hydrogen delivery pipeline, and a second hydrogen delivery pipeline, wherein the first hydrogenation reactor comprises an upper catalyst bed and a lower catalyst bed, The Fischer-Tropsch heavy oil delivery pipeline is connected to the central input end of the first hydrogenation reactor, and the Fischer-Tropsch light oil delivery pipeline is connected to the bottom input end of the first hydrogenation reactor, and the bottom input end of the first hydrogenation reactor is located first Below the catalyst bed under the hydrogenation reactor, the central input end of the first hydrogenation reactor is located first
Between the catalyst bed and the lower catalyst bed of the hydrogenation reactor, the first hydrogen gas transmission pipeline is connected with the Fischer-Tropsch heavy oil transportation pipeline, and the second hydrogen gas transmission pipeline is connected with the Fischer-Tropsch light oil transportation pipeline, the first hydrogenation reactor The output pipe is connected to the bottom input end of the second hydrogenation reactor, and the top output end of the second hydrogenation reactor is connected to the input end of the gas-liquid separator, and the liquid phase output end of the gas-liquid separator is connected to the input end of the fractionation column. The fractionation column has a naphtha product outlet and a low-condensation diesel outlet, and the circulating oil output of the fractionation tower is connected to the bottom input end of the second hydrogenation reactor.
一种利用上述***生产低凝中间馏分油的方法，其特征在于，它包括如下步骤：A method for producing a low-condensation middle distillate using the above system, characterized in that it comprises the following steps:
步骤1：第二氢气输送管道中的氢饱和溶于费托轻油输送管道中的费托轻油中，形成氢饱和费托轻油，该氢饱和费托轻油由第一加氢反应器的底部输入端输入第一加氢反应器，第一氢气输送管道中的氢饱和溶于费托重油输送管道中的费托重油中，形成氢饱和费托重油，该氢饱和费托重油由第一加氢反应器的中部输入端输入第一加氢反应器，氢饱和费托轻油和氢饱和费托重油分别在加氢精制催化剂和加氢裂化催化剂的作用下进行加氢裂化反应生成中间馏分油，中间馏分油通过第二加氢反应器的底部输入端输入第二加氢反应器；Step 1: Hydrogen saturation in the second hydrogen delivery conduit is dissolved in Fischer-Tropsch light oil in the Fischer light oil delivery pipeline to form a hydrogen-saturated Fischer-Tropsch light oil, the hydrogen-saturated Fischer-Tropsch light oil from the first hydrogenation reactor The bottom input end is input to the first hydrogenation reactor, and the hydrogen in the first hydrogen delivery pipeline is saturated and dissolved in the Fischer-Tropsch heavy oil in the Fischer-Tropsch heavy oil delivery pipeline to form a hydrogen-saturated Fischer-Tropsch heavy oil, and the hydrogen-saturated Fischer-Tropsch heavy oil is The central input end of a hydrogenation reactor is input to the first hydrogenation reactor, and the hydrogen-saturated Fischer-Tropsch light oil and the hydrogen-saturated Fischer-Tropsch heavy oil are respectively subjected to a hydrocracking reaction under the action of a hydrotreating catalyst and a hydrocracking catalyst to form an intermediate Distillate, middle distillate is fed to the second hydrogenation reactor through the bottom input of the second hydrogenation reactor;
步骤2：中间馏分油在第二加氢反应器分别通过第一催化剂反应床层的加氢裂化催化剂和第二催化剂反应床层的加氢异构催化剂进行加氢异构反应，生成低凝中间馏分油；Step 2: The middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed, respectively, to form a low condensation intermediate Distillate oil
步骤3：低凝中间馏分油进入气液分离器进行气液分离处理，分离出的液相进入分馏塔分馏得到石脑油产品和目的产物低凝柴油。Step 3: The low-condensation middle distillate enters the gas-liquid separator for gas-liquid separation treatment, and the separated liquid phase enters the fractionation column to fractionate to obtain the naphtha product and the target product low-condensed diesel oil.
