WO2014044195A1 - 一种重整生成油加氢处理方法 - Google Patents

一种重整生成油加氢处理方法 Download PDF

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Publication number
WO2014044195A1
WO2014044195A1 PCT/CN2013/083786 CN2013083786W WO2014044195A1 WO 2014044195 A1 WO2014044195 A1 WO 2014044195A1 CN 2013083786 W CN2013083786 W CN 2013083786W WO 2014044195 A1 WO2014044195 A1 WO 2014044195A1
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Prior art keywords
oil
hydrogen
reforming
gas
reformed
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PCT/CN2013/083786
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English (en)
French (fr)
Inventor
李华
刘建平
佘喜春
贺晓军
李庆华
陈庆岭
江磊
曾志煜
杨清贫
刘呈立
Original Assignee
中国石油化工股份有限公司
湖南长岭石化科技开发有限公司
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Application filed by 中国石油化工股份有限公司, 湖南长岭石化科技开发有限公司 filed Critical 中国石油化工股份有限公司
Priority to SG11201502230YA priority Critical patent/SG11201502230YA/en
Priority to US14/430,456 priority patent/US9879186B2/en
Priority to RU2015114769A priority patent/RU2609780C2/ru
Priority to KR1020157010327A priority patent/KR101804488B1/ko
Priority to EP13840101.3A priority patent/EP2899253B1/en
Publication of WO2014044195A1 publication Critical patent/WO2014044195A1/zh

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    • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
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    • B01F23/2376—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media characterised by the gas being introduced
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    • C10G35/04—Catalytic reforming
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    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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    • C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
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    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
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    • 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

Definitions

  • the invention relates to a reforming oil hydrotreating process. Background technique
  • Catalytic reforming is one of the main processes of petroleum refining. It converts naphtha and other feedstock oil into aromatic hydrocarbon-rich reforming oil at a certain temperature, pressure, hydrogen and catalyst, and produces hydrogen by-product. process.
  • the reformed oil obtained by gas-liquid separation of the mixture obtained by catalytic reforming can be directly used as a blending component of a vehicle fuel, and can also be subjected to an aromatic hydrocarbon extraction process to produce chemical raw materials such as benzene, toluene and xylene. .
  • the reformed oil is not only rich in aromatic hydrocarbon and solvent oil fractions, but also contains small amounts of olefins. Therefore, to reproduce the oil to produce a qualified aromatic and solvent oil product, it is necessary to remove the olefin.
  • the olefin content in the reformed oil has also increased correspondingly, so that the problem of removing the olefin from the reforming oil is more prominent.
  • the main methods for reforming oil to remove olefins are: white earth adsorption refining, reforming oil-derived distillate oil or full-distillate post-hydrogenation.
  • white earth adsorption refining reforming oil-derived distillate oil or full-distillate post-hydrogenation.
  • the adsorption and purification of clay is limited in the adsorption capacity of clay, and the waste clay cannot be regenerated.
  • Pd or Pt-based precious metal catalysts have been used to selectively hydrogenate distillate or whole fractions of reformed oil to remove olefins.
  • CN1004421B discloses a hydrotreating process for reforming oil, which uses a reforming oil having a bromine number of 0.5-8 g bromine/100 g and an aromatic content of 35-55 wt% as a raw material, and the reaction temperature is 200. -300 ° C, the partial pressure of hydrogen is 5-20 kg / cm 2 , the liquid space velocity is 6-20 hours - the hydrogen / oil volume ratio is 200-1000, using 0.15-0.6 wt% Pd (for the carrier) Thin-shell strip-shaped Pd-Al 2 0 3 catalyst.
  • CN1049001C discloses a reforming oil refining process, which uses a reforming oil having a bromine number of 0.5-8.0 g bromine/10.0 g as a raw material, and a catalytic hydrogenating agent having a Pd content of 0.15-6 wt% (for the carrier), the shell ⁇ / ⁇ - ⁇ 1 2 0 3 , wherein the raw material has been removed by more than C 9 aromatic hydrocarbons and the aromatic content is 20-85% by weight, the reaction temperature is 150-200 ° C, and the hydrogen partial pressure in the reactor It is 0.5-3.0 MPa, and the liquid space velocity is 3-15 h - the hydrogen oil volume ratio is 100-500.
  • the object of the present invention is to provide a reforming oil hydrotreating method which adopts a liquid phase hydrogenation process, on the one hand, eliminates the demand for circulating hydrogen, and on the other hand, can fully utilize the dissolution in the reforming oil. hydrogen.
  • the inventors of the present invention found in practice that: the mixture obtained by contacting the hydrocarbon oil with the catalyst having catalytic reforming under catalytic reforming conditions is subjected to gas-liquid separation in a gas-liquid separation tank, and the obtained reforming oil is produced. The hydrogen generated during the catalytic reforming process is still dissolved. If the reformed oil is obtained from the bottom of the gas-liquid separation tank, the liquid phase hydrotreating is directly performed, and the dissolved hydrogen in the reformed oil is used as the hydrogenation.
  • One of the treated hydrogen source or hydrogen source can fully utilize the residual hydrogen remaining in the reforming oil to remove the olefin in the reforming oil, and on the other hand, can eliminate the need for circulating hydrogen. On the basis of this, the present invention has been completed.
  • the present invention provides a reforming oil hydrotreating process, the method comprising: contacting a reformed oil with a catalyst having catalytic hydrogenation in a hydrogenation reactor under liquid phase hydrotreating conditions,
  • the hydrogen used in the hydrotreating is derived at least in part from the dissolved hydrogen in the reforming oil.
  • the reforming oil separated from the reforming product separation tank is directly subjected to liquid phase hydrotreating, which fully utilizes the dissolved hydrogen in the reforming oil, and It is capable of removing olefins from reforming oils, while also eliminating the need for recycled hydrogen and its recycling equipment. Therefore, the reforming oil hydrotreating method according to the present invention simplifies the process flow, reduces investment costs and operating costs, and realizes efficient and low-cost industrial production.
  • the reforming oil obtained by the reforming oil hydrotreating method of the present invention can have a bromine index of 50 mgBr 2 /100 g or less, or even 10 mgBr 2 /100 g or less; and the amount of aromatic hydrocarbon loss is small and can be less than 0.5% by weight.
  • Figure 1 is a schematic view showing the structure of an embodiment of a mixing apparatus used in a reforming oil hydrotreating method according to the present invention
  • Figure 2 is a schematic view showing the structure of another embodiment of the mixing apparatus used in the reforming oil hydrotreating method according to the present invention.
  • Figure 3 is a schematic view showing the structure of a preferred embodiment of the mixing device used in the reforming oil hydrotreating method according to the present invention
  • Figure 4 is a schematic cross-sectional view showing a preferred embodiment of a member having a perforated region in a mixing device used in a reforming oil hydrotreating method according to the present invention
  • FIG. 5 is a preferred embodiment of a reforming oil hydrotreating process according to the present invention
  • FIG. 6 is a view for explaining a plurality of hydrogenation reactors connected in series in a reforming oil hydrotreating method according to the present invention; Implementation method;
  • Figure 7 is a diagram for explaining an embodiment in which a plurality of hydrogenation reactors are connected in parallel in a reforming oil hydrotreating method according to the present invention
  • Fig. 8 is for explaining a part I in Fig. 5.
  • the present invention provides a reforming oil hydrotreating process, the method comprising: contacting a reformed oil with a catalyst having catalytic hydrogenation in a hydrogenation reactor under liquid phase hydrotreating conditions,
  • the hydrogen used in the hydrotreating is derived at least in part from the dissolved hydrogen in the reforming oil.
  • the reforming oil is injected into a gas-liquid separation tank from a catalytic reforming mixture obtained by contacting a hydrocarbon oil with a catalyst having reforming catalysis under catalytic reforming conditions, from the The reforming obtained from the bottom of the gas-liquid separation tank produces oil. That is, according to the hydrotreating method of the present invention, a mixture obtained by contacting a hydrocarbon oil with a catalyst having catalytic reforming under catalytic reforming conditions is subjected to gas-liquid separation in a gas-liquid separation tank, from which the separation tank is The reformed oil obtained from the bottom of the tank is directly subjected to liquid phase hydrotreating.
  • the reforming oil contains hydrogen remaining in the catalytic reforming process
  • the reforming mixture outputted from the reforming reactor is subjected to gas-liquid separation to obtain reforming oil, thereby
  • the hydrogen in the whole produced oil i.e., the hydrogen remaining in the catalytic reforming process
  • the dissolved hydrogen in the reformed produced oil refers to the residual hydrogen in the catalytic reforming process.
  • the content of dissolved hydrogen in the reformed oil is slightly different depending on the conditions of gas-liquid separation and the composition of the reformed oil. Generally, based on the total amount of the reformed oil, the weight The content of dissolved hydrogen in the whole produced oil is 0.001 to 0.025% by weight.
