WO2014117309A1 - 多级溶氢的液相加氢反应方法 - Google Patents

多级溶氢的液相加氢反应方法 Download PDF

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WO2014117309A1
WO2014117309A1 PCT/CN2013/000903 CN2013000903W WO2014117309A1 WO 2014117309 A1 WO2014117309 A1 WO 2014117309A1 CN 2013000903 W CN2013000903 W CN 2013000903W WO 2014117309 A1 WO2014117309 A1 WO 2014117309A1
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hydrogen
reactor
liquid phase
oil
reaction
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PCT/CN2013/000903
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English (en)
French (fr)
Inventor
马守涛
张瑞芹
田然
刘永刚
王刚
张长森
张文成
郭金涛
赵野
翟赟璞
于春梅
徐兴敏
王燕
马宝利
董春明
徐铁钢
吴显军
靳丽丽
朱金玲
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中国石油天然气股份有限公司
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Priority to SG11201505262PA priority Critical patent/SG11201505262PA/en
Publication of WO2014117309A1 publication Critical patent/WO2014117309A1/zh
Priority to ZA2015/06228A priority patent/ZA201506228B/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
    • 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
    • C10G45/22—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 with hydrogen dissolved or suspended in the oil
    • 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

Definitions

  • the present invention relates to a liquid phase hydrogenation reaction process for multistage hydrogen storage, and more particularly to a process for liquid phase hydrotreating of a product.
  • BACKGROUND OF THE INVENTION As people's environmental awareness continues to increase, many countries have adopted environmental legislation to limit the sulfur content of diesel fuel to a very low level (10-15 g/g) to reduce harmful gas emissions and improve air quality.
  • the United States reduced the sulfur content of diesel to 15 g/g in 2006. In January 2003, Germany reduced the sulfur content to l ( ⁇ g/g. In other EU countries and Japan, the sulfur content was reduced to l ( ⁇ g/g in 2008.
  • China National Standard for Vehicle Diesel GB 19147-2009 The European Class III standard has a sulfur content requirement of less than 350 g/g.
  • the Ministry of Environmental Protection issued the fifth stage of the vehicle gasoline and diesel emission index with a diesel sulfur content requirement of less than 10 ⁇ .
  • the amount of hydrogen required is much greater than the amount of hydrogen consumed by the hydrogenation reaction.
  • the hydrogenation reaction is a strong exothermic reaction, in order to control the reaction temperature, a large amount of hydrogen and feedstock oil are required to carry away the heat of reaction through the catalyst bed; on the other hand, in the gas-liquid-solid three phase
  • maintaining a high partial pressure of hydrogen favors the hydrogenation reaction, inhibits coke formation, and prolongs catalyst life.
  • hydrogen that has not participated in the reaction is pressurized by a circulating hydrogen compressor and then re-delivered to the reactor to participate in the reaction.
  • the circulating hydrogen compressor has high investment and operating costs.
  • liquid phase hydrogenation technology In order to eliminate the circulating hydrogen and circulating hydrogen compressor and reduce the investment cost of the device, the liquid phase hydrogenation technology is proposed.
  • the hydrogen and the feedstock oil are premixed to dissolve the hydrogen in the feedstock oil. , and then enter the reactor to carry out the reaction, the hydrogen required in the reaction process is completely from the dissolved hydrogen, without the need to additionally add cold hydrogen.
  • the liquid phase cycle hydrogenation process has the advantages of relatively small reactor, low investment cost and easy control of reaction temperature.
  • liquid phase cycle hydrogenation also has a problem, that is, in order to meet the amount of hydrogen required in the hydrogenation process, it is necessary to use A large amount of circulating oil or additional solvent is added to dissolve the hydrogen, resulting in a decrease in hydrogenation efficiency.
  • the organic nitride is a poison of the hydrogenation catalyst and has a significant inhibitory effect on hydrodenitrogenation, hydrodesulfurization and hydrodearomatization. This inhibition is mainly due to the fact that some intermediate products of some nitrides and most nitrides have very strong adsorption energy with the hydrogenation reaction center of the catalyst, and other hydrogenation reactions are inhibited from the viewpoint of competitive adsorption.
  • the distillation of the hydrogenation product will greatly dilute the impurity content of the raw material, which is beneficial to the performance of the catalyst.