本发明的有益效果：The beneficial effects of the invention:
1、本发明中加氢裂化和加氢异构都采用下进料方式，使氢浓度沿反应器轴向分布更合理，反应器温度梯度最小，同时克服了催化剂床层上部压降大的问题。1. In the present invention, both the hydrocracking and the hydroisomerization adopt the lower feeding mode, so that the hydrogen concentration is more rationally distributed along the axial direction of the reactor, the reactor temperature gradient is the smallest, and the problem of large pressure drop in the upper part of the catalyst bed is overcome. .
2、费托合成产物以饱和直链烃为主，饱和度较高，化学氢耗低。2. The Fischer-Tropsch synthesis products are mainly saturated linear hydrocarbons with high saturation and low chemical hydrogen consumption.
3、本发明中费托轻油和费托重油如本发明所述分开进料，一来可以保持精制反应床层温度控制平稳，二来又降低了费托重油进料的温度，降低了能耗。
3. In the present invention, the Fischer-Tropsch light oil and the Fischer-Tropsch heavy oil are separately fed as described in the present invention, so that the temperature of the refined reaction bed can be kept stable, and the temperature of the Fischer-Tropsch heavy oil feed is lowered, and the energy is lowered. Consumption.
图1为本发明的结构示意图；Figure 1 is a schematic view of the structure of the present invention;
其中，1—第一加氢反应器、2—第二加氢反应器、3—气液分离器、4—分馏塔、5—费托重油输送管道、6—费托轻油输送管道、7—第一氢气输送管道、8—第二氢气输送管道、9—石脑油产品输出口、10—低凝柴油输出口。Among them, 1 - first hydrogenation reactor, 2 - second hydrogenation reactor, 3 - gas liquid separator, 4 - fractionation tower, 5 - Fischer heavy oil pipeline, 6 - Fischer light oil pipeline, 7 - First hydrogen delivery pipe, 8 - second hydrogen delivery pipe, 9 - naphtha product output port, 10 - low condensation diesel output port.
以下结合附图和具体实施例对本发明作进一步的详细说明：The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments:
如图1所述的费托合成全馏分油生产低凝中间馏分油***，它包括第一加氢反应器1、第二加氢反应器2、气液分离器3、分馏塔4、费托重油输送管道5、费托轻油输送管道6、第一氢气输送管道7和第二氢气输送管道8，其中，所述第一加氢反应器1包含上催化剂床层和下催化剂床层，所述费托重油输送管道5连接第一加氢反应器1的中部输入端，费托轻油输送管道6连接第一加氢反应器1的底部输入端，所述第一加氢反应器1的底部输入端位于第一加氢反应器1下催化剂床层的下方，所述第一加氢反应器1的中部输入端位于第一加氢反应器1上催化剂床层和下催化剂床层之间，第一氢气输送管道7与费托重油输送管道5连通，第二氢气输送管道8与费托轻油输送管道6连通，第一加氢反应器1的输出管道连接第二加氢反应器2的底部输入端，第二加氢反应器2的顶部输出端连接气液分离器3的输入端，气液分离器3的液相输出端连接分馏塔4的输入端，所述分馏塔4具有石脑油产品输出口9和低凝柴油输出口10，分馏塔4的循环油输出端连接第二加氢反应器2的底部输入端。A Fischer-Tropsch full-distillate oil production system as shown in Figure 1 comprises a first hydrogenation reactor 1, a second hydrogenation reactor 2, a gas-liquid separator 3, a fractionation column 4, and Fischer-Tropsch a heavy oil delivery conduit 5, a Fischer light oil delivery conduit 6, a first hydrogen delivery conduit 7 and a second hydrogen delivery conduit 8, wherein the first hydrogenation reactor 1 comprises an upper catalyst bed and a lower catalyst bed, The Fischer heavy oil delivery pipe 5 is connected to the central input end of the first hydrogenation reactor 1, and the Fischer-Tropical light oil delivery pipe 6 is connected to the bottom input end of the first hydrogenation reactor 1, the first hydrogenation reactor 1 The bottom input end is located below the catalyst bed under the first hydrogenation reactor 1, and the central input end of the first hydrogenation reactor 1 is located between the catalyst bed and the lower catalyst bed on the first hydrogenation reactor 1. The first hydrogen delivery conduit 7 is in communication with the Fischer-Tropsch heavy oil delivery conduit 5, the second hydrogen delivery conduit 8 is in communication with the Fischer-Tropsch light oil delivery conduit 6, and the output conduit of the first hydrogenation reactor 1 is coupled to the second hydrogenation reactor 2 Bottom input, the top output of the second hydrogenation reactor 2 is connected At the input end of the gas-liquid separator 3, the liquid phase output end of the gas-liquid separator 3 is connected to the input end of the fractionation column 4, the fractionation column 4 has a naphtha product output port 9 and a low-condensation diesel output port 10, and a fractionation tower The circulating oil output of 4 is connected to the bottom input of the second hydrogenation reactor 2.