  • the source of hydrogen when the reforming oil is hydrotreated, the source of hydrogen may be only hydrogen contained in the reforming oil itself, or hydrogen contained in the reforming oil itself.
  • the hydrogen added to the oil is reformed. That is, according to the hydrotreating method of the present invention, the hydrotreating may be carried out in the absence of supplemental hydrogen gas or in the presence of supplemental hydrogen.
  • the supplemental hydrogen refers to hydrogen gas injected into the reformed oil in one or a portion of the contact and/or the contact.
  • the hydrotreating method of the present invention whether the amount of hydrogen to be replenished and the amount of supplemental hydrogen can be adjusted according to the reforming
  • the content of dissolved hydrogen in the produced oil and the content of olefin in the reformed oil are appropriately selected.
  • the reforming oil hydrotreating method according to the present invention preferably does not replenish the reforming oil when the amount of dissolved hydrogen in the reforming oil is sufficient to remove the olefin in the reforming oil to meet the requirements.
  • Hydrogen only uses dissolved hydrogen remaining in the catalytic reforming process contained in the reformed oil to be a hydrogen source for hydrogenation.
  • the hydrotreating method according to the present invention is preferably carried out in the presence of supplemental hydrogen.
  • the supplementary hydrogen in the presence of supplemental hydrogen, may be injected into the reforming oil at a time, for example: before the reforming oil may be sent to the hydrogenation reactor Injecting the supplementary hydrogen into the reforming oil; the supplementary hydrogen may also be injected into the reforming oil in stages, for example: at least one supplementary hydrogen inlet may be disposed on the hydrogenation reactor, The supplemental hydrogen is injected into the reforming oil at the inlet end of the hydrogenation reactor, and the remaining portion of the supplemental hydrogen is injected into the reforming oil at the inlet of the supplemental hydrogen.
  • hydrogen gas in the presence of supplemental hydrogen, hydrogen gas can be injected into the reforming oil to form an oil.
  • the manner of injecting the supplemental hydrogen into the reformed oil to produce comprises: injecting the supplemental hydrogen into the reformed oil through pores having an average pore size of nanometer size.
  • the supplementary hydrogen is injected into the reforming oil through the pores having an average pore diameter of nanometer size, and the supplementary hydrogen can be highly dispersed and dissolved in the reforming oil at a faster rate, thereby eliminating the liquid phase addition to the existing hydrocarbon oil.
  • the hole is a through hole.
  • the pores may have an average pore diameter of from 1 nm to 1000 nm, preferably
  • the average pore diameter of the pores is more preferably from 30 nm to 800 nm, further preferably from 50 nm to 500 nm.
  • the average pore size is determined by scanning electron microscopy.
  • Hydrogen gas may be injected into the static reforming oil, or hydrogen may be injected into the reforming oil in a flowing state. It is preferable to inject hydrogen into the reforming oil in a flowing state, so that hydrogen can be injected into the reforming oil while transporting the reforming oil to obtain further improved production efficiency.
  • the hydrogen injection rate is V1 and is expressed as g_h- ⁇ m- 2 (in terms of the total amount of hydrogen per unit area per unit time)
  • the hydrogen dispersion dissolves the effect.
  • Vl / v 2 0.005-0.01, so that not only can Good hydrogen dispersing and dissolving effect, and high production efficiency can be obtained.
  • the rate of hydrogen injection reforming to form oil can generally be 0.0001-2000 kg_h- ⁇ m- 2 .
  • the supplementary hydrogen gas can be injected into the reforming oil through a hole having an average pore diameter of nanometer size by various methods.
  • the supplemental hydrogen is injected into the reformate-forming oil through a mixing device having a pore size of nanometer-sized pores, the mixing device comprising at least one liquid passage for containing reforming oil and at least a gas passage for accommodating the supplemental hydrogen gas, the liquid passage and the gas passage being abutted by a member, at least a portion of the member being a perforated region, the perforated region having the average pore size being a nanometer size
  • the pores through which the supplemental hydrogen gas is injected into the reforming oil are provided.
  • liquid passage means a space capable of accommodating reforming oil
  • gas passage means a space capable of accommodating the supplementary hydrogen
  • the positional relationship between the liquid passage and the gas passage is not particularly limited as long as the liquid passage and the gas passage are adjacent to each other by the member.
  • the gas passage 2 is located inside the liquid passage 1, and the inner wall of the member 3 constitutes the gas passage 2.
  • the gas passage 2 is located on one side of the liquid passage 1, and the liquid passage 1 and the gas passage 2 pass through the member 3. Separated.
  • the gas passage 2 surrounds the outside of the liquid passage 1, and the passage between the gas passage 2 and the liquid passage 1 3 and separated.
  • At least a portion of the member is a perforated region that extends along a length of the member.
  • the apertured region covers the entire member (ie, the liquid channel and the gas channel are adjacent by a member having the hole having the average pore size of nanometer size, and the supplementary hydrogen gas is passed through the hole Injected into the reforming oil).
  • the pored region has pores having an average pore diameter of nanometers so that hydrogen gas is injected into the hydrocarbon oil through the pores having an average pore diameter of nanometers.
  • the porosity of the apertured region is preferably from 5 to 28%, which enables a sufficient amount of hydrogen to be better dispersed and dissolved in the hydrocarbon oil.
  • the porosity of the porous region is more preferably from 10 to 25%.
  • the porosity ratio refers to the percentage of the pore volume in the pored region occupying the total volume of the pore region, which is determined by a nitrogen adsorption method.
  • the member may be of various kinds capable of allowing supplementary hydrogen contained in the gas passage to pass through the hole into the reforming oil contained in the liquid passage, A member having bubbles of a nanometer size is formed.
  • the member is a pipe.
  • the member is formed of a porous material, and the average of the holes in the member
  • the pore size is nanometer size.
  • the member in another embodiment, includes a substrate and a porous film attached to the substrate, the substrate having a hole, and the porous film may be located in the substrate and housed in the liquid passage
  • the surface of the inner reforming oil-forming contact may also be located on the surface of the substrate that is in contact with the supplemental hydrogen contained in the gas passage.
  • the porous membrane is located on a surface of the substrate that is in contact with reformate-forming oil contained in the liquid passage.
  • the pores in the porous membrane have an average pore size of nanometer size. The average pore diameter of the pores in the substrate is not particularly limited as long as it can pass a gas.
  • the pores on the substrate have an average pore size of a micron size (ie, greater than 1 micrometer to 1000 micrometers) or a nanometer size (ie, 1 nanometer to 1000 nanometers), that is, an average pore diameter of the pores on the substrate is 1 Nano to 1000 microns.
  • the member is preferably a membrane tube (i.e., a porous tube having pores as a matrix, and the porous membrane having the porous membrane on the inner wall and/or the outer wall).
  • the film tube may be a common inorganic film tube (e.g., an inorganic ceramic film tube) or an organic film tube as long as the material forming the film tube does not chemically interact with reforming oil and hydrogen.
  • the member may be prepared by a conventional method, or may be commercially available, and will not be described herein.
  • the pipe can be used in combination with a casing. That is, the duct is placed in a casing with a space between the outer wall of the duct and the inner wall of the casing.
  • the space formed by the inner wall of the duct is the liquid passage for accommodating the reformed oil, and the space formed by the outer wall of the duct and the inner wall of the casing is the gas passage for accommodating the supplemental hydrogen;
  • the space formed by the inner wall of the duct is the gas passage for accommodating supplemental hydrogen, and the space formed by the outer wall of the duct and the inner wall of the casing is the liquid passage for accommodating reforming oil.
  • a space formed by an inner wall of the duct is the liquid passage for accommodating reforming oil, and a space formed by an outer wall of the duct and an inner wall of the casing is a gas for accommodating supplementary hydrogen aisle.
  • the member is a film tube
  • a space in contact with the porous film on the film tube as a liquid passage.
  • a space formed by the inner wall of the membrane tube serves as the liquid passage for accommodating reforming oil
  • the outer wall of the membrane tube and the shell The space formed by the inner wall of the body acts as the gas passage for accommodating the supplemental hydrogen.
  • the pipe when the member is a pipe, the pipe may have one of the liquid passages, or may have a plurality of the liquid passages.
  • the duct 4 has a plurality (for example 4-20) of liquid passages 1 that are parallel to each other.
  • the plurality of liquid passages are plural, the plurality of liquid passages are preferably evenly distributed.
  • the housing may be various members having a hollow structure and at least one opening, the opening being in communication with a gas source for supplementing hydrogen or a reforming oil storage tank to supplement hydrogen or heavy
  • a gas source for supplementing hydrogen or a reforming oil storage tank to supplement hydrogen or heavy
  • the entire generated oil is introduced into a space between the inner wall of the casing and the outer wall of the pipe (i.e., the gas passage or the liquid passage).
  • the amount of the supplemental hydrogen gas can be appropriately selected according to the saturated dissolved amount of hydrogen in the reforming oil and the chemical hydrogen consumption of the reforming oil to enable hydrogenation.
