WO2014117310A1 - 一种馏分油两相加氢反应器和加氢工艺方法 - Google Patents

一种馏分油两相加氢反应器和加氢工艺方法 Download PDF

Info

Publication number
WO2014117310A1
WO2014117310A1 PCT/CN2013/000904 CN2013000904W WO2014117310A1 WO 2014117310 A1 WO2014117310 A1 WO 2014117310A1 CN 2013000904 W CN2013000904 W CN 2013000904W WO 2014117310 A1 WO2014117310 A1 WO 2014117310A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen
liquid
reactor
hydrogenation
catalyst bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2013/000904
Other languages
English (en)
French (fr)
Inventor
马守涛
田然
张志华
王刚
孙发民
张瑞芹
于春梅
孙生波
冯秀芳
李凤铉
朱金玲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to US14/764,485 priority Critical patent/US9534178B2/en
Priority to SG11201505319SA priority patent/SG11201505319SA/en
Publication of WO2014117310A1 publication Critical patent/WO2014117310A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • 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
    • C10G45/14—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 moving solid particles
    • C10G45/20—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 moving solid particles according to the "fluidised-bed" technique
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/00849—Stationary elements outside the bed, e.g. baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00938—Flow distribution elements
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the present invention relates to a distillate two-phase hydrogenation reactor and a liquid phase hydrogenation process, and more particularly to a liquid phase reactor for circulating a product, particularly a product cycle containing dissolved hydrogen in a liquid phase material of a hydrocarbon.
  • 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 does not participate in the reaction is increased in pressure 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 reaction rate of hydrodesulfurization of feedstocks containing simple sulphide in a fixed bed hydrogenation reactor is related to the wetting condition of the catalyst, the organic nitride and H 2 S concentration in the reactor system, in addition to the concentration of the organic sulphide.
  • the wetting factor of the catalyst is a measure of the extent to which the surface of the catalyst is wetted by the liquid reactant under hydrogenation conditions. The higher the degree of catalyst wetting, the higher the wetting factor of the catalyst, that is, the higher the effective utilization of the catalyst. Under the conditions determined by factors such as catalyst, the main factors affecting the wetting factor of the catalyst are the flow rate of the liquid in the reactor and the ratio of the gas to the liquid flow rate.
  • the organic nitride is a poison of the hydrogenation catalyst and has a significant inhibitory effect on the hydrodenitrogenation, hydrodesulfurization and hydrodearomatization reactions. This inhibition is mainly due to the fact that the intermediate reaction product of some nitrides and most nitrides has a very strong adsorption energy with the hydrogenation reaction center of the catalyst, and inhibits the progress of other hydrogenation reactions from the viewpoint of competitive adsorption.
  • the impurity content in the raw material is greatly diluted, which is advantageous for the performance of the catalyst.
  • 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 all the hydrogen required for the hydrogenation reaction comes from the dissolved hydrogen in the liquid phase, and no additional hydrogen is required. However, it is necessary to use a solvent or diluent having a relatively high hydrogen solubility to dissolve the hydrogen, which affects the subsequent hydrogenation efficiency.
  • Chinese patent CN86108622 discloses a hydrorefining process for reforming oil.
  • the volume ratio of hydrogen to oil is 200: 1-1000: 1; the patent of CN93101935.4 discloses a hydrocracking process for inferior feedstock, hydrogen.
  • Chinese patent CN94102955.7 discloses a catalytic pyrolysis gasoline hydrotreating method, hydrogen oil volume ratio 150: 1 ⁇ 500: 1;
  • Chinese patent CN96109792.2 discloses a series connection Hydrogenation process for producing high quality petrolatum, hydrogen oil volume ratio 300: 1 ⁇ 1400: 1;
  • Chinese patent CN96120125.8 discloses a method for direct hydrogenation of cycloalkyl straight-run fraction to produce white oil, hydrogen oil volume More than 500: 1 ⁇ 1500: 1.
  • the object of the present invention is to provide a distillate two-phase hydrogenation reactor and a hydrogenation process.
  • the reactor adopts a suitable structure to effectively replenish hydrogen in a liquid phase feedstock while removing hydrogen sulfide entering the catalyst bed.
  • ammonia to avoid the adverse effects of harmful impurities on the catalytic reaction, improve hydrogenation efficiency and raw material adaptability.
  • the hydrogenation reactor of the present invention comprises a reactor cylinder and a catalyst bed, a reactor inlet and a reactor outlet, characterized in that: the hydrogenation reactor upper space size is slightly larger than the lower catalyst bed portion, including at least two a catalyst bed having an internal member for gas replenishing and stripping the liquid phase stream containing impurities between at least one adjacent catalyst bed, the internal member comprising a gas-liquid contact and stripping member, a gas-liquid contacting member and a stripping member disposed Together, the inner member comprises a separating plate and an exhaust pipe, and the separating plate has a downflow through hole: the separating plate is connected with the exhaust pipe, the exhaust pipe is arranged above the separating plate, the top of the exhaust pipe and the lower part of the upper catalyst bed Contact.