上述技术方案中，所述第一加氢反应器1的上催化剂床层填加加氢裂化催化剂，第一加氢反应器1的下催化剂床层填加氢精制催化剂。In the above technical solution, the upper catalyst bed of the first hydrogenation reactor 1 is filled with a hydrocracking catalyst, and the lower catalyst bed of the first hydrogenation reactor 1 is filled with a hydrotreating catalyst.
上述技术方案中，所述加氢精制催化剂中加氢活性金属为Ni和Mo，含氧化合物含量范围按质量百分比为1％～40％，催化剂载体为多孔耐熔氧化物，如氧化铝、氧化硅或复合氧化物等。所述加氢精制催化剂的比表面积范围为200～600m2/g，加氢精制催化剂的孔容范围为0.3～0.6ml/g。In the above technical solution, the hydrogenation active metal in the hydrorefining catalyst is Ni and Mo, the content of the oxygen compound is in the range of 1% to 40% by mass, and the catalyst carrier is a porous refractory oxide such as alumina, oxidized. Silicon or composite oxide. The hydrotreating catalyst has a specific surface area in the range of 200 to 600 m 2 /g, and the hydrorefining catalyst has a pore volume in the range of 0.3 to 0.6 ml/g.
上述技术方案中，所述加氢裂化催化剂中的无定形硅铝的含量按质量百分
比为40％～80％，加氢裂化催化剂中的加氢活性金属为Ni和W，加氢裂化催化剂中的含氧化合物总含量按质量百分比为10％～30％。所述加氢裂化催化剂中的分子筛为Y型分子筛、β分子筛、ZSM-5分子筛、SAPO分子筛和MCM-41介孔分子筛中的一种或几种。所述加氢裂化催化剂中分子筛的含量按质量百分比为1％～20％，所述加氢裂化催化剂的比表面积范围为200～500m2/g，加氢裂化催化剂的孔容范围为0.3～0.7ml/g。In the above technical solution, the content of the amorphous silicon aluminum in the hydrocracking catalyst is 40% to 80% by mass, and the hydrogenation active metals in the hydrocracking catalyst are Ni and W, in the hydrocracking catalyst. The total content of oxygenates is 10% to 30% by mass. The molecular sieve in the hydrocracking catalyst is one or more of Y-type molecular sieve, β molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesoporous molecular sieve. The hydrocracking catalyst has a molecular sieve content of 1% to 20% by mass, the hydrocracking catalyst has a specific surface area of 200 to 500 m 2 /g, and the hydrocracking catalyst has a pore volume of 0.3 to 0.7. Ml/g.
上述技术方案中，所述第二加氢反应器2包含两个催化剂反应床层，从下往上分别为第一催化剂反应床层和第二催化剂反应床层，第一催化剂反应床层装填加氢裂化催化剂，第二催化剂反应床层装填加氢异构催化剂。加氢异构催化剂的裂化性能相对较弱，以直链烃异构为主要反应，凝点可以明显降低。In the above technical solution, the second hydrogenation reactor 2 comprises two catalyst reaction beds, and the first catalyst reaction bed layer and the second catalyst reaction bed layer are respectively from bottom to top, and the first catalyst reaction bed layer is loaded and added. The hydrogen cracking catalyst, the second catalyst reaction bed is loaded with a hydroisomerization catalyst. The cracking performance of the hydroisomerization catalyst is relatively weak, and the isomerization of linear hydrocarbons is the main reaction, and the freezing point can be significantly reduced.
上述技术方案中，加氢精制催化剂、加氢裂化催化剂和加氢异构催化剂可以选用现有的匹配的商业催化剂。In the above technical solution, the hydrotreating catalyst, the hydrocracking catalyst and the hydroisomerization catalyst may be selected from existing matched commercial catalysts.