  • the product can meet the requirements of use.
  • the hydrotreating method of the present invention when the supplementary hydrogen gas is injected into the reforming oil through the pores having an average pore diameter of nanometer size, the hydrogen gas can be highly dispersed and dissolved in the reforming oil at a faster rate. Therefore, the hydrotreating method according to the present invention can ensure the hydrogen carrying amount of the reforming oil even if hydrogen is not injected into the reforming oil.
  • the amount of the supplemental hydrogen may be 0.01 to 4 times the saturated dissolved amount of hydrogen in the reforming oil under the liquid phase hydrotreating conditions, It is preferably 0.01 to 2 times the saturated dissolved amount, more preferably 0.1 to 1 times the saturated dissolved amount, and still more preferably 0.1 to less than 1 times the saturated dissolved amount.
  • the saturated dissolved amount refers to the number of grams of hydrogen dissolved in 100 g of reformed oil under liquid phase hydrotreating conditions. The various methods commonly used in the art can be used to determine the amount of saturated hydrogen dissolved in the reformed oil, which will not be described in detail herein.
  • the condition for injecting the supplementary hydrogen into the reformed oil is not particularly limited and may be a conventional choice in the art.
  • supplemental hydrogen can be injected into the reforming produced oil at the temperature and pressure of the hydrotreating.
  • the contact of the reformed oil to the catalyst having catalytic hydrogenation can be carried out in various hydrogenation reactors conventionally used in the art, and is not particularly limited.
  • the contacting may be carried out in a tank reactor or in a tubular reactor.
  • the contacting is carried out in a tubular reactor.
  • the tubular reactor refers to a reactor having a large aspect ratio, for example; the ratio of the length to the inner diameter of the tubular reactor may be 5-50:1.
  • the inner diameter of the tubular reactor may be a conventional choice in the art.
  • the tubular reactor has an inner diameter of 20 to 1000 mm.
  • hydrogen is preferably injected into the reforming oil by the mixing device described above.
  • the number of the mixing devices may be one or plural.
  • the mixing device is preferably disposed at the inlet of the tubular reactor At the end, in the process of injecting reforming oil into the tubular reactor, hydrogen is injected into the reforming oil by the mixing device.
  • the mixing device can be disposed at the inlet end of the tubular reactor by various methods commonly used in the art, as long as the reforming oil is allowed to pass through the liquid passage of the mixing device, and the gas passage is passed through the member
  • the supplemental hydrogen inside can be injected into the reforming oil to form oil.
  • hydrogen is injected into the reforming oil to form a reforming oil containing hydrogen gas, and the reforming oil containing hydrogen gas is fed to the reactor, and the mixing is carried out by using the mixing device described above.
  • the inner diameter of the outlet 0 of the apparatus for outputting the reformed oil to which hydrogen is added is ri
  • the method of the present invention in addition to providing at least one of said mixing devices at the inlet end of said tubular reactor, preferably at least one of said mixing devices is provided on said tubular reactor, which enables the hydrotreating process
  • the supplementary hydrogen is injected into the reformed oil in batches according to the chemical hydrogen consumption of the reformed oil and the hydrogen content in the reformed oil to further improve the efficiency of the hydrotreating method according to the present invention.
  • the mixing device can be disposed in the tubular reactor in various ways, for example, in the manner described in Figure 1 : the space formed by the inner wall of the tubular reactor is used as a liquid passage, and in the tubular reactor Opening a wall; forming a member having an average pore size of nanometers as a pipe sealed at one end, the space formed by the inner wall of the pipe serving as a gas passage; and extending the pipe through the opening into the tubular reactor (wherein The outer wall of the pipe is sealingly connected to the opening, and one end of the pipe in the tubular reactor is a sealed end, and the other end of the pipe is connected with a source of supplemental hydrogen gas, thereby injecting supplementary hydrogen through the pipe.
  • the outer wall of the pipe is sealingly connected to the opening, and one end of the pipe in the tubular reactor is a sealed end, and the other end of the pipe is connected with a source of supplemental hydrogen gas, thereby injecting supplementary hydrogen through the pipe.
  • the hydrotreating is carried out in a tubular reactor
  • the mixing device preferably comprises: a pipe as the member, and a fitting with the pipe a housing used, wherein a space formed by an inner wall of the duct serves as a liquid passage, and a space formed by an outer wall of the duct and an inner wall of the casing serves as a gas passage, and the liquid passage and the tubular reactor Used for space communication for hydrotreating.
  • the number of the hydrogenation reactors may be one or plural (i.e., two or more).
  • the plurality of hydrogenation reactors may be connected in series or in parallel.
  • the mixing device described above feeds the supplemental hydrogen into the reforming oil).
  • the catalyst having catalytic hydrogenation can be present in various forms.
  • the hydrogenation reactor is a fixed bed reactor.
  • the number of the catalyst beds may be a conventional choice in the art, for example: the number of the catalyst beds may be one or two or two. the above.
  • the volumetric space velocity of the reforming oil may be 5-20 h - preferably 10-20 11 persons
  • the hydrotreating is carried out in a tubular fixed bed hydrogenation reactor.
  • the hydrotreating method according to the present invention achieves the object of the present invention by utilizing the dissolved hydrogen remaining in the catalytic reforming process contained in the reforming oil, and the liquid phase hydrotreating conditions are not particularly limited and may be Conventional choices in the art.
  • the liquid phase hydrotreating conditions include: the temperature may be from 130 to 200 ° C, preferably from 140 to 160 ° C; and the pressure may be from 1.5 to 3.5 MPa, preferably from 1.5 to 2 MPa, in terms of gauge pressure.
  • the catalyst having catalytic hydrogenation can be various catalysts having catalytic hydrogenation which are commonly used in the art, and will not be described herein.
  • the hydrotreating method according to the present invention further comprising: removing light components in the product obtained by the contacting (ie, hydrotreating) to remove a catalytic reforming process contained in the product obtained by hydrotreating and adding Light components (eg, components below C 5 ) produced during hydrogen processing.
  • the hydrotreating method according to the present invention is not particularly limited for the method of removing the light component, and a conventional method in the art can be employed.
  • the hydrogenated product can be heated to desorb the light component in the hydrogenated product.
  • the hydrotreating method according to the present invention when the light component in the hydrogenated product is taken off by heating the hydrogenated product, the hydrotreating method according to the present invention further comprises removing the product obtained by the contacting The light component is obtained to obtain a light-removing component oil, and the reformed oil is subjected to heat exchange with the light-removing component oil before the reforming oil is sent to the hydrogenation reactor for the hydrotreating.
  • the waste heat in the light-removing component oil can be fully utilized, and the reforming oil can be preheated, thereby eliminating the need for the reforming oil preheating furnace, and further reducing the equipment investment of the hydrotreating method according to the present invention. Cost and energy consumption.
  • the hydrotreating method according to the present invention may further comprise removing heavy components from the light component oil to obtain aromatic hydrocarbon extraction. raw material.
  • the heavy components in the de-light component oil can be removed by methods commonly used in the art, and will not be described herein.
  • Figure 5 is a preferred embodiment of a reforming oil hydrotreating process in accordance with the present invention.
  • the hydrocarbon oil is contacted with the catalyst having reforming catalysis in the catalytic reforming reactor 5 under catalytic reforming conditions to obtain a catalytic reforming mixture; and the obtained catalytic reforming mixture is injected into the gas liquid Separation tank 6
  • the gas-liquid separation is carried out to remove the volatile component 7, and the reforming oil is obtained at the bottom of the gas-liquid separation tank; if necessary, a predetermined amount of hydrogen is injected into the reformed oil to be reformed by the mixing device 8, and reforming Producing oil mixture, and injecting the obtained hydrogen-reforming reforming oil into a hydrogenation reactor 9 (preferably a tubular reactor), and contacting the catalyst having catalytic hydrogenation under liquid phase hydrotreating conditions;
  • the hydrogenation product output from the hydrogenation reactor 9 enters the delightizing component column 10, the light component 12 is removed, and the light component oil is obtained at the bottom of the delighting component column 10
  • a plurality of hydrogenation reactors may be provided, and the plurality of hydrogenation reactors may be connected in series or in parallel.
  • the mixing device may be disposed at the inlet end of the first hydrogenation reactor along the flow direction of the oil produced by the reforming; or as shown in Fig. 6, in each of the hydrogenation reactors
  • a mixing device 8 is provided at the inlet end of the reactor 9.
  • only one mixing device may be provided, the reforming oil is mixed with hydrogen, and the obtained mixture is separately sent to a plurality of hydrogenation reactors connected in parallel;
  • a mixing device 8 is provided at the inlet end of each hydrogenation reactor 9 as indicated.