  • Hydrodesulfurization by-product s also has a significant inhibitory effect on hydrodesulfurization, hydrodenitrogenation and hydrodearomatization, literature Sie S T. [J]. Reaction order and role of hydrogen sulfide in deep
  • Hydrodesulfurization of gas oil consequences for industrial reactor configuration, Fuel Processing Technology, 1999, 61(1-2) : 149-171. It is believed that the effect of H 2 S on the hydrodesulfurization reaction is to increase the activation energy of the hydrodesulfurization reaction.
  • the activation energy of the reaction is 16 kcal/mol.
  • the partial pressure of hydrogen sulfide reaches 42 kPa, the activation energy rises to 20 kcal/mol; another effect is that a small amount of H 2 S exists.
  • the hydrodesulfurization rate will be greatly reduced, and the adsorption of H 2 S on the catalyst surface is a single layer adsorption. Once the adsorption center is occupied by s, the reaction rate will no longer decrease with the increase of s partial pressure. Therefore, the use of effective means to eliminate the impact of s is the key to solving the problem of deep desulfurization.
  • U.S. Patent No. 2,060, 144, 756 A1 discloses a two-phase hydrogenation control system method and apparatus. In the continuous liquid phase hydrogenation process, the recycled hydrogen is eliminated, and the hydrogen required for the hydrogenation reaction comes from the dissolved hydrogen in the liquid phase, and no additional hydrogen is required. However, it requires the use of a solvent or diluent with a high solubility of hydrogen to dissolve the hydrogen, which affects the subsequent hydrogenation efficiency.
  • the multi-stage hydrogen hydrogenation liquid phase hydrogenation reaction method of the present invention comprises the following contents: a part of the liquid material which has been subjected to hydrogenation in a stripping column is mixed with fresh raw material oil to be a liquid phase material, and the liquid phase material is heated into a heating furnace; The hydrogen is divided into n ways to be heated by the heating furnace, or heated by the heating furnace and divided into n ways, n being equal to the number of reactor catalyst beds or the number of multistage reactors.
  • One of the hydrogen and oil is mixed in the mixer to carry out the first stage of hydrogen storage, and the remaining (n-1) of the hydrogen passes through the inlet between the reactor beds to react with the hydrogen-hydrogen mixing member and the previous bed.
  • the second stage of hydrogen is dissolved, and the reaction by-product hydrogen sulfide and ammonia are stripped, and one stage of hydrogen is added to each bed or one reactor, and a reaction pressure control system is arranged at the top of the reactor.
  • An exhaust system is provided in each reactor, and the liquid level of each reactor is realized by controlling the discharge of gas generated by the next section and excess hydrogen.
  • the reaction product enters the stripping tower.
  • the hydrogen stripping mixer is arranged in the stripping tower. The product can strip off the by-product hydrogen sulfide and ammonia, and at the same time increase the hydrogen-dissolving ability. A part of the oil coming out of the stripping tower enters the product tank and is partially recycled.
  • the number of reactor catalyst beds or the number n of multistage reactors is from 3 to 5 stages.
  • the liquid phase stream after dissolving hydrogen enters the reactor from the upper portion of the liquid phase circulating hydrogenation reactor and flows out from the lower portion of the reactor; or the liquid phase stream enters the reactor from the lower portion of the liquid phase circulating hydrogenation reactor, from the reaction The upper part of the device flows out.
  • a hydrogen oil mixing member is disposed in the reactor.
  • a hydrogen oil mixer is disposed in the stripping tower, and a hydrogen oil mixing member may also be disposed.
  • the catalyst bed hydrogen oil volume ratio is 2:1 ⁇ 10:1.
  • the mixing ratio of the circulating oil to the raw oil is determined in accordance with the amount of hydrogen required for the reaction and the stability of the catalyst bed to ensure the amount of dissolved hydrogen in the mixed material.
  • the temperature of the reactor is controlled by the ratio of the feedstock to the recycle oil.
  • the amount of circulating oil is appropriately increased, and conversely, the amount of circulating oil is lowered.
  • the volume ratio of circulating oil to raw material is 0.1: 1 ⁇ 5: 1, and the volume ratio of hydrogen to oil in the catalyst bed is 2: 1 ⁇ 10:1.
  • the liquid phase hydrogenation process and reaction system with a multistage hydrogen storage system is a two-phase hydrogenation reaction carried out in a fixed bed reactor, and the hydrogen required for the reaction is dissolved in the feedstock oil. Excess hydrogen is provided.