  • the upper space of the reactor is slightly larger than the portion of the lower catalyst bed, and the upper reactor is prevented from flooding and the top gas line is blocked.
  • the inner member comprises a separator plate and an exhaust pipe, and the separator plate has a downflow through hole, and the gas and liquid two phases are in contact through the downflow through hole.
  • a plurality of downcomer through holes and exhaust ducts are provided, and an exhaust duct is disposed above the partition plate.
  • the hydrogenation reactor of the present invention has an exhaust system at the top of the reactor, a reactor set pressure and a liquid level monitoring system, an exhaust system and a pressure level monitoring system interlocked, by controlling the amount of gas discharged from the reactor and The amount of liquid controls the pressure and level of the reactor.
  • the above-mentioned gas may be provided at the top of the reactor and/or at the bottom of the reactor to replenish and strip the internal components of the liquid phase containing impurities.
  • the key of the hydrogenation reactor of the present invention is to adopt a steam stripping member with suitable structure (other structures of the reactor can adopt the conventional structure in the art), so that the gas containing the impurities after the reaction can be directly discharged through the lower catalyst bed. The effect of impurities on the next reaction after the reaction is reduced.
  • the hydrogenation reactor of the present invention is a hydrocarbon feedstock liquid phase hydrogenation reactor in which the liquid phase product after the reaction is partially recycled, and the catalyst bed is a hydrocarbon hydrogenation catalyst.
  • the liquid phase hydrogenation process method of the present invention uses the reactor of the present invention, and the process comprises: mixing a part of the liquid phase product after the hydrotreatment with a fresh raw material to be a liquid phase material, and forming a saturated liquid phase stream after the hydrogen is dissolved from the upper portion into the reaction.
  • the hydrogenation reaction is carried out on the hydrogenation catalyst bed in the upper part of the reactor. After the reaction, the effluent is mixed with hydrogen through the internal components, and the amount of dissolved hydrogen in the liquid phase material is supplemented, and the liquid material in which the hydrogen is dissolved is added to the next addition.
  • the hydrogen catalyst bed the gas phase hydrogen enters the catalyst bed through the exhaust pipe of the stripping member, forms a gas-liquid countercurrent in the catalyst bed, increases the hydrogen concentration of the catalyst bed, increases the reaction efficiency, and simultaneously hydrogen sulfide generated by the reaction And ammonia impurities are stripped up.
  • the volume ratio of the recycled liquid phase product to the fresh raw material is 0.1:1 to 10: 1
  • the catalyst bed is provided with 2 to 4
  • the amount of hydrogen supplemented between the catalyst beds is hydrogen.
  • the oil volume ratio is 0.5: Bu 10:1.
  • the reaction conditions of the liquid phase material passing through the catalyst bed can be specifically determined by those skilled in the art according to the nature of the raw materials and the quality of the product, and generally: the reaction temperature is 130 to 450 ° C, and the reaction pressure is For l ⁇ 20MPa, the liquid hourly space velocity is. ⁇ ! !— 1 .
  • Figure 1 is a schematic view of a two-phase hydrogenation reactor for a distillate oil of the present invention.
  • FIG. 2 is a schematic view of the internal components of the distillate two-phase hydrogenation reactor of the present invention.
  • Figure 3 is a top plan view of the inner member of the distillate two-phase hydrogenation reactor of the present invention.
  • a reactor inlet 1, a hydrogen inlet 2, and a reactor outlet 9 the upper space of the reactor is larger than that of the lower catalyst bed portion, and two catalyst beds are used.
  • An inner member for gas replenishing and stripping the liquid phase stream containing impurities is disposed between the two catalyst beds, the inner member comprising a separator plate 5 and an exhaust pipe 6, the separator plate 5 having a downflow through hole 7; the separator plate 5 and The exhaust ducts 6 are connected, and the exhaust duct 6 is disposed above the partition plate 5, and the top of the exhaust duct 6 is in contact with the lower portion of the upper catalyst bed.
  • a part of the liquid phase product after the hydrotreatment is mixed with the fresh raw material to be a liquid phase material, and after the hydrogen is dissolved, a saturated liquid phase stream is formed from the upper portion into the reactor, and the hydrogenation reaction is carried out through the first catalyst bed, and the effluent after the reaction
  • the gas phase hydrogen enters the first catalyst bed through the exhaust pipe of the stripping member,
  • the first catalyst bed forms a gas-liquid countercurrent, while hydrogen vaporizes the hydrogen sulfide and ammonia impurities generated by the reaction.
  • the second catalyst bed reaction effluent enters the product tank through a portion of the recycle portion after exiting the reactor.