  • Figure 8 is a view for explaining a portion I in Figure 5, showing the structure of the mixing device 8 of Figure 5, and a mixing device
  • the mixing device 8 includes a gas passage 2 and a liquid passage 1, and the gas passage 2 and the liquid passage 1 are adjacent by a member 3, wherein the inner wall of the member 3 forms a liquid passage 1, and the outer wall of the member 3 is
  • the inner wall of the housing 22 constitutes a gas passage 2, the two ends of which are closed, and the housing 22 has an opening (not shown) communicating with a source of hydrogen gas.
  • the mixing device 8 is connected to the inlet line 18 of the tubular reactor 9.
  • the reformed produced oil enters the hydrogenation reactor 9 through the liquid passage 1, and when the reformed oil is produced through the liquid passage 1, the supplementary hydrogen in the gas passage 2 is injected into the reforming oil through the member 3. And dispersing and dissolving in the reforming oil; carrying hydrogen reforming to form an oil and then entering the hydrogenation reactor 9 to carry out a hydrogenation reaction in the presence of a catalyst having catalytic hydrogenation.
  • the mixing device 8 can be attached to the inlet line 18 in a variety of ways, for example: a flange can be provided at each end of the mixing device 8 (one of the flanges 16 is shown in Figure 8), each corresponding to The flange sealing connection on the inlet line (as shown in Figure 8, the flange 16 at one end of the mixing device is sealingly connected to the flange 17 on the inlet line 18); the other end of the inlet line 18 is flanged Disks 19 and 20 are connected to the inlet end 21 of the hydrogenation reactor 9.
  • the invention will be described in detail below with reference to examples and comparative examples.
  • the bromine index was determined by potentiometric titration in the following examples and comparative examples.
  • the average pore size was determined by scanning electron microscopy in the following examples and comparative examples.
  • Examples 1-6 are used to illustrate the reforming oil hydrotreating process according to the present invention.
  • the catalytic reforming mixture outputted from the reforming reactor is injected into a reforming product gas-liquid separation tank for gas-liquid separation, and reforming oil is obtained from the bottom of the separation tank.
  • the temperature in the separation tank was 40 ° C and the pressure was 0.7 MPa; based on the total amount of the reformed oil obtained, the reformed oil contained 0.015 wt% of dissolved hydrogen.
  • the hydrogen-reformed oil is sent to a tubular fixed-bed reactor through a pipe having an inner diameter of 40 mm (the inner diameter of the tubular reactor is 65 mm, the aspect ratio is 30; and the catalyst reactor is provided with a catalyst bed layer, The catalyst bed had an aspect ratio of 25) and was contacted with a catalyst having catalytic hydrogenation under the conditions shown in Table 1.
  • Table 1 The aromatic hydrocarbon content of the obtained hydrogenated product and the bromine index are shown in Table 2.
  • the mixing device comprises a pipe formed of a porous material (commercially available from Beijing Zhongtianyuan Environmental Engineering Co., Ltd., the outer diameter is 25.4 mm, the cross section of the pipe is as shown in Fig. 4, and 19 liquid channels are uniformly distributed, each liquid
  • the inner diameter of the channel is 3.3 mm
  • the average pore diameter of the pores in the tube wall is 50 nm
  • the pore diameter in the range of 50-55 nm accounts for 95% of the total pores
  • the porosity is 20%
  • the temperature is 160 ° C and the pressure is 1.8 MPa;
  • the catalyst used for catalytic hydrogenation is a catalyst commercially available from Sinopec Fushun Petrochemical Research Institute under the designation HDO-18.
  • the reforming oil was hydrotreated in the same manner as in Example 1, except that no hydrogen was introduced into the gas passage of the hydrogen mixing device (that is, no supplementary hydrogen was injected into the reforming oil).
  • the aromatics content of the hydrogenation product and the bromine index are shown in Table 2.
  • the reformed oil was hydrotreated in the same manner as in Example 1, except that:
  • the temperature in the gas-liquid separation tank is 40 ° C, and the pressure is 0.3 MPa, based on the total amount of the reformed oil obtained, the reformed oil contains 0.01% by weight of dissolved hydrogen;
  • the mixing device includes a membrane tube (commercially purchased from Beijing Zhongtianyuan Environmental Engineering Co., Ltd., the outer diameter is
  • the average pore diameter of the pores on the substrate is ⁇
  • the average pore diameter of the pores on the porous membrane is 250 nm
  • the pore diameter of the pores in the range of 250-260 nm accounts for 95% of the total pores
  • the porosity is 25%.
  • the temperature is 150 ° C and the pressure is 1.5 MPa; the chemical hydrogen consumption of 100 parts by weight of the feedstock oil is 0.03 parts by weight, and under the hydrorefining conditions shown in Table 1, the hydrogen is in the feedstock oil.
  • the saturated dissolved amount is 0.025% by weight; the hydrogen injection rate is 2180g_h- ⁇ m- 2 , the hydrogen injection rate (in g_h-m- 2 ) and the ratio of the feedstock oil flow rate (in kg ⁇ m- 2 )
  • the catalyst is commercially available from Sinopec Fushun Petrochemical Research Institute under the designation HDO-18.
  • the reformed oil was hydrotreated in the same manner as in Example 1, except that:
  • the mixing device comprises a membrane tube (commercially available from Beijing Zhongtianyuan Environmental Engineering Co., Ltd., the outer diameter is 25.4 mm, the average pore diameter of the pores on the substrate is ⁇ , and the average pore diameter of the pores on the porous membrane is 500 nm.
  • the cross section of the pipe is shown in Figure 4. There are 19 liquid channels evenly distributed, and the inner diameter of each liquid channel is 3.3mm.
  • the outer wall and shell of the membrane tube The space formed by the inner wall is a gas passage.
  • Example 6 The reformed oil was hydrotreated in the same manner as in Example 4 except that in the mixing apparatus, the pores on the tube wall of the pipe formed of the porous material had an average pore diameter of 5 ⁇ (commercially available from Beijing Zhongtianyuan). Environmental Engineering Co., Ltd.) The aromatic hydrocarbon content and bromine index of the obtained hydrogenated product are shown in Table 2.
  • Example 6 The aromatic hydrocarbon content and bromine index of the obtained hydrogenated product are shown in Table 2.
  • the reformed oil was hydrotreated in the same manner as in Example 4 except that the fixed bed reactor was a fixed bed reactor (having an inner diameter of 1600 mm, a catalyst bed in the reactor, and a catalyst).
  • the aspect ratio of the charge was 6.0), and the properties of the obtained hydrogenated product are shown in Table 2.
  • Example 2 show that the reformed produced oil can be hydrotreated efficiently by using the dissolved hydrogen in the reforming oil.