上述技术方案中，第一加氢反应器1包含精制和裂化处理过程，第二加氢反应器2包含裂化和异构处理过程。In the above technical solution, the first hydrogenation reactor 1 comprises a refining and cracking treatment process, and the second hydrogenation reactor 2 comprises a cracking and heterogeneous treatment process.
一种利用上述***生产低凝中间馏分油的方法，它包括如下步骤：A method for producing a low-condensation middle distillate using the above system, comprising the steps of:
步骤1：第二氢气输送管道8中的氢饱和溶于费托轻油输送管道6中的费托轻油(温度＜350℃)中，形成氢饱和费托轻油，该氢饱和费托轻油由第一加氢反应器1的底部输入端输入第一加氢反应器1，第一氢气输送管道7中的氢饱和溶于费托重油输送管道5中的费托重油中，形成氢饱和费托重油(温度≥350℃)，该氢饱和费托重油由第一加氢反应器1的中部输入端输入第一加氢反应器1，氢饱和费托轻油和氢饱和费托重油分别在加氢精制催化剂和加氢裂化催化剂的作用下进行加氢裂化反应生成中间馏分油，中间馏分油通过第二加氢反应器2的底部输入端输入第二加氢反应器2；Step 1: Hydrogen saturation in the second hydrogen delivery conduit 8 is dissolved in Fischer-Tropsch light oil (temperature <350 ° C) in the Fischer-Tropsch light oil delivery pipe 6, forming a hydrogen-saturated Fischer-Tropsch light oil, which is lightly charged. The oil is supplied to the first hydrogenation reactor 1 from the bottom input end of the first hydrogenation reactor 1, and the hydrogen in the first hydrogen delivery conduit 7 is saturated and dissolved in the Fischer-Tropsch heavy oil in the Fischer-Tropsch heavy oil delivery conduit 5 to form a hydrogen saturation. Fischer heavy oil (temperature ≥350 ° C), the hydrogen-saturated Fischer-Tropsch heavy oil is input into the first hydrogenation reactor 1 from the central input end of the first hydrogenation reactor 1, and the hydrogen-saturated Fischer-Tropsch light oil and the hydrogen-saturated Fischer-Tropsch heavy oil are respectively The hydrocracking reaction and hydrocracking catalyst are subjected to hydrocracking reaction to form a middle distillate oil, and the middle distillate oil is fed into the second hydrogenation reactor 2 through the bottom input end of the second hydrogenation reactor 2;
步骤2：中间馏分油在第二加氢反应器2分别通过第一催化剂反应床层的加氢裂化催化剂和第二催化剂反应床层的加氢异构催化剂进行加氢异构反应，生成低凝中间馏分油；Step 2: The middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor 2 through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed to form a low-condensation reaction. Middle distillate;
步骤3：低凝中间馏分油进入气液分离器3进行气液分离处理，分离出的液相进入分馏塔4分馏得到石脑油产品和目的产物低凝柴油，分离出的气相很
少，可以作燃料气。Step 3: The low-condensation middle distillate enters the gas-liquid separator 3 for gas-liquid separation treatment, and the separated liquid phase enters the fractionation column 4 to fractionate and obtain the naphtha product and the target product low-condensed diesel oil, and the separated gas phase is very
Less, it can be used as fuel gas.
步骤4，分馏塔4中的循环油返回第二加氢反应器2的底部输入端，循环油在第二加氢反应器2中产生循环油溶解氢，对加氢异构反应所用氢中不足的部分进行补充。 Step 4, the circulating oil in the fractionation column 4 is returned to the bottom input end of the second hydrogenation reactor 2, and the circulating oil generates hydrogen in the second hydrogenation reactor 2 to generate hydrogen, and the hydrogen used in the hydroisomerization reaction is insufficient. The part is supplemented.
本发明可以选择在第一加氢反应器1的底部输入端和中部输入端装填加氢保护剂，也可以在第二加氢反应器2的顶部输出端前装填后精制催化剂。The present invention may optionally be filled with a hydrogenation protecting agent at the bottom input end and the middle input end of the first hydrogenation reactor 1, or may be refined after the top output end of the second hydrogenation reactor 2 is charged.