  • the catalyst used in the experiment is hydrotreating and hydrocracking catalyst for industrial application, PHF-101 diesel hydrodesulfurization catalyst developed by China Petroleum and Petrochemical Research Institute, PHT-01 heavy oil hydrotreating pretreatment catalyst, PHC-03 hydrogenation
  • the cracking catalyst, its physical and chemical properties are shown in Table 1.
  • the mixed diesel oil and hydrogen are fully mixed and dissolved in hydrogen, and then enter the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure 6.0 MPa, reaction temperature 31 C, and the amount of hydrogen supplemented between the catalyst beds is 1:1 by volume of hydrogen oil.
  • a portion of the liquid phase product is introduced into the reactor by circulating the pump as a circulating oil mixed with fresh raw materials, and another portion of the liquid phase product enters the product tank as a product.
  • the properties of raw oil and product properties are listed in Table 2.
  • the heavy wax oil raw material is mixed with hydrogen and dissolved in hydrogen, and then enters the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure 12.0 MPa, reaction temperature 370V, and the amount of hydrogen supplemented between the catalyst beds is 3:1 according to the hydrogen oil volume ratio. .
  • a part of the liquid phase product enters the reactor through a circulating pump as a circulating oil mixed with fresh raw materials, and another part 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.
  • Example 3 The wax oil raw material treated by the example 2 is mixed with hydrogen to dissolve hydrogen, and then enters the hydrogenation reactor.
  • the reaction conditions are: hydrogen partial pressure 12.0 MPa, reaction temperature 385 ° C, and the amount of hydrogen supplemented between the catalyst beds is hydrogen oil.
  • the volume ratio is 7:1.
  • a part of the liquid phase product is introduced into the reactor through a circulating pump as a circulating oil mixed with fresh raw materials, and another part of the liquid phase product enters the product tank in the form of a product, and then is subjected to solid boiling point cutting.
  • the properties of the raw oil are listed in Table 4.
  • the distribution and properties of the products are shown in Table 5.
  • the mixed diesel oil of the same nature is treated, and there is no internal component between the two catalyst beds of the reactor, all of the hydrogen gas enters the reactor from the reactor inlet, and other process conditions are refined according to the operating conditions of the embodiment 1.
  • the properties of diesel are shown in Table 6. As can be seen from Table 6, the reaction temperature of the reactor of the present invention is 15 ° C lower than that of the conventional reactor, and the product properties are superior.
  • two or more reactors may be connected in series (the effluent of one reactor into the next reactor) or in parallel (the materials are separately fed into different reactors) as needed.
  • the hydrogenation catalyst can be subjected to different hydrogenation according to the needs of the reaction using a suitable hydrogenation catalyst.
  • a hydrotreating catalyst, a hydrotreating catalyst, a hydrotreating catalyst, a hydrocracking catalyst, etc. various catalysts may be selected from commercial catalysts, or may be prepared according to the prior art.
  • the liquid phase hydrogenation process of the invention uses the above reactor to effectively replenish hydrogen in the liquid phase raw material, form a gas-liquid countercurrent in the catalyst bed, increase the hydrogen concentration, and simultaneously remove the hydrogen sulfide and ammonia generated by the reaction, The inhibition of H 2 S and N3 ⁇ 4 on the next hydrogenation reaction is reduced, the hydrogenation efficiency is improved, and the adaptability of the raw materials is improved.
  • This method does not require circulating hydrogen and a circulating hydrogen compressor, which can reduce equipment investment and operating costs.
  • 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 fuel, lubricating oil, paraffin, etc. to produce high quality oil, and for wax. Oil feedstocks ease hydrocracking to produce high quality clean jet fuel and diesel processes.
  • the amount of hydrogen used is increased by a little more than the amount of dissolved hydrogen in the system based on the chemical hydrogen consumption, and the reaction part is not provided with a hydrogen circulation system, and is carried into the reaction system by a large amount of circulation of the liquid product.
  • the dissolved hydrogen and hydrogen supplement the dissolved hydrogen to provide the hydrogen required for the hydrogenation reaction of the fresh feedstock, and the active stability of the catalyst can be maintained due to the recycling of the hydrogenated product.
  • the invention has the advantages of eliminating the influence of the wetting factor of the catalyst and the influence of H 2 S and NH 3 in the circulating hydrogen; since the specific heat capacity of the circulating oil is large, the temperature rise of the reactor can be lowered, and the utilization efficiency of the catalyst can be improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明涉及一种馏分油两相加氢反应器和加氢工艺方法；反应器上部空间尺寸比下部催化剂床层部分大，包括2～4个催化剂床层，在至少一个相邻催化剂床层之间设置气体补充和汽提含杂质液相物流的内构件，该内构件包括气液接触构件及汽提构件，气液接触构件和汽提构件设置在一起，内构件包括隔离板和排气管道，隔离板设有多个降液通孔；隔离板与多个排气管道相连接，排气管道垂直设置在隔离板上面，排气管道顶部与上一催化剂床层下部相接触；本反应器有效地补充液相原料中的氢气，在催化剂床层形成气液逆流，增大氢气浓度，脱除了反应生成的硫化氢和氨，减少H2S和NH3对下一步加氢反应的抑制作用，提高了加氢效率，提高了原料适应性，降低设备投资和操作成本。

