WO2016138832A1 - 一种低温费托全馏分油多产中间馏分油的加氢精制方法 - Google Patents

一种低温费托全馏分油多产中间馏分油的加氢精制方法 Download PDF

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WO2016138832A1
WO2016138832A1 PCT/CN2016/074629 CN2016074629W WO2016138832A1 WO 2016138832 A1 WO2016138832 A1 WO 2016138832A1 CN 2016074629 W CN2016074629 W CN 2016074629W WO 2016138832 A1 WO2016138832 A1 WO 2016138832A1
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distillate
feed port
oil
tropsch
component
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PCT/CN2016/074629
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English (en)
French (fr)
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杨伟光
石友良
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武汉凯迪工程技术研究总院有限公司
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Priority to KR1020177025245A priority Critical patent/KR101960627B1/ko
Priority to CA2978221A priority patent/CA2978221A1/en
Priority to EP16758448.1A priority patent/EP3266853A4/en
Priority to RU2017133949A priority patent/RU2678443C1/ru
Priority to AU2016228066A priority patent/AU2016228066B2/en
Priority to JP2017544348A priority patent/JP6501899B2/ja
Publication of WO2016138832A1 publication Critical patent/WO2016138832A1/zh
Priority to US15/693,467 priority patent/US10450519B2/en

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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
    • C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/72—Controlling or regulating
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range