  • the hydrogenation process conditions are determined based on the nature of the feedstock and the quality requirements of the final product. Generally, the reaction temperature is
  • FIG. 1 is a flow chart of a liquid phase hydrogenation process and reaction system with a multistage hydrogen storage system according to the present invention.
  • 1 stock oil, 2-cycle oil, 3-hydrogen, 4-heating furnace, 5-mixer, 6-reactor, 7-pressure control valve, 8/13/14/15/18-gas phase product , 9/10/1 1/12-Level Control Valve, 16-Liquid Reaction Product, 17-Stripper, 19-Steam Gas, 20-Circulation Pump, 21-Product
  • the fresh feedstock oil 1 and the circulating oil 2 are heated by the heating furnace 4, then enter the mixer 5 and the hydrogen gas 3 from the heating furnace 4 is mixed to form a presaturated liquid phase stream, and the pre-saturated liquid phase stream is fed into a single stage.
  • the multi-bed reactor or multi-stage hydrogenation reactor 6 is subjected to a hydrogenation reaction in which the gas phase product 8/13/14/15/18 is discharged from the reactor.
  • the liquid phase reaction product 16 enters the stripping column 17. After stripping by the stripping gas 19, the gas phase product 18 is discharged overhead, and a portion of the stripped liquid product is introduced into the heating furnace 4 through the circulation pump 20 as circulating oil 2. Another portion of the liquid phase product enters the product tank in the form of product 21.
  • Set the reaction pressure control valve at the top of the reactor. 7. Set the exhaust system level control valve 9/10/11 2 in each reactor.
  • the catalyst used in the experiment is a hydrotreating catalyst for industrial applications, a PHF-101 diesel hydrodesulfurization catalyst developed by the China Petroleum and Petrochemical Research Institute, a PHT-01 heavy oil hydrotreating pretreatment catalyst, and an SD-2 paraffin hydrogenation catalyst.
  • the physical and chemical properties are shown in Table 1.
  • the mixed diesel oil is heated to a desired temperature and dissolved in the gas-liquid mixer, and then enters the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure 6.5 MPa, reaction temperature 310 ° C, hydrogen oil volume ratio 300. : 1.
  • the liquid phase product is stripped into a stripping column for stripping, and a portion of the liquid phase product after stripping is passed through the circulation pump as a circulating oil into the heating furnace, and another portion of the liquid phase product enters the product tank in the form of a product.
  • the properties of raw oil and product properties are listed in Table 2.
  • the heavy wax oil raw material is heated to a desired temperature and dissolved in a gas-liquid mixer, and then enters the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure of 12.0 MPa, reaction temperature of 365 ° C, and hydrogen oil volume.
  • the ratio is 800: 1.
  • the liquid phase product is stripped into a stripping column for stripping, and a portion of the liquid phase product after stripping is passed through the circulation pump as a circulating oil into the heating furnace, and another portion of the liquid phase product enters the product tank in the form of a product.
  • the properties of raw oil and product properties are listed in Table 3.
  • the process technology can significantly reduce the content of sulfur and nitrogen impurities in heavy wax oil.
  • the crude paraffin raw material is heated to a desired temperature and dissolved in a gas-liquid mixer, and then enters the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure 7.0 MPa, reaction temperature 24 CTC, and hydrogen oil volume ratio of 400: 1.
  • the liquid phase product enters the stripping column for stripping, and a part of the liquid phase product after stripping is introduced into the heating furnace as a circulating oil through a circulation pump, and another part of the liquid phase product enters the product tank in the form of a product.
  • Raw material oil properties and product properties are listed in Table 4.
  • the process technology can improve the color and light stability of paraffin products.
  • the comparative data of this method and the conventional method are shown in Table 5. It can be seen from Table 5 that the reaction temperature of the method is 16 ° C lower than that of the conventional method, the hydrogen to oil ratio is only 300, which is three-fifths of that of the conventional method, and the product property is superior to the conventional method.
  • Example 1 Reaction temperature, c 326 310 Hydrogen partial pressure, MPa 6.5 6.5 Hydrogen oil volume ratio, v/v 500: 1 300: 1
  • Mixed diesel conventional method Liquid phase hydrogenation method, oil product, mixed diesel
  • the hydrogenation reactor used in the present invention simultaneously has a function of catalytic hydrogenation reaction and discharge of reaction by-product hydrogen sulfide and ammonia from the reaction system, and is in contact with the solid phase catalyst. The phase reacts the material, thereby increasing the efficiency of the hydrogenation reaction.