Description

一种馏分油两相加氢反应器和加氢工艺方法
技术领域 本发明涉及一种馏分油两相加氢反应器及液相加氢工艺方法，具体地说涉及 种 产物循环的液相反应器，特别是烃类液相物料中含有溶解氢气的产物循环液相加氢处 理的反应器及使用该反应器的液相加氢工艺方法。
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 10 g/g。 欧盟其他国家和日本在 2008年将硫含量降低到 10 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
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。在传统的固 定床加氢工艺中， 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。 在常规的固定床加氢工艺过程中， 为了脱除原料中的硫、 氮、 氧、 金属等杂质或 减小原料油分子的火小， 需要进行催化加氢反应。为了控制催化剂床层的反应温度和 避免催化剂积炭失活， 通常采用较大的氢油体积比， 在加氢反应完成后必然有大量的 氢气富余。这些富余的氢气通常经循环氢压缩机增压后与新氢混合继续作为反应的氢 气进料。这个工艺过程也可以定义为气相循环固定床加氢工艺。该工艺循环氢压缩机 的投资占整个加氢装置成本的比例较高，氢气换热系统能耗较大， 如果能够将加氢处 理过程中的氢气流量减小并省去氢气循环系统和循环氢压缩机， 可以为企业节省投 资， 为清洁燃料生产降低成本。
含有简单硫化物的原料在固定床加氢反应器中加氢脱硫的反应速率除了与有机 硫化物的浓度有关，还受催化剂的润湿状况、反应器系统中的有机氮化物和 H2S 浓度 等因素的影响。催化剂的润湿因子是对在加氢反应条件下催化剂表面被液体反应物所 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。 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烃反应有明 显的抑制作用。这种抑制作用主要是由于某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制了其他加 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。
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全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 解决加氢精制反应过程中产生的 S、 Nft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， 上述专 利也没有公开反应器的具体结构。
中国专利 CN86108622 公开了 种重整生成油的加氢精制工艺， 氢油体积比为 200: 1-1000: 1； 屮国专利 CN93101935.4 公开了一种劣质原料油一段加氢裂化工艺方 法， 氢油体积比 1300: 1〜1500: 1； 中国专利 CN94102955.7 公开了一种催化裂解汽油 加氢精制方法， 氢油体积比 150: 1~500: 1； 中国专利 CN96109792.2 公开了一种串联 加氢工艺生产高质量凡士林的方法， 氢油体积比 300: 1~1400: 1； 中国专利 CN96120125.8 公开了一种由环烷基直馏馏分直接加氢生产白油的方法， 氢油体积比 500: 1〜1500: 1。
这些专利的特点是具有较高的氢油体积比，因此必须具有氢气循环环节和循环氢 压缩机。
发明内容 本发明的目的是提供馏分油两相加氢反应器和加氢工艺方法，反应器采用适宜的 结构形式， 有效地补充液相原料中的氢气， 同时脱除进入催化剂床层的硫化氢和氨， 避免有害杂质对催化反应的不利影响， 提高加氢效率和原料适应性。
本发明所述的加氢反应器包括反应器筒体和催化剂床层、反应器入口和反应器出 口， 特征在于： 加氢反应器上部空间尺寸比下部催化剂床层部分略大， 包括至少两个 催化剂床层，在至少一个相邻催化剂床层之间设置气体补充和汽提含杂质液相物流的 内构件， 该内构件包括气液接触及汽提构件， 气液接触构件和汽提构件设置在一起， 内构件包括隔离板和排气管道， 隔离板具有降液通孔： 隔离板与排气管道相连接， 排 气管道设置在隔离板上面， 排气管道顶部与上一催化剂床层下部相接触。
本发明所述的加氢反应器中， 反应器上部空间尺寸比下部催化剂床层部分略大， 避免上部反应器液泛， 堵塞顶部气体管线。
本发明所述的加氢反应器中， 内构件包括隔离板和排气管道， 隔离板具有降液通 孔， 气液两相通过降液通孔进行接触。
本发明所述的内构件中， 降液通孔和排气管道设置若干个， 排气管道设置在隔离 板上面。