Definitions

  • the invention relates to a hydrorefining method for a low-temperature Fischer-Tropsch full-distillate oil-producing middle distillate, and belongs to a hydrogenation and upgrading technology for a Fischer-Tropsch synthesis product.
  • the main products of low temperature Fischer-Tropsch synthesis are complex mixtures of C 4 -C 70 hydrocarbons and a small amount of oxygenates, which are characterized by sulfur-free, nitrogen-free, metal-free and low aromatic hydrocarbons.
  • Each fraction obtained from the Fischer-Tropsch synthesis product needs to be subjected to a corresponding hydrotreating to obtain a qualified liquid fuel and chemical.
  • liquid hydrocarbons and synthetic waxes can be hydrotreated to produce products such as diesel, gasoline, naphtha and refined wax.
  • the hydrotreating process of the process of CN200710065309 does not consider the difference of light, heavy and middle distillate components in the Fischer-Tropsch synthetic oil, and the intermediate component has a longer residence time in the hydrogenation reactor, and it is easy to increase the secondary cracking.
  • 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 hydrotreating method for the low-cost Fischer-Tropsch full-distillate oil-producing middle distillate to ensure the stability and life of the catalyst, improve the product quality, and at the same time, the temperature rise is easy to control.
  • the light distillate, heavy distillate and middle distillate are metered into the hydrogenation reactor by the metering pump, and the hydrogenation reactor is filled with the refining catalyst, and the hydrogenation reactor is firstly arranged from the upper part to the middle part.
  • the feed port, the second feed port, the third feed port, the light component is fed from the first feed port, the heavy component is fed from the second feed port, and the intermediate component is fed from the third feed port
  • the circulating hydrogen is mixed with the light distillate, the heavy distillate and the middle distillate from the hydrogen inlet port to enter the hydrogenation reactor through the first feed port, the second feed port and the third feed port;
  • the pressure is 4-8 MPa
  • the hydrogen to oil ratio is 100:1 to 2000:1
  • the liquid space velocity is 0.1-5.0 h -1
  • the reaction temperature is 300 ° C to 420 ° C;
  • step 3 The product of the above step 2) is separated into a gas-liquid separator, and the separated gas circulating hydrogen is combined with new hydrogen to be injected into the first feed port, the second feed port, the third feed port of the hydrogenation reactor, respectively.
  • the light distillate, heavy distillate and middle distillate components are combined and the liquid phase product is passed to a fractionation column for subsequent separation.
  • the step 2) has a reaction pressure of 4 to 8 MPa, a hydrogen to oil ratio of 100:1 to 2000:1, a liquid space velocity of 0.1 to 5.0 h -1 , a reaction temperature of 300 to 420 ° C, and a more preferable reaction pressure. It is 5 to 7.5 MPa, the hydrogen to oil ratio is 700:1 to 1200:1, the liquid space velocity is 0.5 to 2.0 h -1 , and the reaction temperature is 320 to 400 °C.
  • the positions of the first feed port, the second feed port and the third feed port of the hydrogenation reactor are: the first feed port is located at the top of the hydrogenation reactor, and the second feed port is located at the reaction From the top to the bottom of 1/3H ⁇ 1/2H, the third feed port is located at the lower part of the second feed port 1 / 6H ⁇ 1/3H, H is the height of the hydrogenation reactor.
  • the step 1) is to divide the low-temperature Fischer-Tropsch full-distillate oil-producing middle distillate into light distillate, heavy distillate and middle distillate.
  • the Fischer-Tropsch full-fraction product has a distillation range of less than 180 ° C as a light fraction.
  • the oil component, the distillation range is between 180-360 ° C for the middle distillate component, and the distillation range is higher than 360 ° C as the heavy distillate component.
  • the step 1) dividing the low-temperature Fischer-Tropsch full-distillate oil-producing middle distillate into light distillate, heavy distillate and middle distillate may also be: Fischer-Tropsch synthesis full-distillate product distillation range below 150 ° C
  • the light distillate component has a distillation range of between 180 and 350 ° C as a middle distillate component and a distillation range of more than 350 ° C as a heavy distillate component.
  • the invention has the advantages that the invention provides a three-stage feeding method using Fischer-Tropsch synthesis light, heavy and intermediate components as raw materials, thereby maintaining the temperature control of the refined reaction bed to be stable, and further reducing the middle and upper heavy components.
  • the temperature of the feed reduces the energy consumption.
  • the intermediate component is fed from the middle section of the reactor to reduce the residence time of the intermediate component in the reactor bed, thereby slowing the secondary cracking of the light component and providing a guarantee for the production of the middle distillate.
  • FIG. 1 is a process flow diagram of a low temperature Fischer-Tropsch synthesis full distillate hydrofining process of the present invention.
  • the method for hydrotreating the low-temperature Fischer-Tropsch full-distillate oil-producing middle distillate of the present invention has the following steps:
  • the light distillate, heavy distillate and middle distillate are metered into the hydrogenation reactor 1 by the metering pump, and all the hydrogenation reactor 1 is filled with the refining catalyst, and the hydrogenation reactor 1 is sequentially from the upper part to the middle part.
  • the first feed port 1a, the second feed port 1b, and the third feed port 1c are provided, the light component is fed from the first feed port 1a, and the heavy component is fed from the second feed port 1b, the intermediate component Feeding from the third feed port 1c; at the same time, the circulating hydrogen is mixed with the light distillate, the heavy distillate and the middle distillate by the hydrogen inlet port 1d, respectively, by the first feed port 1a, the second feed port 1b, and the third
  • the feed port 1c enters the reaction in the hydrogenation reactor 1;
  • the reaction pressure is 4-8 MPa, the hydrogen to oil ratio is 100:1 to 2000:1, the liquid space velocity is 0.1 to 5.0 h -1 , and the reaction temperature is 300 ° C to 420
  • Step 2) The product of the reaction enters the gas-liquid separator separation 2, and the separated gas circulating hydrogen is combined with the new hydrogen to be injected into the first feed port 1a, the second feed port 1b, and the first of the hydrogenation reactor (1), respectively.
  • the three feed port 1c is mixed with the light distillate, heavy distillate and middle distillate components, and the liquid phase product enters the fractionation column 3 for subsequent separation.
  • the reaction pressure in step 2) is 5 to 7.5 MPa
  • the hydrogen to oil ratio is 700:1 to 1200:1
  • the liquid space velocity is 0.5 to 2.0 h -1
  • the reaction temperature is 320 to 400 °C.
  • the positions of the first feed port 1a, the second feed port 1b, and the third feed port 1c are respectively: the first feed port 1a is located at the top of the hydrogenation reactor 1, and the second feed port 1b is located The reactor is from 1/3H to 1/2H from the top to the bottom, and the third feed port is located at the lower portion of the second feed port at 1/6H to 1/3H, and H is the height of the hydrogenation reactor 1.
  • the low step 1) divides the low-temperature Fischer-Tropsch full-distillate oil-producing middle distillate into light distillate, heavy distillate and middle distillate; the light, heavy and intermediate components can be fed in any proportion. .
  • Fischer-Tropsch synthesis full-distillate product distillation range below 180 °C for light distillate component distillation range between 180-360 °C for middle distillate component, distillation range higher than 360 °C for heavy fraction Oil component. It can also be divided into: Fischer-Tropsch synthesis full-distillate product distillation range below 150 °C as light distillate component, distillation range between 180-350 °C for middle distillate component, distillation range above 350 °C Distillate component.
  • the conventional hydrotreating catalyst used in the present invention can be selected from various commercial catalysts, such as FF-14, FF-24, 3936, FF-16, FF-26, FF-36 developed by Fushun Petrochemical Research Institute.
  • a hydrotreating catalyst such as FF-46 can also be prepared according to common knowledge in the art as needed.
  • Fischer-Tropsch synthesized unsaturated olefins and oxygenates are mainly concentrated in light components.
  • the light components are hydrotreated and exothermic.
  • the heavy components in the upper part of the upper part can be diluted from the upper part.
  • the large amount of reaction heat released by hydrogen refining makes the temperature rise more controllable, effectively reduces the temperature rise of the bed, prolongs the life of the catalyst, and makes the operation stable; at the same time, it can heat the heavy components, so that the heavy components reach the reaction temperature and reduce the energy consumption.
  • the intermediate component is fed from the middle section, so the residence time in the reactor becomes shorter, and the intermediate component can be prevented from being excessively cracked, which provides support for the production of the middle distillate.
  • the low-temperature Fischer-Tropsch synthesis full-distillate hydrotreating method provided by the invention adopts a single reactor to hydrotreat the Fischer-Tropsch synthesis product, which simplifies the process flow, reduces equipment investment and reduces energy consumption.
  • the Fischer-Tropsch full-fraction product was used as raw material, and a self-made fixed-bed reactor with an inner diameter of 2 cm was used.
  • the first, second and third feed ports were respectively located at the upper vertex of the reactor, 1/3H and 1/2H, and filled.
  • 30ml of conventional hydrotreating catalyst prepared in the laboratory the Fischer-Tropsch full-fraction product distillation range is lower than 180 °C as light component, the distillation range is between 180-360 °C as intermediate component, and the distillation range is higher than 360 °C. It is counted as a heavy component.
  • the light, heavy and intermediate components are metered by a metering pump and mixed with hydrogen respectively to enter the hydrogenation reactor.
  • Examples 1 to 5 are different proportions of light and heavy component Fischer-Tropsch synthetic oil in a reactor device designed according to the method of the present invention.
  • Comparative Examples 1 and 2 are cases in which light, heavy and intermediate components are mixed in different proportions and fed together from the upper end of the reaction tube.
  • the following table shows the reaction conditions and index parameters of Examples 1 to 5 and Comparative Examples 1 and 2.