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Abstract

本发明提供了一种重整生成油加氢处理方法，该方法包括在液相加氢处理条件下，将重整生成油与具有催化加氢作用的催化剂在加氢反应器中进行接触，所述加氢处理中使用的氢气至少部分来自于所述重整生成油中的溶解氢。根据本发明的方法，将从重整产物分离罐中分离得到的重整生成油直接进行液相加氢处理，既充分利用了重整生成油中的溶解氢，又能够脱除重整生成油中的烯烃，同时还消除了对于循环氢及其循环设备的需求。由本发明的方法得到的重整生成油，溴指数能够为50mgBr2/100g以下，芳烃损失量能够为小于0.5重量%。

Description

一种重整生成油加氢处理方法
技术领域
本发明涉及一种重整生成油加氢处理方法。 背景技术
催化重整是石油炼制的主要过程之一， 是在一定温度、 压力、 临氢和催化剂存在 下， 使石脑油等原料油转变成富含芳烃的重整生成油， 并副产氢气的过程。 催化重整得 到的混合物经气液分离后得到的重整生成油可直接用作车用燃料的调和组分，也可再经 过一个芳烃抽提过程， 来生产苯、 甲苯和二甲苯等化工原料。
由于重整生成油不仅富含芳烃和溶剂油馏分， 而且还含有少量的烯烃。 因此， 重 整生成油要生产出合格的芳烃和溶剂油产品， 就必须脱除其中的烯烃。 并且， 近年来， 随着宽馏分重整技术的发展及反应苛刻度提高， 重整生成油中烯烃含量也相应增加， 因 此， 脱除重整生成油中烯烃的问题更加突出。
目前， 重整生成油脱除烯烃的方法主要有： 白土吸附精制、 重整生成油的馏分油 或全馏分后加氢。 其中， 白土吸附精制存在白土的吸附能力有限， 并且废白土无法再生 的弊端。 近年来， 开始采用 Pd或 Pt基贵金属催化剂对重整生成油的馏分油或全馏分进 行选择性加氢， 以脱除烯烃。
CN1004421B公开了一种重整生成油的加氢精制工艺， 该工艺采用溴价为 0.5-8克 溴 /100克， 芳烃含量为 35-55重量％的重整生成油作为原料， 反应温度为 200-300°C， 反 应氢分压为 5-20公斤 /平方厘米， 液体空速为 6-20小时— 氢 /油体积比为 200-1000， 采 用含 0.15-0.6重量％Pd (对载体） 的薄壳型条状 Pd-Al203催化剂。
CN1049001C公开了一种重整生成油加氢精制工艺， 该工艺采用溴价为 0.5-8.0克 溴 /10.0克的重整生成油为原料， 催化加氢剂为 Pd含量为 0.15-6重量％ (对载体） 的薄 壳 Ι /γ-Α1203， 其中， 原料已脱除大于 C9芳烃且芳烃含量为 20-85重量％， 反应温度为 150-200 °C ,反应器中氢分压为 0.5-3.0MPa，液体空速为 3-15h— 氢油体积比为 100-500。
CN1004421B和 CN1049001C公开的方法均采用的是滴流床加氢工艺，装置中需要 维持大量的循环氢， 一方面需要配备循环氢压縮机， 另一方面使得反应装置较为庞大。 发明内容
本发明的目的在于提供一种重整生成油加氢处理方法， 该方法采用液相加氢工艺， 一方面消除了对于循环氢的需求， 另一方面还能够充分利用重整生成油中的溶解氢。
本发明的发明人在实践过程中发现： 烃油在催化重整条件下与具有催化重整作用 的催化剂接触而得到的混合物在气液分离罐中进行气液分离，得到的重整生成油中仍然 溶解有催化重整过程中生成的氢气，如果将从所述气液分离罐的罐底得到重整生成油直 接进行液相加氢处理， 并将重整生成油中的溶解氢作为加氢处理的氢源或氢源之一， 一 方面可以充分利用重整生成油中残留的溶解氢来脱除重整生成油中的烯烃， 另一方面还 能够消除对于循环氢的需求。 在此基础上， 完成了本发明。
本发明提供了一种重整生成油加氢处理方法， 该方法包括： 在液相加氢处理条件 下， 将重整生成油与具有催化加氢作用的催化剂在加氢反应器中进行接触， 所述加氢处 理中使用的氢气至少部分来自于所述重整生成油中的溶解氢。
根据本发明的重整生成油加氢处理方法， 将从重整产物分离罐中分离得到的重整 生成油直接进行液相加氢处理， 既充分利用了重整生成油中的溶解氢， 又能够脱除重整 生成油中的烯烃， 同时还消除了对于循环氢及其循环设备的需求。 因此， 根据本发明的 重整生成油加氢处理方法简化了工艺流程路线， 降低了投资成本和操作费用， 实现了高 效低耗的工业生产。
并且， 根据本发明的重整生成油加氢处理方法得到的重整生成油， 溴指数能够为 50mgBr2/100g以下， 甚至可以为 10mgBr2/100g以下； 同时， 芳烃损失量小， 能够为小 于 0.5重量％。 附图说明
附图是用来提供对本发明的进一步理解， 并且构成说明书的一部分， 与下面的具 体实施方式一起用于解释本发明， 但并不构成对本发明的限制。 在附图中：
图 1 为根据本发明的重整生成油加氢处理方法中使用的混合装置的一种实施方式 的结构示意图；
图 2 为根据本发明的重整生成油加氢处理方法中使用的混合装置的另一种实施方 式的结构示意图；
图 3 为根据本发明的重整生成油加氢处理方法中使用的混合装置的一种优选的实 施方式的结构示意图； 图 4 为根据本发明的重整生成油加氢处理方法使用的混合装置中的具有有孔区的 构件的一种优选的实施方式的横截面示意图；
图 5为根据本发明的重整生成油加氢处理方法的一种优选的实施方式； 图 6用于说明根据本发明的重整生成油加氢处理方法中多个加氢反应器串联连接 的实施方式；
图 7用于说明根据本发明的重整生成油加氢处理方法中多个加氢反应器并联连接 的实施方式； 以及
图 8用于说明图 5中的部分 I。
具体实施方式
本发明提供了一种重整生成油加氢处理方法， 该方法包括： 在液相加氢处理条件 下， 将重整生成油与具有催化加氢作用的催化剂在加氢反应器中进行接触， 所述加氢处 理中使用的氢气至少部分来自于所述重整生成油中的溶解氢。
根据本发明的加氢处理方法， 所述重整生成油为将烃油与具有重整催化作用的催 化剂在催化重整条件下接触得到的催化重整混合物注入气液分离罐中，从所述气液分离 罐的罐底得到的重整生成油。 即， 根据本发明的加氢处理方法， 将烃油与具有催化重整 作用的催化剂在催化重整条件下进行接触而得到的混合物在气液分离罐中进行气液分 离， 从所述分离罐的罐底得到的重整生成油直接进行液相加氢处理。
根据本发明的加氢处理方法， 所述重整生成油含有催化重整过程中残留的氢气， 从重整反应器中输出的重整混合物进行气液分离后才能得到重整生成油， 因此重整生成 油中的氢气 （即， 催化重整过程中残留的氢气）基本以溶解氢的形式存在。 本文中， 重 整生成油中的溶解氢指催化重整过程中残留的氢气。所述重整生成油中的溶解氢的含量 随气液分离的条件以及重整生成油的组成而略有不同， 一般情况下， 以所述重整生成油 的总量为基准， 所述重整生成油中溶解氢的含量为 0.001-0.025重量％。
根据本发明的加氢处理方法， 在将所述重整生成油进行加氢处理时， 氢气的来源 可以仅为重整生成油本身含有的氢气，还可以为重整生成油本身含有的氢气以及向重整 生成油中补充的氢气。 即， 根据本发明的加氢处理方法， 所述加氢处理可以在不存在补 充氢气的条件下进行， 也可以在存在补充氢气的条件下进行。 所述补充氢气是指所述接 触前和 /或所述接触的过程中， 一次或分次注入所述重整生成油中的氢气。
根据本发明的加氢处理方法， 是否需要补充氢气以及补充氢气的量可以根据重整 生成油中溶解氢的含量以及重整生成油中烯烃的含量进行适当的选择。在所述重整生成 油中的溶解氢的量足以将重整生成油中的烯烃脱除至满足要求时，根据本发明的重整生 成油加氢处理方法优选不向重整生成油中补充氢气，仅将重整生成油含有的催化重整过 程中残留的溶解氢作为加氢处理的氢源。在所述重整生成油中的溶解氢的量无法将重整 生成油中的烯烃脱除至满足要求时，根据本发明的加氢处理方法优选在存在补充氢气的 情况下进行。
根据本发明的加氢处理方法， 在存在补充氢气的情况下， 所述补充氢气可以一次 注入所述重整生成油中， 例如： 可以在将重整生成油送入所述加氢反应器之前， 将所述 补充氢气注入所述重整生成油中； 所述补充氢气还可以分次注入所述重整生成油中， 例 如： 可以在加氢反应器上设置至少一个补充氢气入口， 部分所述补充氢气在所述加氢反 应器的入口端注入重整生成油中，剩余部分所述补充氢气在所述补充氢气入口处注入重 整生成油中。
根据本发明的加氢处理方法， 在存在补充氢气的情况下， 可以采用各种方法将氢 气注入重整生成油中。