本发明所述的加氢反应器屮， 反应器顶部设置排气系统， 反应器设置压力和液位 监测系统， 排气系统和压力液位监测系统联锁， 通过控制排出反应器的气体量和液体 量控制反应器的压力和液位。 本发明所述的加氢反应器中， 在反应器顶部和 /或反应器底部也可以设置上述气 体补充和汽提含杂质液相物流的内构件。
本发明所述的加氢反应器的关键在于采用结构适宜的汽提构件（反应器其它结构 可以采用本领域常规结构）， 使含有反应后杂质的气体不再经过下部催化剂床层而直 接排出反应器， 减少了反应后杂质对下一步反应的影响。
本发明所述的加氢反应器为烃类原料液相加氢反应器，其中反应后的液相产物部 分循环操作， 催化剂床层使用烃类加氢催化剂。
本发明液相加氢工艺方法使用本发明反应器， 过程包括： 经加氢处理后的液相产 物的一部分循环与新鲜原料混合为液相物料，溶氢之后形成饱和液相物流从上部进入 反应器， 在反应器上部的加氢催化剂床层进行加氢反应， 反应后流出物通过内构件与 氢气混合， 补充液相物料中溶解的氢气量， 补充了溶解氢的液相物料进入下一加氢催 化剂床层； 气相氢通过汽提构件的排气管道进入催化剂床层， 在催化剂床层形成气液 逆流， 增大催化剂床层的氢气浓度， 提高反应效率， 同时氢气将反应生成的硫化氢和 氨杂质汽提出来。
本发明上述液相加氢工艺方法中， 循环的液相产物与新鲜原料的体积比为 0.1 : 1〜10: 1， 催化剂床层设置 2〜4个， 催化剂床层间补充的氢气量按氢油体积比为 0.5:卜 10: 1。
本发明上述液相加氢工艺方法中，液相物料通过催化剂床层的反应条件可以根据 原料性质、 产品质量要求由本领域技术人员具体确定， 一般为： 反应温度为 130〜 450 °C , 反应压力为 l〜20MPa， 液时体积空速为。^〜^！!—1。
附图说明 图 1为本发明馏分油两相加氢反应器示意图。
图 2为本发明馏分油两相加氢反应器内构件示意图。
图 3为本发明馏分油两相加氢反应器内构件俯视图。
图中： 1-反应器入口， 2-氢气入口， 3-第一催化剂床层， 4-第二催化剂床层， 5-气液 接触和汽提构件， 6-排气管道， 7-降液通孔， 8-反应器排气系统， 9-反应器出口。 具体实施方式
下面结合附图进一步说明本发明反应器的结构及加氢工艺的操作方法。 按照图 1 和图 2 所示，本发明一种具体反应器结构，反应器入口 1、氢气入口 2、 反应器出口 9，反应器上部空间尺寸比下部催化剂床层部分大，采用两个催化剂床层： 第一催化剂床层 3和第二催化剂床层 4。 在两个催化剂床层之间设置气体补充和汽提 含杂质液相物流的内构件， 该内构件包括隔离板 5和排气管道 6， 隔离板 5具有降液 通孔 7 ; 隔离板 5与排气管道 6相连接， 排气管道 6设置在隔离板 5上面， 排气管道 6顶部与上一催化剂床层下部相接触。
经加氢处理后的液相产物的一部分循环与新鲜原料混合为液相物料，溶氢之后形 成饱和液相物流从上部进入反应器， 经过第一催化剂床层进行加氢反应， 反应后流出 物通过内构件与氢气混合， 补充液相物料中溶解的氢气量， 补充了溶解氢的液相物料 进入第二催化剂床层； 气相氢通过汽提构件的排气管道进入第一催化剂床层，在第一 催化剂床层形成气液逆流， 同时氢气将反应生成的硫化氢和氨杂质汽提出来。第二催 化剂床层反应流出物经排出反应器后部分循环部分进入产品罐。
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和加氢裂化催化剂，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、 PHC-03加氢裂化催化剂， 其理化性质指标见表 1。
实施例 1
混合柴油与氢气充分混合溶氢后，进入加氢反应器，反应条件为：氢分压 6.0MPa、 反应温度 31 C , 催化剂床层间补充的氢气量按氢油体积比为 1 : 1。 液相产物一部分 经循环泵作为循环油与新鲜原料混合溶氢后进入反应器，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
重质蜡油原料与氢气充分混合溶氢后， 进入加氢反应器， 反应条件为： 氢分压 12.0MPa、 反应温度 370V , 催化剂床层间补充的氢气量按氢油体积比为 3 : 1。 液相产 物一部分经循环泵作为循环油与新鲜原料混合溶氢后进入反应器，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， 以含 l Owt.%焦蜡的混合蜡油为原料， 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。