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Abstract

一种低温费托全馏分油多产中间馏分油的加氢精制方法：将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油，由上部至中部依次进入加氢反应器的第一、第二、第三进料口进行加氢精制；循环氢由氢气进入口分别与三种组分混合进入加氢反应器；反应产物进行后续分离。该方法保持精制反应床层温度控制平稳，降低了重组分进料温度，缩短了中间组分的停留时间，减轻了二次裂化。

Description

一种低温费托全馏分油多产中间馏分油的加氢精制方法 技术领域
本发明涉及一种低温费托全馏分油多产中间馏分油的加氢精制方法，属于对费托合成产物的加氢提质技术。
背景技术
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。费托合成产物得到的各个馏分需要经过相应的加氢提质，才能得到合格的液体燃料及化学品。通常液态烃和合成蜡经加氢处理后可以生产出柴油、汽油、石脑油和精制蜡等产品。
US6309432没有考虑费托合成油中的烯烃和含氧化合物，直接异构裂化，影响催化剂的稳定性和寿命，且产品质量较差。
CN200710065309工艺的加氢处理没有考虑费托合成油中轻、重及中间馏分组分的差异，中间组分在加氢反应器中停留时间较长，容易增加二次裂化。
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。
发明内容
本发明的目的是给出一种低温费托全馏分油多产中间馏分油的加氢精制方法，保证催化剂的稳定性和寿命，提高产品质量，同时温升易控制。
本发明的技术方案：本发明的低温费托全馏分油多产中间馏分油的加氢精制方法步骤如下：
1)将本低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种；
2)所述的轻馏分油、重馏分油及中间馏分油经计量泵计量后分别进入加氢反应器，加氢反应器内全部装填精制催化剂，加氢反应器由上部至中部依次设第一进料口、第二进料口、第三进料口，轻组分从第一进料口进料，重组分从第二进料口进料，中间组分 从第三进料口进料；同时，循环氢由氢气进入口分别与轻馏分油、重馏分油及中间馏分油混合由第一进料口、第二进料口、第三进料口进入加氢反应器内反应；反应压力为4～8MPa，氢油比为100:1～2000:1，液空速为0.1～5.0h-1，反应温度为300℃～420℃；
3)上述步骤2)反应的产物进入气液分离器分离，分离的气体循环氢与新氢汇合分别注入加氢反应器的第一进料口、第二进料口、第三进料口与轻馏分油、重馏分油及中间馏分油组分混合，液相产物进入分馏塔进行后续分离。
所述的步骤2)反应压力为4～8MPa，氢油比为100:1～2000:1，液空速为0.1～5.0h-1，反应温度为300℃～420℃，更优选的反应压力为5～7.5MPa，氢油比为700：1～1200：1，液空速为0.5～2.0h-1，反应温度为320℃～400℃。
所述的加氢反应器的第一进料口、第二进料口、第三进料口的位置分别是：第一进料口位于加氢反应器上顶部，第二进料口位于反应器从上往下的1/3H～1/2H处，第三进料口位于第二进料口下部1/6H～1/3H处，H为加氢反应器的高度。
所述的步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种是：费托合成全馏分产物馏程低于180℃计为轻馏分油组分，馏程在180～360℃之间为中间馏分油组分，馏程高于360℃计为重馏分油组分。
所述的步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种还可以是：费托合成全馏分产物馏程低于150℃计为轻馏分油组分，馏程在180～350℃之间为中间馏分油组分，馏程高于350℃计为重馏分油组分。
本发明的优点：本发明的提供以费托合成轻、重及中间组分为原料分三段进料法，一来可以保持精制反应床层温度控制平稳，二来又降低了中上段重组分进料的温度，降低了能耗。同时中间组分从反应器中间段进料降低了中间组分在反应器床层的停留时间，从而减缓了轻组分的二次裂化，为多产中间馏分油提供了保证。
附图说明
图1是本发明的低温费托合成全馏分油加氢精制方法的工艺流程图。
具体实施方式
为了进一步说明本发明要点，下面结合附图1对本发明做进一步的说明。
本发明的低温费托全馏分油多产中间馏分油的加氢精制方法，步骤如下：
1)将本低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种；
2)所述的轻馏分油、重馏分油及中间馏分油经计量泵计量后分别进入加氢反应器1，加氢反应器1内全部装填精制催化剂，加氢反应器1由上部至中部依次设第一进料口1a、第二进料口1b、第三进料口1c，轻组分从第一进料口1a进料，重组分从第二进料口1b进料，中间组分从第三进料口1c进料；同时，循环氢由氢气进入口1d分别与轻馏分油、重馏分油及中间馏分油混合由第一进料口1a、第二进料口1b、第三进料口1c进入加氢反应器1内反应；反应压力为4～8MPa，氢油比为100:1～2000:1，液空速为0.1～5.0h-1，反应温度为300℃～420℃；
3)步骤2)反应的产物进入气液分离器分离2，分离的气体循环氢与新氢汇合分别注入加氢反应器(1)的第一进料口1a、第二进料口1b、第三进料口1c与轻馏分油、重馏分油及中间馏分油组分混合，液相产物进入分馏塔3进行后续分离。
优选地，步骤2)反应压力为5～7.5MPa，氢油比为700：1～1200：1，液空速为0.5～2.0h-1，反应温度为320℃～400℃。
所述的第一进料口1a、第二进料口1b、第三进料口1c的位置分别是：第一进料口1a位于加氢反应器1上顶部，第二进料口1b位于反应器从上往下的1/3H～1/2H处，第三进料口位于第二进料口下部1/6H～1/3H处，H为加氢反应器1的高度。
所述的低步骤1)将本低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种；轻、重、中间三种组分进料可以为任意比例。
可以分为：费托合成全馏分产物馏程低于180℃计为轻馏分油组分，馏程在180～360℃之间为中间馏分油组分，馏程高于360℃计为重馏分油组分。也可以分为：费托合成全馏分产物馏程低于150℃计为轻馏分油组分，馏程在180～350℃之间为中间馏分油组分，馏程高于350℃计为重馏分油组分。
本发明采用的常规加氢处理催化剂可以选用现有的各种商业催化剂，例如抚顺石油化工研究院研制开发的FF-14、FF-24、3936、FF-16、FF-26、FF-36、FF-46等加氢精制催化剂，也可以根据需要按本领域的常识进行制备。
本发明的优势在于：
1、费托合成的不饱和烯烃和含氧化合物主要集中在轻组分，轻组分加氢精制放热剧烈，中间偏上段进料的重组分可以稀释从上端进料的轻组分由于加氢精制放出的大量反应热，使温升更加可控，有效降低床层温升，延长了催化剂寿命，使运行平稳；同时又可加热重组分，使重组分达到反应温度，降低了能耗。
2、中间组分从中间段进料，因此在反应器内停留时间变短，可以较好避免中间组分过度裂化，为多产中间馏分油提供了支持。
3、本发明提供的低温费托合成全馏分油加氢精制方法采用单一反应器对费托合成产物进行加氢精制，简化了工艺流程，减少了设备投资，降低了能耗。
为了进一步说明本发明要点和效果及优势，下面结合具体实施例和对比例对本发明作进一步说明，但不限于下述例子。
以费托合成全馏分产物为原料，使用内径为2cm的自制固定床反应器，第一、第二、第三进料口分别位于反应器的上顶点、1/3H和1/2H处，装填实验室内自制的常规加氢精制催化剂30ml，费托合成全馏分产物馏程低于180℃计为轻组分，馏程在180～360℃之间为中间组分，馏程高于360℃计为重组分。轻、重、中间组分经计量泵计量后分别与氢气混合，进入加氢反应器，实施例1～5为不同比例轻、重组分费托合成油在依据本发明方法设计的反应器装置中试验的情况，对比例1和2为不同比例轻、重、中间组分混合后一起从反应管上端入口进料的情况。下表为实施例1～5和对比例1～2的反应条件和指标参数。
Figure PCTCN2016074629-appb-000001