在本发明的一种优选的实施方式中， 将所述补充氢气注入重整生成油中的方式包 括： 将所述补充氢气通过平均孔径为纳米尺寸的孔注入所述重整生成油中。 将补充氢气 通过平均孔径为纳米尺寸的孔注入重整生成油中， 能够将补充氢气高度分散且以更快的 速度溶解在重整生成油中，从而能够消除对于现有的烃油液相加氢处理工艺中旨在提高 氢气在原料油中的携带量的稀释剂或循环油的需求。
本发明中， 所述孔为通孔。 所述孔的平均孔径可以为 1纳米至 1000纳米， 优选为
30纳米至 1000纳米。 从进一步提高所述补充氢气在重整生成油中的分散程度以及溶解 速度的角度出发， 所述孔的平均孔径更优选为 30纳米至 800纳米， 进一步优选为 50纳 米至 500纳米。 所述平均孔径是采用扫描电镜法测定的。
可以将氢气注入为静止的重整生成油中， 也可以将氢气注入处于流动状态的重整 生成油中。优选将氢气注入处于流动状态的重整生成油中， 这样能够在输运重整生成油 的同时， 将氢气注入重整生成油中， 从而获得进一步提高的生产效率。 在将氢气注入处 于流动状态的重整生成油中时， 所述氢气的注入速度为 Vl并以 g_h- ^m- 2 (表示在单位时 间内，通过单位面积上孔的氢气的总量）计，所述重整生成油的流速为 v2并以 kg ^m- 2 (表示单位时间内通过单位截面的重整生成油的质量） 计， ¥ ^2=0.000625-0.09， 这样 能够获得进一步提高的氢气分散溶解效果。 优选地， Vl/v2=0.005-0.01， 这样不仅能够获 得好的氢气分散溶解效果， 而且能够获得较高的生产效率。
氢气注入重整生成油的速度一般可以为 0.0001-2000kg_h- ^m- 2。
根据本发明的加氢处理方法， 可以采用各种方法将所述补充氢气通过平均孔径为 纳米尺寸的孔而注入重整生成油中。优选地， 通过一种混合装置将所述补充氢气通过平 均孔径为纳米尺寸的孔而注入所述重整生成油中，所述混合装置包括至少一个用于容纳 重整生成油的液体通道和至少一个用于容纳所述补充氢气的气体通道，所述液体通道和 气体通道之间通过一构件邻接， 所述构件的至少部分为有孔区， 所述有孔区具有所述平 均孔径为纳米尺寸的孔， 所述补充氢气通过所述孔而被注入重整生成油中。
本发明中， 术语 "液体通道"是指能够容纳重整生成油的空间； 术语 "气体通道" 是指能够容纳所述补充氢气的空间。
根据本发明的加氢处理方法， 所述液体通道和所述气体通道之间的位置关系没有 特别限定， 只要所述液体通道与所述气体通道之间通过所述构件邻接即可。
在根据本发明的加氢处理方法使用的混合装置的一种实施方式中， 如图 1 所示， 气体通道 2位于液体通道 1之内， 构件 3的内壁构成所述气体通道 2。
在根据本发明的加氢处理方法使用的混合装置的另一种实施方式中， 如图 2所示， 气体通道 2位于液体通道 1的一侧， 且液体通道 1与气体通道 2通过构件 3而隔开。
在根据本发明的加氢处理方法使用的混合装置的一种优选的实施方式中， 如图 3 所示， 气体通道 2围绕在液体通道 1的外侧， 气体通道 2和液体通道 1之间通过构件 3 而隔开。
所述构件的至少部分为有孔区， 所述有孔区沿所述构件的长度方向延伸。 优选地， 所述有孔区覆盖整个构件（即， 所述液体通道和所述气体通道之间通过具有所述平均孔 径为纳米尺寸的孔的构件邻接， 所述补充氢气通过所述孔而被注入到所述重整生成油 中）。 所述有孔区具有所述平均孔径为纳米尺寸的孔， 以使氢气通过所述具有平均孔径 为纳米尺寸的孔被注入所述烃油中。 所述有孔区的孔隙率优选为 5-28%， 这样能够将足 量的氢气更好地分散并溶解在烃油中。 所述有孔区的孔隙率更优选为 10-25%。 所述孔 隙率是指有孔区中的孔隙体积占有孔区的总体积的百分数， 采用氮气吸附法方法测定。
根据本发明的加氢处理方法， 所述构件可以为各种能够使容纳于所述气体通道内 的补充氢气通过所述孔而进入容纳于所述液体通道内的所述重整生成油中，形成具有纳 米尺寸的气泡的构件。 优选地， 所述构件为管道。
在本发明的一种实施方式中， 所述构件由多孔材料形成， 所述构件中的孔的平均 孔径为纳米尺寸。
在本发明的另一种实施方式中， 所述构件包括基体以及附着在所述基体上的多孔 膜， 所述基体具有孔， 所述多孔膜可以位于所述基体的与容纳于所述液体通道内的重整 生成油接触的表面上，也可以位于所述基体的与容纳于所述气体通道内的补充氢气接触 的表面上。优选地， 所述多孔膜位于所述基体的与容纳于所述液体通道内的重整生成油 接触的表面上。所述多孔膜中的孔的平均孔径为纳米尺寸。 所述基体上的孔的平均孔径 没有特别限定， 只要能够通过气体即可。 优选地， 所述基体上的孔的平均孔径为微米尺 寸（即， 大于 1微米至 1000微米）或纳米尺寸（即， 1纳米至 1000纳米）， 即所述基体 上的孔的平均孔径为 1纳米至 1000微米。
在该实施方式中， 所述构件优选为膜管 （即， 将具有孔的多孔管道作为基体， 所 述多孔管道的内壁和 /或外壁上具有所述多孔膜）。 所述膜管可以为常见的各种无机膜管 (例如： 无机陶瓷膜管）或有机膜管， 只要形成所述膜管的材料不会与重整生成油和氢 气发生化学相互作用即可。
根据本发明， 所述构件可以采用常规方法制备， 也可以商购得到， 本文不再赘述。 根据本发明的加氢处理方法， 在所述构件为管道时， 所述管道可以与一壳体配合 使用。 即， 将所述管道置于一壳体中， 并使所述管道的外壁与所述壳体的内壁之间存在 空间。所述管道的内壁形成的空间为用于容纳重整生成油的所述液体通道， 所述管道的 外壁与所述壳体的内壁形成的空间为用于容纳补充氢气的所述气体通道； 或者， 所述管 道的内壁形成的空间为用于容纳补充氢气的所述气体通道，所述管道的外壁与所述壳体 的内壁形成的空间为用于容纳重整生成油的所述液体通道。优选地， 所述管道的内壁形 成的空间为用于容纳重整生成油的所述液体通道，所述管道的外壁与所述壳体的内壁形 成的空间为用于容纳补充氢气的所述气体通道。
在所述构件为膜管时， 优选将与所述膜管上的多孔膜接触的空间作为液体通道。 例如： 在所述多孔膜位于所述膜管的内壁上时， 所述膜管的内壁形成的空间作为用于容 纳重整生成油的所述液体通道，所述膜管的外壁与所述壳体的内壁形成的空间作为用于 容纳补充氢气的所述气体通道。
根据本发明， 所述构件为管道时， 所述管道可以具有一个所述液体通道， 也可以 具有多个所述液体通道。 从进一步提高根据本发明的方法的效率 （即， 在相同的时间内 将更大量的补充氢气分散溶解于重整生成油中） 的角度出发， 如图 4 (为所述管道的横 截面的示意图）所示， 所述管道 4具有多个（例如 4-20个）相互平行的液体通道 1。 在 所述液体通道为多个时， 该多个液体通道优选均匀分布。
在该优选的实施方式中， 所述壳体可以为各种具有中空结构和至少一个开口的构 件， 所述开口与补充氢气的气源或重整生成油储罐连通， 以将补充氢气或重整生成油导 入所述壳体的内壁与所述管道的外壁之间的空间 （即， 所述气体通道或所述液体通道） 中。
根据本发明的加氢处理方法， 所述补充氢气的量可以根据氢气在所述重整生成油 中的饱和溶解量以及重整生成油的化学氢耗量进行适当的选择， 以能够使得加氢产物能 够满足使用要求为准。
根据本发明的加氢处理方法， 在将补充氢气通过所述平均孔径为纳米尺寸的孔注 入重整生成油中时， 能够将氢气高度分散且以更快的速度溶解于重整生成油中。 因此， 根据本发明的加氢处理方法即使不向重整生成油中大量注入氢气，也能确保重整生成油 的氢气携带量。 一般地， 根据本发明的加氢处理方法， 所述补充氢气的量可以为在所述 液相加氢处理条件下， 氢气在所述重整生成油中的饱和溶解量的 0.01-4倍， 优选为所述 饱和溶解量的 0.01-2倍， 更优选为所述饱和溶解量的 0.1倍至 1倍， 进一步优选为所述 饱和溶解量的 0.1倍至小于 1倍。 所述饱和溶解量是指在液相加氢处理条件下， 溶解于 100克重整生成油中的氢气的克数。 可以采用本领域常用的各种方法来确定氢气在重整 生成油中的饱和溶解量， 本文不再赘述。
根据本发明的加氢处理方法， 向重整生成油中注入补充氢气的条件没有特别限定， 可以为本领域的常规选择。 一般地， 可以在加氢处理的温度和压力下， 向重整生成油中 注入补充氢气。
根据本发明的加氢处理方法， 重整生成油与具有催化加氢作用的催化剂的接触可 以在本领域常用的各种加氢反应器中进行，没有特别限定。根据本发明的加氢处理方法， 所述接触可以在釜式反应器中进行， 也可以在管式反应器中进行。 优选地， 所述接触在 管式反应器中进行。
本发明中， 所述管式反应器是指具有较大的长径比的反应器， 例如； 管式反应器 的长度与内径的比值可以为 5-50: 1。 根据本发明， 所述管式反应器的内径可以为本领 域的常规选择， 优选地， 所述管式反应器的内径为 20-1000mm。