上述技术方案中，物流经加氢裂化后，部分氢气被消耗，需要补充氢，因是液相加氢，故补充的氢是饱和溶解在物流中的。In the above technical solution, after the hydrocracking of the stream, part of the hydrogen is consumed, and hydrogen needs to be replenished. Since the liquid phase is hydrogenated, the supplemented hydrogen is saturated and dissolved in the stream.
上述技术方案中，本文的低凝意思是经过加氢裂化尤其是加氢异构降凝的柴油，凝点根据实际需要，只要低于0#柴油的都可以称作低凝。In the above technical solution, the low-condensation herein means diesel oil undergoing hydrocracking, especially hydroisomerization and decondensation, and the freezing point can be called low-condensation as long as it is lower than 0# diesel according to actual needs.
表1为实施例所用的实验条件，实验结果。加氢精制催化剂、加氢裂化催化剂和加氢异构催化剂均根据上述本发明所述方法和条件等限制，由实验室常规方法制备。Table 1 shows the experimental conditions and experimental results used in the examples. The hydrotreating catalyst, the hydrocracking catalyst, and the hydroisomerization catalyst are all prepared by a laboratory conventional method in accordance with the above-described methods and conditions of the present invention.
表1 为工艺实验条件和结果Table 1 shows the experimental conditions and results of the process.
|
项目 | 项目1Item 1 |
项目2 |
项目3 |
项目4 |
|
|
实验条件 |
11 | 22 | 33 | 44 | |
| 裂化平均温度/℃Cracking average temperature / ° C | 330330 | 335335 | 340340 | 345345 | |
| ＞350℃馏分转化率/％>350 ° C fraction conversion rate /% | 4747 | 5454 | 6262 | 7272 |
表1说明本发明的产低凝柴油收率好，产品性质好。Table 1 shows that the yield of the low-condensation diesel produced by the present invention is good and the product properties are good.
本说明书未作详细描述的内容属于本领域专业技术人员公知的现有技术。
The contents not described in detail in the specification belong to the prior art known to those skilled in the art.
Claims (10)
- 一种费托合成全馏分油生产低凝中间馏分油***，其特征在于：它包括第一加氢反应器(1)、第二加氢反应器(2)、气液分离器(3)、分馏塔(4)、费托重油输送管道(5)、费托轻油输送管道(6)、第一氢气输送管道(7)和第二氢气输送管道(8)，其中，所述第一加氢反应器(1)包含上催化剂床层和下催化剂床层，所述费托重油输送管道(5)连接第一加氢反应器(1)的中部输入端，费托轻油输送管道(6)连接第一加氢反应器(1)的底部输入端，所述第一加氢反应器(1)的底部输入端位于第一加氢反应器(1)下催化剂床层的下方，所述第一加氢反应器(1)的中部输入端位于第一加氢反应器(1)上催化剂床层和下催化剂床层之间，第一氢气输送管道(7)与费托重油输送管道(5)连通，第二氢气输送管道(8)与费托轻油输送管道(6)连通，第一加氢反应器(1)的输出管道连接第二加氢反应器(2)的底部输入端，第二加氢反应器(2)的顶部输出端连接气液分离器(3)的输入端，气液分离器(3)的液相输出端连接分馏塔(4)的输入端，所述分馏塔(4)具有石脑油产品输出口(9)和低凝柴油输出口(10)，分馏塔(4)的循环油输出端连接第二加氢反应器(2)的底部输入端。A Fischer-Tropsch synthesis whole distillate oil production low condensation middle distillate oil system, characterized in that it comprises a first hydrogenation reactor (1), a second hydrogenation reactor (2), a gas-liquid separator (3), a fractionation tower (4), a Fischer heavy oil delivery pipeline (5), a Fischer-Tropsch light oil delivery pipeline (6), a first hydrogen delivery pipeline (7), and a second hydrogen delivery conduit (8), wherein the first addition The hydrogen reactor (1) comprises an upper catalyst bed and a lower catalyst bed, the Fischer heavy oil delivery pipe (5) is connected to the central input end of the first hydrogenation reactor (1), and the Fischer light oil delivery pipe (6) Connecting a bottom input end of the first hydrogenation reactor (1), the bottom input end of the first hydrogenation reactor (1) being located below the catalyst bed under the first hydrogenation reactor (1), The central input end of the first hydrogenation reactor (1) is located between the catalyst bed and the lower catalyst bed on the first hydrogenation reactor (1), the first hydrogen delivery conduit (7) and the Fischer-Tropsch heavy oil delivery conduit ( 5) connected, the second hydrogen delivery pipe (8) is connected with the Fischer light oil delivery pipe (6), and the output pipe of the first hydrogenation reactor (1) is connected to the bottom of the second hydrogenation reactor (2). The top end of the second hydrogenation reactor (2) is connected to the input end of the gas-liquid separator (3), and the liquid phase output end of the gas-liquid separator (3) is connected to the input end of the fractionation column (4). The fractionation column (4) has a naphtha product outlet (9) and a low-condensation diesel outlet (10), and a circulating oil output end of the fractionation column (4) is connected to a bottom input end of the second hydrogenation reactor (2) .