  • the invention is mainly used for deep desulfurization, denitrification and dearomatization of inferior diesel components, and produces clean diesel oil, and can also be used for hydrorefining of naphtha, jet coal, lubricating oil, paraffin, etc. to produce high quality oil, and for wax. Oil raw materials ease hydrocracking to produce high-quality clean coal and diesel processes.

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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

本发明涉及一种多级溶氢的液相加氢反应方法；循环液体物料与原料油混合，进入加热炉加热；氢气分成n路进入加热炉加热；一路氢气和液相物料在混合器中混合，进行第一级溶氢，其余（n-1）路氢气通过反应器床层的入口进入器内氢油混合构件与上一床层反应后的混合物进行混合，进行第二级溶氢，汽提出反应副产物硫化氢和氨，在反应器顶部设置反应压力控制系统，在每段反应器设置排气系统；反应产物进入汽提塔，汽提塔内设置氢油混合器，汽提出副产物硫化氢和氨，增加溶氢能力，汽提塔出来的油品一部分进入产品罐，一部分再循环；本方法在催化加氢反应的同时将硫化氢和氨排出反应系统，固相催化剂接触的为液相反应物，提高了反应效率。

Description

多级溶氢的液相加氢反应方法 技术领域
本发明涉及一种多级溶氢的液相加氢反应方法，具体地说涉及一种产品循环液相 加氢处理的工艺方法。 背景技术 随着人们的环保意识不断增强， 很多国家通过环境立法来限制柴油的硫含量， 使 其达到很低的水平 （10~15 g/g)， 以降低有害气体的排放， 改善空气质量。 美国在 2006年使柴油中的硫含量降低到 15 g/g。 德国在 2003年一月份将硫含量降低到 l(^g/g。 欧盟其他国家和日本在 2008年将硫含量降低到 l(^g/g。 我国城市车用柴油 国家标准 GB 19147-2009参照欧洲 III类标准制定， 其硫含量要求小于 350 g/g。 国家 环保部发布的第五阶段车用汽柴油排放指标中柴油硫含量要求小于 10 μ 。
国际市场柴油需求在不断增长， 然而， 高品位的原料油供应却在减少。 如何利用 低品位的原料油来生产超低硫柴油以满足日益增长的需求，是炼油厂不得不面对的一 个很大挑战。 为应对挑战， 一方面需要解决关键技术难题， 新建加氢装置进行柴油的 深度加氢脱硫； 另外一方面又需要降低风险和重复投资以保障经济效益。在传统的滴 流床加氢工艺中， 氢气需要从气相传递到液相， 然后溶解氢和含硫化合物在催化剂的 活性中心发生反应， 从而达到脱硫目的。在此过程中， 所需要的氢气量远远大于加氢 反应所消耗的氢气量。 这是因为， 一方面， 加氢反应是一个强放热反应， 为了控制反 应温度， 需要大量的氢气和原料油通过催化剂床层带走反应热； 另外一方面， 在气- 液 -固三相的反应中， 维持较高的氢分压有利于加氢反应， 抑制焦炭生成， 延长催化 剂寿命。此外， 没有参加反应的氢气通过循环氢压缩机将其提高压力后重新输送到反 应器中参与反应。 循环氢压缩机作为加氢过程的关键设备， 投资和操作费用较高。为 了取消循环氢和循环氢压缩机， 降低装置的投资成本， 液相加氢技术被提了出来， 在 液相循环加氢工艺中， 氢气和原料油先预混合， 使氢气溶解在原料油中， 再进入反应 器进行反应， 反应过程中所需氢气完全来自溶解的氢， 而无需额外补入冷氢。液相循 环加氢工艺具有反应器比较小， 投资成本低， 反应温度容易控制等优点， 但是， 液相 循环加氢也存在一个问题， 即为了满足加氢过程中所需要的氢气量， 需要使用大量的 循环油或额外加入溶剂来溶解氢气， 致使加氢效率降低。