在所述接触在管式反应器中进行时， 氢气优选通过上文所述的混合装置而被注入 重整生成油中。 此时， 所述混合装置的数量可以为一个， 也可以为多个。
在所述混合装置的数量为一个时， 该混合装置优选设置在所述管式反应器的入口 端， 在将重整生成油注入管式反应器的过程中， 通过所述混合装置将氢气注入重整生成 油中。 可以采用本领域常用的各种方法将所述混合装置设置在所述管式反应器的入口 端， 只要使重整生成油能够通过所述混合装置的液体通道， 并通过所述构件将气体通道 内的补充氢气注入重整生成油中即可。
根据本发明的方法， 在采用前文所述的混合装置将氢气注入重整生成油， 以得到 含有氢气的重整生成油， 并将含有氢气的重整生成油送入反应器时， 所述混合装置上用 于输出添加了氢气的重整生成油的出口 0的内径为 ri，所述反应器上用于输入重整生成 油的入口 I的内径为 r2， n/r2=0.6- l o 连接所述出口 0和所述入口 I的管的内径为 r3， Γι/ι·3=0.85-1.5。 这样含有氢气的重整生成油在输运过程中更为稳定， 从而能够获得更好 的加氢效果。
根据本发明的方法， 除在所述管式反应器的入口端设置至少一个所述混合装置外， 优选在所述管式反应器上设置至少一个所述混合装置， 这样能够在加氢处理过程中， 根 据重整生成油的化学氢耗量以及重整生成油中氢气的含量，分批向重整生成油中注入补 充氢气， 以进一步提高根据本发明的加氢处理方法的效率。
可以采用各种方式将所述混合装置设置在所述管式反应器上， 例如可以采用图 1 所述的方式： 将管式反应器的内壁形成的空间作为液体通道， 并在管式反应器的管壁上 设置开口； 将具有平均孔径为纳米尺寸的构件形成为一端密封的管道， 该管道的内壁形 成的空间作为气体通道； 将该管道通过所述开口伸入管式反应器内 （其中， 该管道的外 壁与所述开口密封连接）， 且该管道位于所述管式反应器内的一端为密封端， 该管道的 另一端与补充氢气气源连通， 从而将补充氢气通过该管道注入管式反应器内。
根据本发明的加氢处理方法的一种优选的实施方式， 所述加氢处理在管式反应器 中进行， 且所述混合装置优选包括： 作为所述构件的管道、 以及与所述管道配合使用的 壳体， 其中， 所述管道的内壁形成的空间作为液体通道， 所述管道的外壁与所述壳体的 内壁形成的空间作为气体通道，所述液体通道与所述管式反应器的用于进行加氢处理的 空间连通。
根据本发明的加氢处理方法， 所述加氢反应器的数量可以为一个， 也可以为多个 (即， 两个或两个以上）。 在所述加氢反应器的数量为多个时， 多个加氢反应器之间可 以为串联， 也可以为并联。 在所述加氢反应器为多个时， 优选在每个加氢反应器的入口 端将所述补充氢气送入重整生成油中 （例如： 在每个加氢反应器的入口端设置一个前文 所述的混合装置， 将所述补充氢气送入重整生成油中）。 根据本发明的加氢处理方法， 所述具有催化加氢作用的催化剂可以以各种形式存 在。 优选地， 所述加氢反应器为固定床反应器。 在所述加氢反应器为固定床反应器时， 所述催化剂床层的数量可以为本领域的常规选择， 例如： 所述催化剂床层的数量可以为 一个， 也可以为两个或两个以上。 根据本发明的加氢处理方法， 所述加氢处理在固定床 反应器中进行时， 所述重整生成油的体积空速可以为 5-20h- 优选为 10-20 11人
在本发明的一种优选的实施方式中， 所述加氢处理在管式固定床加氢反应器中进 行。
根据本发明的加氢处理方法是通过利用重整生成油中含有的催化重整过程中残留 的溶解氢来实现本发明的目的的， 对于所述液相加氢处理条件没有特别限定， 可以为本 领域的常规选择。 一般地， 所述液相加氢处理条件包括： 温度可以为 130-200°C， 优选 为 140-160°C ; 以表压计， 压力可以为 1.5-3.5MPa， 优选为 1.5-2MPa。
根据本发明的重整生成油加氢处理方法， 所述具有催化加氢作用的催化剂可以为 本领域常用的各种具有催化加氢作用的催化剂， 本文不再赘述。
根据本发明的加氢处理方法， 还包括： 脱出所述接触 （即， 加氢处理） 得到的产 物中的轻组分， 以除去经过加氢处理得到的产物中含有的催化重整过程以及加氢处理过 程中生成的轻组分 （例如： C5以下组分）。 根据本发明的加氢处理方法对于脱出轻组分 的方法没有特别限定，可以采用本领域的常规方法，一般地，可以将加氢产物进行加热， 从而将加氢产物中的轻组分脱出。
根据本发明的加氢处理方法， 在通过将加氢产物进行加热， 从而将加氢产物中的 轻组分脱出时， 根据本发明的加氢处理方法还包括脱出所述接触得到的产物中的轻组 分， 得到脱轻组分油， 并在将重整生成油送入加氢反应器中进行所述加氢处理前， 将所 述重整生成油与脱轻组分油进行热交换。 这样能够充分利用脱轻组分油中的余热， 将重 整生成油预热， 从而能够省去对重整生成油预热炉的需求， 能够进一步降低根据本发明 的加氢处理方法的设备投资成本和能耗。
根据本发明的加氢处理方法得到的加氢产物主要用于制备各种芳烃组分时， 根据 本发明的加氢处理方法还可以包括脱出脱轻组分油中的重组分， 得到芳烃抽提原料。 可 以采用本领域常用的方法脱除脱轻组分油中的重组分， 本文不再赘述。
图 5 为根据本发明的重整生成油加氢处理方法的一种优选的实施方式。 根据该优 选的实施方式，烃油在催化重整反应器 5中与具有重整催化作用的催化剂在催化重整条 件下进行接触， 得到催化重整混合物； 将得到的催化重整混合物注入气液分离罐 6中进 行气液分离， 脱出挥发性成分 7， 在气液分离罐的罐底得到重整生成油； 在需要时， 通 过混合装置 8将预定量的氢气注入得到的重整生成油中， 与重整生成油混合， 并将得到 的携氢重整生成油注入加氢反应器 9 (优选为管式反应器） 中， 与具有催化加氢作用的 催化剂在液相加氢处理条件下进行接触； 从加氢反应器 9中输出的加氢产物进入脱轻组 分塔 10中， 脱出轻组分 12， 在脱轻组分塔 10的塔底得到脱轻组分油； 得到的脱轻组分 油在换热器 11 中与注入混合装置前的重整生成油进行换热； 换热后的脱轻组分油注入 脱重塔 13中进行分离，在脱重塔 13的塔底得到重组分 15，塔顶得到用于芳烃抽提的原 料 14。
根据该实施方式， 可以设置多个加氢反应器， 多个加氢反应器之间可以为串联连 接， 也可以为并联连接。 在多个加氢反应器串联连接时， 沿重整生成油的流动方向， 可 以将混合装置设置在第一个加氢反应器的入口端； 也可以如图 6所示， 在每个加氢反应 器 9的入口端设置一个混合装置 8。 在多个加氢反应器并联连接时， 可以仅设置一个混 合装置， 将重整生成油与氢气混合， 然后将得到的混合物分别送入并联连接的多个加氢 反应器中； 也可以如图 Ί所示在每个加氢反应器 9的入口端设置一个混合装置 8。
图 8用于说明图 5中的部分 I， 示出了图 5中的混合装置 8的结构， 以及混合装置
8与加氢反应器 9之间的连接方式。
如图 8所示， 所述混合装置 8包括气体通道 2与液体通道 1， 气体通道 2与液体通 道 1之间通过构件 3邻接， 其中， 构件 3的内壁形成液体通道 1， 构件 3的外壁与壳体 22的内壁构成气体通道 2， 气体通道 2的两端封闭， 壳体 22上具有与氢气气源连通的 开口 （未示出）。 该混合装置 8连接在管式反应器 9的入口管路上 18。 实际操作时， 重 整生成油通过液体通道 1而进入加氢反应器 9中， 在重整生成油通过液体通道 1时， 将 气体通道 2内的补充氢气通过构件 3而注入重整生成油中，进而分散溶解在重整生成油 中； 携氢重整生成油随后进入加氢反应器 9中在具有催化加氢作用的催化剂的存在下进 行加氢反应。
可以采用各种方式将混合装置 8连接在入口管路 18上， 例如： 可以在混合装置 8 的两端各设置一个法兰盘 （图 8示出了其中一个法兰盘 16)， 各自与相应的入口管路上 的法兰盘密封连接（如图 8所示， 混合装置一端的法兰盘 16与入口管路 18上的法兰盘 17密封连接）； 入口管路 18的另一端通过法兰盘 19和 20与加氢反应器 9的入口端 21 相连。
以下结合实施例和对比例详细说明本发明。 以下实施例和对比例中 采用电位滴定法测定溴指数。
以下实施例和对比例中 采用气相色谱法测定芳烃含量
以下实施例和对比例中 采用扫描电镜法测定平均孔径
以下实施例和对比例中 压力均以表压计。 实施例 1-6用来说明根据本发明的重整生成油加氢处理方法。
实施例 1