- 根据权利要求1所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述第一加氢反应器(1)的上催化剂床层填加加氢裂化催化剂，第一加氢反应器(1)的下催化剂床层填加氢精制催化剂。The Fischer-Tropsch synthesis whole distillate oil production low condensation middle distillate system according to claim 1, wherein the upper catalyst bed of the first hydrogenation reactor (1) is filled with a hydrocracking catalyst, first The lower catalyst bed of the hydrogenation reactor (1) is filled with a hydrotreating catalyst.
- 根据权利要求2所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述加氢精制催化剂中加氢活性金属为Ni和Mo，含氧化合物含量范围按质量百分比为1％～40％，催化剂载体为多孔耐熔氧化物。The Fischer-Tropsch synthesis whole distillate oil producing low-condensation middle distillate system according to claim 2, wherein the hydrogenation active metal in the hydrotreating catalyst is Ni and Mo, and the oxygen content is in a mass percentage range. 1% to 40%, the catalyst carrier is a porous refractory oxide.
- 根据权利要求3所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述加氢精制催化剂的比表面积范围为200～600m2/g，加氢精制 催化剂的孔容范围为0.3～0.6ml/g。The Fischer-Tropsch synthesis whole distillate oil producing low-condensation middle distillate system according to claim 3, wherein the hydrotreating catalyst has a specific surface area in the range of 200 to 600 m 2 /g, and the pore volume of the hydrotreating catalyst The range is from 0.3 to 0.6 ml/g.
- 根据权利要求2所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述加氢裂化催化剂中的无定形硅铝的含量按质量百分比为40％～80％，加氢裂化催化剂中的加氢活性金属为Ni和W，加氢裂化催化剂中的含氧化合物总含量按质量百分比为10％～30％。The Fischer-Tropsch synthesis whole distillate oil producing low-condensation middle distillate system according to claim 2, wherein the content of the amorphous silicon aluminum in the hydrocracking catalyst is 40% to 80% by mass, plus The hydrogenation-active metal in the hydrogen cracking catalyst is Ni and W, and the total content of the oxygen-containing compound in the hydrocracking catalyst is 10% to 30% by mass.
- 根据权利要求5所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述加氢裂化催化剂中的分子筛为Y型分子筛、β分子筛、ZSM-5分子筛、SAPO分子筛和MCM-41介孔分子筛中的一种或几种。The Fischer-Tropsch synthesis whole distillate oil producing low-condensation middle distillate system according to claim 5, wherein the molecular sieve in the hydrocracking catalyst is Y-type molecular sieve, β molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and One or more of MCM-41 mesoporous molecular sieves.
- 根据权利要求6所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述加氢裂化催化剂中分子筛的含量按质量百分比为1％～20％，所述加氢裂化催化剂的比表面积范围为200～500m2/g，加氢裂化催化剂的孔容范围为0.3～0.7ml/g。The Fischer-Tropsch synthesis whole distillate oil production process according to claim 6, wherein the content of the molecular sieve in the hydrocracking catalyst is from 1% to 20% by mass, and the hydrocracking The specific surface area of the catalyst ranges from 200 to 500 m 2 /g, and the pore ratio of the hydrocracking catalyst ranges from 0.3 to 0.7 ml/g.