一般含有简单硫化物的原料在滴流床加氢反应器中加氢脱硫的反应速率除了与 H2 度寺 ia东的影啊。惟化刑的润湿 H卞定 仕刀 反 杀忏 惟 1 刑衣面傲涖1不 反应物所浸润程度的一种度量。 催化剂的浸润程度越高、 催化剂的润湿因子就越高， 也就是说催化剂的有效利用率越高。在催化剂等因素确定的条件下， 影响催化剂润湿 因子的主要因素是反应器中液体的流速， 以及气体和液体流速的比（ 氢油比)。 一般 认为， 液体流速增加增强催化剂润湿效果， 而常规加氢工艺多采用远远超过反应所需 的大氢油比， 从而降低了催化剂的润湿效果， 对润湿因子有不利的影响。 此外， 炼油 过程中氢气循环环节的投资占整个过程成本的比例较大。
有机氮化物是加氢催化剂的毒物， 对加氢脱氮、加氢脱硫和加氢脱芳反应有明显 的抑制作用。这种抑止作用主要是由于有些氮化物和大多数氮化物的中间反应产物与 催化剂的加氢反应活性中心具有非常强的吸附能，从竞争吸附的角度抑止了其他加氢 反应的进行。而通过加氢产物循环将大大稀释原料中的杂质含量， 有利于发挥催化剂 的性能。
加氢脱硫副产物 s 对加氢脱硫反应、 加氢脱氮和加氢脱芳反应也有明显的抑 制作用， 文献 Sie S T. [J]. Reaction order and role of hydrogen sulfide in deep
hydrodesulfurization of gas oil ： consequences for industrial reactorconfiguration, Fuel Processing Technology, 1999， 61(1-2) ： 149-171. 认为 H2S 对加氢脱硫反应的影响一 是使加氢脱硫反应的活化能上升。 以甲苯加氢为例， 硫化氢分压为 0 时， 反应活化能 为 16kcal/mol， 当硫化氢分压达到 42kPa 时， 活化能上升到 20kcal/mol ； 另一影响是 少量 H2S 存在就会大大降低加氢脱硫速率， 并且 H2S 在催化剂表面的吸附为单层吸 附， 一旦吸附中心被 s 占据， 反应速率将不再随 s 分压提高而下降。 因此， 采 用有效的手段消除 s 的影响是解决深度脱硫的关键问题。
美国专利 US20060144756A1公开了一种两相加氢控制系统方法和装置。 在连续 的液相加氢过程中， 取消了循环氢， 加氢反应所需要的氢都来自于液相溶解的氢， 不 需要额外的氢气。但其需要使用氢气溶解度较大的溶剂或稀释剂来溶解氢气，影响后 续的加氢效率。
US6213835、 US6428686, CN200680018017.3 等公开了一种预先溶解氢气的加 氢工艺， 通过控制液体进料中的氢气量控制反应器中的液体量或气压。但其没有完全 解决将在加氢精制反应过程中产生的 s、 N 等有害杂质脱除的问题， 导致其不断 在反应器内累积， 大大降低了反应效率， 也无法有效处理硫、 氮含量较高的原料， 上 述文献也没有公开反应器 发明内容 本发明的目的是提供一种多级溶氢的液相加氢反应方法。
本发明所述的多级溶氢的液相加氢反应方法包括以下内容：经过汽提塔混氢的液 体物料的一部分循环与新鲜原料油混合为液相物料， 液相物料进入加热炉加热； 氢气 分成 n路进入加热炉加热， 或者经加热炉加热后分成 n路， n等于反应器催化剂床层 的数量或多级反应器的数量。其中一路氢气和油品在混合器中进行混合， 进行第一级 溶氢， 其余 （n-1 ) 路氢气通过反应器床层之间的入口进入器内氢油混合构件与上一 床层反应后的混合物进行混合，进行第二级溶氢，同时汽提出反应副产物硫化氢和氨， 每多一个床层或一个反应器就增加一级溶氢， 在反应器顶部设置反应压力控制系统， 在每段反应器设置排气系统，每段反应器的液位通过控制下一段生成的气体和多余的 氢气的排放来实现。 反应产物进入汽提塔， 汽提塔内设置氢油混合器， 产品可以汽提 出副产物硫化氢和氨， 同时增加溶氢能力， 汽提塔出来的油品一部分进入产品罐， 一 部分再循环。
本发明方法中， 反应器催化剂床层的数目或多级反应器的数目 n为 3〜5级。 本发明方法中， 溶解氢后的液相物流从液相循环加氢反应器上部进入反应器， 从 反应器下部流出； 或者液相物流从液相循环加氢反应器下部进入反应器， 从反应器上 部流出。
本发明方法中， 反应器内设置氢油混合构件。
本发明方法中， 汽提塔内设置氢油混合器， 也可以设置氢油混合构件。
本发明方法中， 催化剂床氢油体积比为 2： 1〜10： 1。