Claims (8)

  1. 一种低温费托全馏分油多产中间馏分油的加氢精制方法，步骤如下：
    1)将本低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种；
    2)所述的轻馏分油、重馏分油及中间馏分油经计量泵计量后分别进入加氢反应器(1)，加氢反应器(1)内全部装填精制催化剂，加氢反应器(1)由上部至中部依次设第一进料口(1a)、第二进料口(1b)、第三进料口(1c)，轻组分从第一进料口(1a)进料，重组分从第二进料口(1b)进料，中间组分从第三进料口(1c)进料；同时，循环氢由氢气进入口(1d)分别与轻馏分油、重馏分油及中间馏分油混合由第一进料口(1a)、第二进料口(1b)、第三进料口(1c)进入加氢反应器(1)内反应；反应压力为4～8MPa，氢油比为100:1～2000:1，液空速为0.1～5.0h-1，反应温度为300℃～420℃；
    3)步骤2)反应的产物进入气液分离器分离，分离的气体循环氢与新氢汇合分别注入加氢反应器(1)的第一进料口(1a)、第二进料口(1b)、第三进料口(1c)与轻馏分油、重馏分油及中间馏分油组分混合，液相产物进入分馏塔进行后续分离。
  2. 根据权利要求1所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤2)反应压力为4～8MPa，氢油比为100:1～2000:1，液空速为0.1～5.0h-1，反应温度为300℃～420℃。
  3. 根据权利要求1或2所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：加氢反应器(1)的第一进料口(1a)、第二进料口(1b)、第三进料口(1c)的位置分别是：第一进料口(1a)位于加氢反应器(1)上顶部，第二进料口(1b)位于反应器从上往下的1/3H～1/2H处，第三进料口位于第二进料口下部1/6H～1/3H处，H为加氢反应器(1)的高度。
  4. 根据权利要求1或2所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及 中间馏分油三种是：费托合成全馏分产物馏程低于180℃计为轻馏分油组分，馏程在180～360℃之间为中间馏分油组分，馏程高于360℃计为重馏分油组分。
  5. 根据权利要求1或2所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种是：费托合成全馏分产物馏程低于150℃计为轻馏分油组分，馏程在180～350℃之间为中间馏分油组分，馏程高于350℃计为重馏分油组分。
  6. 根据权利要求3所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种是：费托合成全馏分产物馏程低于180℃计为轻馏分油组分，馏程在180～360℃之间为中间馏分油组分，馏程高于360℃计为重馏分油组分。
  7. 根据权利要求3所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤1)将低温费托全馏分油多产中间馏分油分成轻馏分油、重馏分油及中间馏分油三种是：费托合成全馏分产物馏程低于150℃计为轻馏分油组分，馏程在180～350℃之间为中间馏分油组分，馏程高于350℃计为重馏分油组分。
  8. 根据权利要求2所述的低温费托全馏分油多产中间馏分油的加氢精制方法，其特征在于：步骤2)更优选的反应压力为5～7.5MPa，氢油比为700：1～1200：1，液空速为0.5～2.0h-1，反应温度为320℃～400℃。
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