实施例 3 经实例 2处理后的蜡油原料与氢气充分混合溶氢后， 进入加氢反应器， 反应条件 为： 氢分压 12.0MPa、 反应温度 385°C， 催化剂床层间补充的氢气量按氢油体积比为 7: 1。 液相产物一部分经循环泵作为循环油与新鲜原料混合溶氢后进入反应器， 另一 部分液相产物以产品的形式进入产品罐，然后进行实沸点切割。原料油性质列于表 4， 产品分布及性质见表 5。
由表 5 可见，含 10wt.%焦蜡的混合蜡油为原料，控制 >370°C尾油收率约 20 wt.% 的工艺条件下， 采用该工艺技术可以生产优质喷气燃料和清洁柴油。
比较例 1
与实施例 1相比， 处理相同性质的混合柴油， 反应器两个催化剂床层之间无内构 件， 所有的氢气全部从反应器入口进入反应器， 其它工艺条件按实施例 1操作条件， 精制柴油性质见表 6。 由表 6可以看出， 本发明反应器的反应温度与常规反应器的温 度相比低 15°C， 而产品性质较优。
表 1 催化剂的理化性质指标
Figure imgf000008_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 精制生成油 精制生成油 项 目 混合柴油
( 160-230 °C ) (>230°C ) ( 160-230 °C ) (>230°C ) 密度 (20°C)， g/cm3 0.8350 0.81 10 0.8731 0.8122 0.8614 硫含量， 1020.0 541.8 1602.1 2.3 7.9 氮含量， g/g 881.8 267.7 1330.6 8.9 9.8 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/cm- 0.8559 0.8502 硫含量， g/g 780.0 8.1
氮含量， g/g 697.0 5.2
表 4 实施例 3原料油性质
项 目 分析结果
密度 (20°C)， g/cm3 0.8559
馏程， 。C
IBP/10% 249/333
30%/50% 376/405
70%/90% 438/478
95%/EBP 492/519
硫含量， g/g 780.0
氮含量， g/g 697.0
BMCI值 22.2
表 5 实施例 3实验结果
项目 产品分布与性质
C5+液体收率， wt.% 98.5
产品收率及质量
65~165°C重石脑油收率， wt.% 15.69
硫含量， g/g <0.5
氮含量， g/g <0.5
165〜260°C喷气燃料收率， wt.% 23.83
冰点， 。C -51
烟点， V 30
260~370°C柴油收率， wt.% 35.42
十六烷指数 83.2
凝点， °C -2
165~370°C柴油收率， wt.% 59.25
>370°C尾油收率， wt.% 19.80
BMCI值 7.6
表 6 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 326 311 氢分压， MPa 6.0 6.0 混合柴油 无内构件 本发明反应器 油品性质 混合柴油
( >230°C ) 反应器生成油 生成油 ( >230°C ) ( >230°C ) 密度 (20°C)， g/cm3 0.8350 0.8731 0.8501 0.8614 硫含量， g/g 1020.0 1602.1 40.0 7.9
Ϊ , lg 881.8 1330.6 48.0 9.8 工业实用性
本发明产物循环的加氢处理方法中，可以根据需要将两个或多个反应器串联（ - 个反应器的流出物进入下一个反应器） 或并联（ 物料分别进入不同的反应器） 使用。
本发明上述液相加氢工艺方法中，加氢催化剂可以根据反应的需要使用适宜的加 氢催化剂， 实现不同的加氢 的。 如加氢精制催化剂、 加氢改质催化剂、 加氢处理催 化剂、 加氢裂化催化剂等， 各种催化剂可以选择商品催化剂， 也可以根据现有技术制 备。
本发明液相加氢工艺方法使用上述反应器， 可以有效地补充液相原料中的氢气， 在催化剂床层形成气液逆流， 增大氢气浓度， 同时脱除了反应生成的硫化氢和氨， 能 够减少 H2S和 N¾对下一步加氢反应的抑制作用， 提高加氢效率， 提高了原料适应 性。 该方法不需要循环氢气和循环氢压缩机， 能够降低设备投资和操作成本。
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、 喷气燃料、 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喷气燃料、 柴油工艺过程。
本发明加氢反应过程中，使用的氢气量为在化学氢耗量基础上增加略多于系统的 溶解氢量， 反应部分不设置氢气循环系统， 依靠液相产品大量循环时携带进反应系统 的溶解氢以及氢气补充溶解的氢来提供新鲜原料进行加氢反应所需要的氢气，由于加 氢产物的循环使用， 仍可以保持催化剂的活性稳定性。其优点是可以消除催化剂的润 湿因子影响和循环氢中 H2S 及 NH3 的影响； 由于循环油的比热容大， 可以降低反应 器的温升， 提高催化剂的利用效率。