本发明方法中，根据反应所需要的氢量以及催化剂床层的稳定性确定循环油与原 料油的混合比例， 以保证混合物料中溶解的氢量。利用原料油与循环油的比例控制进 入反应器的温度。 当化学氢耗高以及反应热较高时适当提高循环油量， 反之则降低循 环油的量。 循环油与原料的体积比为 0.1： 1〜5： 1， 催化剂床氢油体积比为 2： 1〜 10： 1。
本发明所述的一种带有多级溶氢系统的液相加氢工艺方法和反应系统是在固定 床反应器中进行的两相加氢反应， 反应所需要的氢由原料油中溶解的过量氢气提供。 加氢工艺条件根据原料的性质、 最终产品质量要求来确定。 一般来说， 反应温度在
220〜420°C， 反应氢分压为 0.5〜15 MPa， 体积空速为 0.8〜15 h— 图 1为本发明一种带有多级溶氢系统的液相加氢工艺方法和反应系统流程图。 图中： 1 -原料油， 2-循环油， 3-氢气， 4-加热炉， 5-混合器， 6-反应器， 7-压力控 制阀， 8/13/14/15/18-气相产物， 9/10/1 1/12-液位控制阀， 16-液相反应产物， 17-汽提 塔， 19-汽提气， 20-循环泵， 21-产品
具体实施方式
如图 1所示，新鲜原料油 1和循环油 2经加热炉 4加热后进入混合器 5与从加热 炉 4出来的氢气 3进行混合形成预饱和液相物流，预饱和液相物流进单级多床层反应 器或多级加氢反应器 6进行加氢反应，反应中气相产物 8/13/14/15/18排出反应器。液 相反应产物 16进入汽提塔 17, 经汽提气 19汽提后， 气相产物 18经塔顶排出， 汽提 后的液相产物一部分经循环泵 20作为循环油 2进入加热炉 4。 另一部分液相产物以 产品 21的形式进入产品罐。 在反应器顶部设置反应压力控制阀 7， 在每段反应器设 置排气系统液位控制阀 9/10/11 2。
下面的实施例将对本发明作进一步说明。
实验使用催化剂为工业应用的加氢处理催化剂，为中国石油石油化工研究院研制 生产的 PHF-101柴油加氢脱硫催化剂、 PHT-01重油加氢预处理催化剂、 SD-2石蜡加 氢催化剂， 其理化性质指标见表 1。
实施例 1
混合柴油经过加热炉达到所需温度与氢气在气液混合器中充分混合溶解后，进入 加氢反应器， 反应条件为： 氢分压 6.5MPa、 反应温度 310°C， 氢油体积比为 300: 1。 液相产物进入汽提塔进行汽提，汽提后的液相产物一部分经循环泵作为循环油进入加 热炉，另一部分液相产物以产品的形式进入产品罐。原料油性质及产品性质列于表 2。
由表 2 可见， 采用该工艺技术可以使柴油中的硫、 氮含量明显降低。
实施例 2
重质蜡油原料经过加热炉达到所需温度与氢气在气液混合器中充分混合溶解后， 进入加氢反应器，反应条件为：氢分压 12.0MPa、反应温度 365°C，氢油体积比为 800: 1。 液相产物进入汽提塔进行汽提，汽提后的液相产物一部分经循环泵作为循环油进入加 热炉，另一部分液相产物以产品的形式进入产品罐。原料油性质及产品性质列于表 3。
由表 3 可见， 采用该工艺技术可以使重质蜡油中的硫氮杂质含量明显降低。 粗石蜡原料经过加热炉达到所需温度与氢气在气液混合器中充分混合溶解后，进 入加氢反应器，反应条件为：氢分压力 7.0MPa、反应温度 24CTC，氢油体积比为 400:1。 液相产物进入汽提塔进行汽提，汽提后的液相产物一部分经循环泵作为循环油进入加 热炉，另一部分液相产物以产品的形式进入产品罐。原料油性质及产品性质列于表 4。
由表 4 可见， 采用该工艺技术可以提高石蜡产品的颜色和光安定性。
比较例 1
处理相同性质的混合柴油， 采用本方法与常规方法的对比数据见表 5。 由表 5可 以看出， 本方法反应温度与常规方法相比低 16°C， 氢油比仅为 300， 是常规方法的五 分之三， 而产品性质优于常规方法。
表 1 催化剂的理化性质指标
Figure imgf000007_0001
表 2 实施例 1原料油性质及试验结果
混合柴油 混合柴油 生成油 生成油 项 目 混合柴油
( 160~230°C ) (>230°C ) ( 160-230*0 (>230"C ) 密度 (2(TC)， g/cm3 0.8350 0.8110 0.8731 0.8130 0.8501 硫含量， g/g 1020.0 541.8 1602.1 1.5 40.0 氮含量， g/g 881.8 267.7 1330.6 7.9 48.0
表 3 实施例 2原料油性质及试验结果
项 目 重质蜡油 生成油