( 1 ) 如图 5所示， 将重整反应器中输出的催化重整混合物注入重整产物气液分离 罐中进行气液分离， 从分离罐的罐底得到重整生成油。 其中， 分离罐中的温度为 40°C， 压力为 0.7MPa; 以得到的重整生成油的总量为基准， 该重整生成油含有 0.015重量％的 溶解氢。
(2) 通过混合装置向作为原料油的重整生成油中注入补充氢气 （100重量份原料 油的化学氢耗量为 0.03重量份，在表 1所示的加氢精制条件下，氢气在原料油中的饱和 溶解量为 0.025重量％)。氢气的注入速度为 2435g_h- ^m- 2， 氢气的注入速度（以 ^m- 2 计） 与原料油的流速 （以 kg ^m- 2计） 的比值为 0.006。 将携氢重整生成油通过内径为 40mm的管道送入管式固定床反应器 （管式反应器的内径为 65mm， 长径比为 30; 管式 反应器中设置有 1个催化剂床层， 催化剂床层的高径比为 25 )中， 在表 1所示的条件下 与具有催化加氢作用的催化剂接触。得到的加氢产物的芳烃含量以及溴指数在表 2中示 出。
其中， 混合装置包括由多孔材料形成的管道 （商购自北京中天元环境工程有限公 司， 外径为 25.4mm， 管道的横截面如图 4所示， 均匀分布有 19个液体通道， 每个液体 通道的内径为 3.3mm， 管壁上的孔的平均孔径为 50nm， 孔径处于 50-55nm范围内的孔 的占总孔的比例为 95%， 孔隙率为 20% ) 和与该管道配合使用的一个壳体 （内径为 40mm), 管道的外壁与壳体的内壁形成的空间为气体通道； 混合装置上用输出含有氢气 的烃油的出口的内径为 40mm;
混合装置的液体通道中， 温度为 160°C， 压力为 1.8MPa; 采用的具有催化加氢作 用的催化剂为商购自中石化抚顺石油化工研究院的牌号为 HDO-18的催化剂。
( 3 )将得到的加氢产物注入脱轻组分塔中，脱除加氢处理得到的混合物中 C5以下 组分， 得到脱轻组分油在换热器中与重整生成油进行换热之后， 注入脱重塔中脱除 C8 以上组分， 在塔顶得到用于芳烃抽提的原料。 实施例 2
采用与实施例 1 相同的方法对重整生成油进行加氢处理， 不同的是， 氢气混合装 置的气体通道中没有通入氢气 （即， 不向重整生成油中注入补充氢气）， 得到的加氢产 物的芳烃含量以及溴指数在表 2中示出。 实施例 3
采用与实施例 1相同的方法对重整生成油进行加氢处理， 不同的是：
步骤 （1 ) 中， 气液分离罐中的温度为 40°C， 压力为 0.3MPa， 以得到的重整生成 油的总量为基准， 该重整生成油含有 0.01重量％的溶解氢；
步骤 （2) 中， 混合装置包括膜管 （商购自北京中天元环境工程有限公司， 外径为
25.4mm, 基体上的孔的平均孔径为 ΙΟΟμηι, 多孔膜上的孔的平均孔径为 250nm， 孔径 处于 250-260nm范围内的孔的占总孔的比例为 95%，孔隙率为 25%)和与该管道配合使 用的一个壳体 （内径为 40mm) ; 多孔膜位于膜管的外壁上； 膜管的横截面如图 4所示， 均匀分布有 7个液体通道， 每个液体通道的内径为 6mm; 膜管的外壁与壳体的内壁形 成的空间为气体通道；
混合装置的液体通道中， 温度为 150°C， 压力为 1.5MPa; 100重量份原料油的化学 氢耗量为 0.03重量份，在表 1所示的加氢精制条件下，氢气在原料油中的饱和溶解量为 0.025重量％; 氢气的注入速度为 2180g_h- ^m- 2， 氢气的注入速度 （以 g_h- m- 2计） 与原 料油的流速 （以 kg ^m- 2计） 的比值为 0.007; 催化剂为商购自中石化抚顺石油化工研 究院的牌号为 HDO-18的催化剂。
在表 1 列出的条件下进行加氢处理得到的加氢产物的芳烃含量以及溴指数在表 2 中示出。 实施例 4
采用与实施例 1相同的方法对重整生成油进行加氢处理， 不同的是：
步骤 （2) 中， 混合装置包括膜管 （商购自北京中天元环境工程有限责任公司， 外 径为 25.4mm， 基体上的孔的平均孔径为 ΙΟΟμηι, 多孔膜上的孔的平均孔径为 500nm， 孔径处于 500-550nm范围内的孔的占总孔的比例为 95%，孔隙率为 25%)和与该管道配 合使用的一个壳体 （内径为 40mm); 多孔膜位于膜管的内壁上， 管道的横截面如图 4 所示， 均匀分布有 19个液体通道， 每个液体通道的内径为 3.3mm; 膜管的外壁与壳体 的内壁形成的空间为气体通道。
在表 1 列出的条件下进行加氢处理得到的加氢产物的芳烃含量以及溴指数在表 2 中示出。 实施例 5
采用与实施例 4相同的方法对重整生成油进行加氢处理， 不同的是， 混合装置中， 由多孔材料形成的管道的管壁上的孔的平均孔径为 5μηι (商购自北京中天元环境工程有 限责任公司）， 得到的加氢产物的芳烃含量以及溴指数在表 2中示出。 实施例 6
采用与实施例 4相同的方法对重整生成油进行加氢处理， 不同的是， 固定床反应 器为釜式固定床反应器 （内径为 1600mm， 反应器中设置有 1个催化剂床层， 催化剂装 填的高径比为 6.0)， 得到的加氢产物的性质在表 2中示出。 表 1
Figure imgf000015_0001
表 2
Figure imgf000015_0002
实施例 2 的结果表明， 利用重整生成油中的溶解氢能够有效地对重整生成油进行 加氢处理。
实施例 4和 5的结果表明， 在注入的补充氢气的量相同的条件下， 将补充氢气通 过平均孔径为纳米尺寸的孔注入重整生成油中， 能够将补充氢气高度分散且以更快的速 度溶解在重整生成油中， 进而能够获得更好的加氢处理效果。 以上详细描述了本发明的优选实施方式， 但是， 本发明并不限于上述实施方式中 的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型， 这些简单变型均属于本发明的保护范围。
此外， 本发明的各种不同的实施方式之间也可以进行任意组合， 只要其不违背本 发明的思想， 其同样应当视为本发明所公开的内容。

Claims

权利要求
1、 一种重整生成油加氢处理方法， 该方法包括： 在液相加氢处理条件下， 将重整 生成油与具有催化加氢作用的催化剂在加氢反应器中进行接触， 所述加氢处理中使用的 氢气至少部分来自于所述重整生成油中的溶解氢。
2、 根据权利要求 1 所述的方法， 其中， 所述加氢处理在存在补充氢气的条件下进 行， 所述补充氢气为所述接触前和 /或所述接触的过程中， 一次或分次注入所述重整生成 油中的氢气。
3、 根据权利要求 2所述的方法， 其中， 将所述补充氢气注入重整生成油中的方式 包括： 将所述补充氢气通过平均孔径为纳米尺寸的孔注入所述重整生成油中。
4、 根据权利要求 3所述的方法， 其中， 在一种混合装置中将所述补充氢气通过所 述平均孔径为纳米尺寸的孔注入所述重整生成油中， 该混合装置包括至少一个用于容纳 所述重整生成油的液体通道和至少一个用于容纳所述补充氢气的气体通道， 所述液体通 道和所述气体通道之间通过一构件邻接， 所述构件的至少部分为有孔区， 所述有孔区具 有所述平均孔径为纳米尺寸的孔， 所述补充氢气通过所述孔而被注入到所述重整生成油 中。
5、 根据权利要求 3或 4所述的方法， 其中， 所述孔的平均孔径为 30-1000nm。
6、根据权利要求 2-4中任意一项所述的方法， 其中， 所述补充氢气的量为在所述液 相加氢处理条件下， 氢气在所述重整生成油中的饱和溶解量的 0.01-4倍。
7、根据权利要求 6所述的方法，其中，所述补充氢气的量为所述饱和溶解量的 0.01-2 倍。
8、 根据权利要求 7所述的方法， 其中， 所述补充氢气的量为所述饱和溶解量的 0.1 倍至小于 1倍。
9、 根据权利要求 1 所述的方法， 其中， 该方法还包括： 脱除所述接触得到的产物 中的轻组分， 得到脱轻组分油， 并将所述重整生成油与脱轻组分油进行热交换后送入所 述加氢反应器中。
10、 根据权利要求 1或 9所述的方法， 其中， 所述加氢反应器为管式反应器。
11、 根据权利要求 10所述的方法， 其中， 所述加氢反应器为管式固定床加氢反应 器。
12、 根据权利要求 11所述的方法， 其中， 所述重整生成油的体积空速为 5-20h-
13、 根据权利要求 1-4和 9中任意一项所述的方法， 其中， 所述重整生成油为将烃 油与具有重整催化作用的催化剂在催化重整条件下接触得到的催化重整混合物注入气液 分离罐中， 从所述气液分离罐的罐底得到的重整生成油。
14、根据权利要求 1所述的方法，其中，所述液相加氢处理条件包括：温度为 130-200 °C ; 以表压计， 压力为 1.5-3.5MPa。
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