Claims

权 利 要 求 书
1. 一种馏分油两相加氢反应器， 其特征在于： 反应器上部空间尺寸比下部催化 剂床层部分大， 包括至少 2个催化剂床层。
2. 根据权利要求 1所述的馏分油两相加氢反应器， 其特征在于： 包括 2〜4个催 化剂床层
3.根据权利要求 1所述的馏分油两相加氢反应器， 其特征在于： 在至少一个相邻 催化剂床层之间设置气体补充和汽提含杂质液相物流的内构件。
4. 根据权利要求 3所述的馏分油两相加氢反应器， 其特征在于： 该内构件包括 气液接触构件及汽提构件。
5. 根据权利要求 4所述的馏分油两相加氢反应器， 其特征在于： 气液接触构件 和汽提构件设置在一起。
6. 根据权利要求 3所述的馏分油两相加氢反应器， 其特征在于： 内构件包括隔 离板和排气管道。
7. 根据权利要求 6所述的馏分油两相加氢反应器， 其特征在于： 隔离板设有多 个降液通孔。
8. 根据权利要求 6所述的馏分油两相加氢反应器， 其特征在于： 隔离板与多个 排气管道相连接。
9. 根据权利要求 6所述的馏分油两相加氢反应器， 其特征在于： 排气管道垂直 设置在隔离板上面。
10. 根据权利要求 6所述的馏分油两相加氢反应器， 其特征在于： 排气管道顶部 与上一催化剂床层下部相接触。
11. 一种液相加氢工艺方法， 其特征在于： 使用权利要求 1所述的加氢反应器
12. 根据权利要求 11 所述的液相加氢工艺方法， 其特征在于： 过程包括： 经加 氢处理后的液相产物的一部分循环与新鲜原料混合为液相物料，溶氢之后形成饱和液 相物流从上部进入反应器， 在反应器上部的加氢催化剂床层进行加氢反应， 反应后流 出物通过内构件与氢气混合， 补充液相物料中溶解的氢气量， 补充了溶解氢的液相物 料进入下一加氢催化剂床层； 气相氢通过汽提构件的排气管道进入催化剂床层，在催 化剂床层形成气液逆流， 使催化剂床层的氢气浓度提高， 氢气将反应生成的硫化氢和 氨杂质汽提出来。
13. 根据权利要求 1 1 所述的液相加氢工艺方法， 其特征在于： 循环的液相产物 与新鲜原料的体积比为 0.1： 1〜 10: 1。
14. 根据权利要求 11 所述的液相加氢工艺方法， 其特征在于： 催化剂床层间补 充的氢气量按氢油体积比为 0.5: 1〜 10: 1 ;
15. 根据权利要求 11 所述的液相加氢工艺方法， 其特征在于： 液相物料通过催 化剂床层的反应温度为 130〜450°C。
16.根据权利要求 11所述的液相加氢工艺方法， 其特征在于： 液相物料通过催化 剂床层的反应压力为 l〜20MPa。
17. 根据权利要求 11 所述的液相加氢工艺方法， 其特征在于： 液相物料通过催 化剂床层的液时体积空速为 0.5〜15h— '。
PCT/CN2013/000904 2013-01-30 2013-08-01 一种馏分油两相加氢反应器和加氢工艺方法 Ceased WO2014117310A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/764,485 US9534178B2 (en) 2013-01-30 2013-08-01 Distillate two-phase hydrogenation reactor and hydrogenation method
SG11201505319SA SG11201505319SA (en) 2013-01-30 2013-08-01 Distillate two-phase hydrogenation reactor and hydrogenation method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310035980.4A CN103965953B (zh) 2013-01-30 2013-01-30 一种馏分油两相加氢反应器和加氢工艺方法
CN201310035980.4 2013-01-30

Publications (1)

Publication Number Publication Date
WO2014117310A1 true WO2014117310A1 (zh) 2014-08-07

Family

ID=51235967

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/000904 Ceased WO2014117310A1 (zh) 2013-01-30 2013-08-01 一种馏分油两相加氢反应器和加氢工艺方法

Country Status (4)

Country Link
US (1) US9534178B2 (zh)
CN (1) CN103965953B (zh)
SG (1) SG11201505319SA (zh)
WO (1) WO2014117310A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116445185A (zh) * 2022-01-06 2023-07-18 中国石油化工股份有限公司 一种柴油深度脱硫的方法
RU220551U1 (ru) * 2022-05-11 2023-09-21 Общество с ограниченной ответственностью "Юнайтед Кэталист Текнолоджис" Адиабатический реактор гидрирования со встроенным внутрь конусообразным устройством