- 根据权利要求2所述的费托合成全馏分油生产低凝中间馏分油***，其特征在于：所述第二加氢反应器(2)包含两个催化剂反应床层，从下往上分别为第一催化剂反应床层和第二催化剂反应床层，第一催化剂反应床层装填加氢裂化催化剂，第二催化剂反应床层装填加氢异构催化剂。The Fischer-Tropsch synthesis whole distillate oil producing low condensation middle distillate system according to claim 2, wherein the second hydrogenation reactor (2) comprises two catalyst reaction beds, from bottom to top The first catalyst reaction bed and the second catalyst reaction bed, the first catalyst reaction bed is loaded with a hydrocracking catalyst, and the second catalyst reaction bed is charged with a hydroisomerization catalyst.
- 一种利用权利要求1所述***生产低凝中间馏分油的方法，其特征在于，它包括如下步骤：A method of producing a low-condensation middle distillate using the system of claim 1 comprising the steps of:步骤1：第二氢气输送管道(8)中的氢饱和溶于费托轻油输送管道(6)中的费托轻油中，形成氢饱和费托轻油，该氢饱和费托轻油由第一加氢反应器(1)的底部输入端输入第一加氢反应器(1)，第一氢气输送管道(7)中的氢饱和溶于费托重油输送管道(5)中的费托重油中，形成氢饱和费托重油，该氢饱和费托重油由第一加氢反应器(1)的中部输入端输入第一加氢反应器(1)， 氢饱和费托轻油和氢饱和费托重油分别在加氢精制催化剂和加氢裂化催化剂的作用下进行加氢裂化反应生成中间馏分油，中间馏分油通过第二加氢反应器(2)的底部输入端输入第二加氢反应器(2)；Step 1: Hydrogen saturation in the second hydrogen delivery pipe (8) is dissolved in Fischer-Tropsch light oil in the Fischer light oil delivery pipe (6) to form a hydrogen-saturated Fischer-Tropsch light oil, and the hydrogen-saturated Fischer-Tropsch light oil is The bottom input end of the first hydrogenation reactor (1) is fed to the first hydrogenation reactor (1), and the hydrogen in the first hydrogen delivery line (7) is saturated with Fischer in the Fischer-Tropsch heavy oil delivery pipe (5). In the heavy oil, a hydrogen-saturated Fischer-Tropsch heavy oil is formed, which is input into the first hydrogenation reactor (1) from the central input end of the first hydrogenation reactor (1), The hydrogen-saturated Fischer-Tropsch light oil and the hydrogen-saturated Fischer-Tropsch heavy oil are respectively subjected to hydrocracking reaction under the action of a hydrotreating catalyst and a hydrocracking catalyst to form a middle distillate oil, and the middle distillate oil passes through the second hydrogenation reactor (2) The bottom input is input to the second hydrogenation reactor (2);步骤2：中间馏分油在第二加氢反应器(2)分别通过第一催化剂反应床层的加氢裂化催化剂和第二催化剂反应床层的加氢异构催化剂进行加氢异构反应，生成低凝中间馏分油；Step 2: The middle distillate is subjected to hydroisomerization reaction in the second hydrogenation reactor (2) through the hydrocracking catalyst of the first catalyst reaction bed and the hydroisomerization catalyst of the second catalyst reaction bed, respectively. Low condensation middle distillate;步骤3：低凝中间馏分油进入气液分离器(3)进行气液分离处理，分离出的液相进入分馏塔(4)分馏得到石脑油产品和目的产物低凝柴油。Step 3: The low-condensation middle distillate enters the gas-liquid separator (3) for gas-liquid separation treatment, and the separated liquid phase enters the fractionation column (4) to fractionate and obtain the naphtha product and the target product low-condensation diesel oil.
- 根据权利要求9所述的生产低凝中间馏分油的方法，其特征在于：所述步骤3后还包括步骤4，分馏塔(4)中的循环油返回第二加氢反应器(2)的底部输入端，循环油在第二加氢反应器(2)中产生循环油溶解氢，对加氢异构反应所用氢中不足的部分进行补充。 The method for producing a low-condensation middle distillate according to claim 9, wherein the step 3 further comprises the step 4, wherein the circulating oil in the fractionation column (4) is returned to the second hydrogenation reactor (2). At the bottom input end, the circulating oil produces a circulating oil dissolved hydrogen in the second hydrogenation reactor (2) to supplement the insufficient portion of the hydrogen used in the hydroisomerization reaction.
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