密度 (20°C)， g/cm3 0.8559 0.8498
硫含量， g/g 780.0 4.2
氮含量， g/g 697.0 6.3 项 目 粗石蜡 石蜡产品
熔点， 。C 58.6 ―
含油量 i , wt. % 1.37 1.33
颜色， (赛)号 3 30
光安定性， 号 8 4
表 5 对比例 1原料油性质及试验结果 项 目 比较例 1 实施例 1 反应温度， c 326 310 氢分压， MPa 6.5 6.5 氢油体积比， v/v 500: 1 300: 1 混合柴油 常规方法生成 液相加氢法生 油品性质 混合柴油
( >230°C ) 油 （>230°C ) 成油（>230°C ) 密度 (20°C)， g/cm3 0.8350 0.8731 0.8501 0.8547 硫含量' \x.glg 1020.0 1602.1 40.0 8.0 氮含量， g/g 881.8 1330.6 48.0 7.1 工业实用性 本发明所采用的加氢反应器同时具有催化加氢反应和将反应副产物硫化氢和氨 排出反应系统功能的作用， 与固相催化剂接触的均为液相反应物料， 因而提高了加氢 反应效率。
本发明主要用于劣质柴油组分的深度脱硫、 脱氮、 脱芳烃， 生产清洁柴油， 也可 用于石脑油、 航煤、 润滑油、 石蜡等加氢精制生产优质油品， 以及用于蜡油原料缓和 加氢裂化生产优质清洁航煤、 柴油工艺过程。

Claims

1 . 一种多级溶氢的液相加氢反应方法； 其特征在于： 该方法包括： 经过汽提塔 混氢的液体物料的一部分循环与新鲜原料油混合为液相物料，液相物料进入加热炉加 热； 氢气分成 n路进入加热炉加热， 或者经加热炉加热后分成 n路， n等于反应器催 化剂床层的数量或多级反应器的数量； 其中一路氢气和液相物料在混合器中进行混 合， 进行第一级溶氢， 其余 （n-1 ) 路氢气通过反应器床层之间的入口进入器内氢油 混合构件与上一床层反应后的混合物进行混合， 进行第二级溶氢， 同时汽提出反应副 产物硫化氢和氨， 每多一个床层或一个反应器就增加一级溶氢， 在反应器顶部设置反 应压力控制系统， 在每段反应器设置排气系统， 每段反应器的液位通过控制下一段生 成的气体和多余的氢气的排放来实现； 反应产物进入汽提塔， 汽提塔内设置氢油混合 器， 汽提出副产物硫化氢和氨， 同时增加溶氢能力， 汽提塔出来的油品一部分进入产 品罐， 一部分再循环。
2. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 11为3〜 5级。
3. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 溶解氢 后的液相物流从液相循环加氢反应器上部进入反应器， 从反应器下部流出。
4.根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 或液相物 流从液相循环加氢反应器下部进入反应器， 从反应器上部流出。
5. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 反应器 内设置氢油混合构件。
6. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 汽提塔 内设置氢油混合器。
7. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 汽提塔 内或设置氢油混合构件。
8. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 催化剂 床氢油体积比为 2： 1〜10： 1。
9. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 循环油 与原料的体积比为 0.1： 1〜5： 1。
10. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 反应温
1 1.根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 反应氢 分压为 0.5〜15 MPa。
12. 根据权利要求 1所述的多级溶氢的液相加氢反应方法， 其特征在于： 体积空 速为（^〜^！！人
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