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3331969B1 (en) * 2015-08-06 2020-06-17 Uop Llc Process for reconfiguring existing treating units in a refinery
CN105602619B (zh) * 2015-12-18 2017-10-17 中国石油天然气股份有限公司 一种液相加氢异构系统及其工艺和应用
CN108203600A (zh) * 2016-12-16 2018-06-26 中国石油天然气股份有限公司 一种提高煤油氧化安定性的方法
CN111068587B (zh) * 2018-10-22 2021-08-31 中国石油化工股份有限公司 一种液相加氢反应装置及反应方法
CN113209780B (zh) * 2021-05-17 2025-03-28 山东钢铁股份有限公司 一种焦炉煤气微晶吸附再生尾气的净化处理方法
CN116059926B (zh) * 2021-10-29 2024-09-03 中国石油化工股份有限公司 加氢精馏反应器以及联合反应器
CN116064123B (zh) * 2021-10-29 2024-07-02 中国石油化工股份有限公司 一种催化裂化轻循环油加氢处理生产芳烃原料的方法及装置
CN115404100B (zh) * 2022-09-28 2023-10-24 石家庄睿途生物科技有限公司 一种沸腾床和固定床耦合的加氢装置及加氢方法
CN117568066B (zh) * 2023-11-16 2025-12-05 中国海洋石油集团有限公司 一种用于油相加氢的系统装置和油相加氢方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101338219A (zh) * 2008-08-11 2009-01-07 中国石油化工集团公司 一种两相加氢方法
CN102039105A (zh) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 气液逆流反应器和气液逆流加氢工艺方法
CN102039104A (zh) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 一种反应器和液相加氢工艺方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4456461A (en) * 1982-09-09 1984-06-26 Phillips Petroleum Company Separation of low boiling constituents from a mixed gas
CN1004421B (zh) 1986-12-18 1989-06-07 中国科学院山西煤炭化学研究所 重整生成油加氢精制工艺
GB8728156D0 (en) * 1987-12-02 1988-01-06 Davy Mckee Ltd Process
CN1028650C (zh) 1993-03-05 1995-05-31 大庆石油化工总厂研究院 劣质原料油—段加氢裂化方法
CN1035775C (zh) 1994-03-28 1997-09-03 中国石油化工总公司 催化裂解汽油加氢精制方法
CN1061678C (zh) 1996-09-12 2001-02-07 中国石油化工集团公司抚顺石油化工研究院 串联加氢法生产高质量凡士林
CN1062584C (zh) 1996-10-09 2001-02-28 中国石油化工集团公司抚顺石油化工研究院 加氢法生产白油
US7569136B2 (en) 1997-06-24 2009-08-04 Ackerson Michael D Control system method and apparatus for two phase hydroprocessing
EP0993498B1 (en) 1997-06-24 2004-08-11 Process Dynamics, Inc. Two phase hydroprocessing
US6284104B1 (en) * 1999-03-04 2001-09-04 Catalytic Distillation Technologies Apparatus and process for hydrogenations
EP1041113A1 (en) 1999-03-30 2000-10-04 Fina Research S.A. Polyolefins and uses thereof
US6213835B1 (en) 1999-12-30 2001-04-10 Charles Edwin Wolthoff Changeable neon letters
EP1482023B1 (en) 2000-11-11 2008-04-09 Haldor Topsoe A/S Method of retrofitting existing hydroprocessing reactors
CN102634367A (zh) * 2008-08-11 2012-08-15 中国石油化工集团公司 一种两相加氢方法
CN102732299A (zh) * 2011-04-12 2012-10-17 中国石油化工股份有限公司 一种烃油两相加氢方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101338219A (zh) * 2008-08-11 2009-01-07 中国石油化工集团公司 一种两相加氢方法
CN102039105A (zh) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 气液逆流反应器和气液逆流加氢工艺方法
CN102039104A (zh) * 2009-10-21 2011-05-04 中国石油化工股份有限公司 一种反应器和液相加氢工艺方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116445185A (zh) * 2022-01-06 2023-07-18 中国石油化工股份有限公司 一种柴油深度脱硫的方法
RU220551U1 (ru) * 2022-05-11 2023-09-21 Общество с ограниченной ответственностью "Юнайтед Кэталист Текнолоджис" Адиабатический реактор гидрирования со встроенным внутрь конусообразным устройством

Also Published As

Publication number Publication date
US20150361357A1 (en) 2015-12-17
CN103965953A (zh) 2014-08-06
CN103965953B (zh) 2015-07-22
US9534178B2 (en) 2017-01-03
SG11201505319SA (en) 2015-08-28

Similar Documents

Publication Publication Date Title
WO2014117310A1 (zh) 一种馏分油两相加氢反应器和加氢工艺方法
CN101993721B (zh) 液相循环加氢处理方法和反应系统
WO2014117309A1 (zh) 多级溶氢的液相加氢反应方法
CN201644076U (zh) 一种液相加氢反应器
CN103509598B (zh) 一种生产超低硫柴油的加氢系统及方法
CN102041071B (zh) 柴油加氢工艺方法
CN104560132A (zh) 一种连续液相蜡油加氢处理方法
CN103571533B (zh) 一种煤焦油加氢系统及方法
CN101787305A (zh) 一种液相循环加氢处理方法和反应系统
CN203238222U (zh) 一种带有多级溶氢系统的液相加氢反应装置
CN103805240B (zh) 一种低成本组合加氢精制工艺方法
CN106701179B (zh) 液相加氢装置及方法
CN104449814B (zh) 一种生产超低硫柴油的加氢系统及加氢方法
CN104232154B (zh) 一种馏分油加氢改质方法
CN103074102B (zh) 一种连续液相烃油加氢处理方法
CN103059954B (zh) 一种降低催化裂化汽油硫含量的方法
CN106701180B (zh) 液相加氢装置及方法
CN202063881U (zh) 一种液相加氢反应器
CN105713656A (zh) 一种微泡器内溶氢反应器及其应用方法
CN111068588B (zh) 一种柴油超深度脱硫装置及柴油加氢反应系统
CN104099127A (zh) 一种馏分油加氢处理工艺方法
CN103059955B (zh) 一种催化裂化汽油生产清洁汽油的方法
CN106701174B (zh) 液相加氢装置及方法
CN114437809B (zh) 一种液相加氢装置及液相加氢方法
CN102732299A (zh) 一种烃油两相加氢方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13874068

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 14764485

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 18.11.2015)

122 Ep: pct application non-entry in european phase

Ref document number: 13874068

Country of ref document: EP

Kind code of ref document: A1