CN112705122A - Liquid phase hydrogenation reactor and hydrogenation method - Google Patents
Liquid phase hydrogenation reactor and hydrogenation method Download PDFInfo
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- CN112705122A CN112705122A CN201911020905.4A CN201911020905A CN112705122A CN 112705122 A CN112705122 A CN 112705122A CN 201911020905 A CN201911020905 A CN 201911020905A CN 112705122 A CN112705122 A CN 112705122A
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- 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
-
- 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
-
- 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
- B01J8/0496—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- 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
- B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
- B01J2208/023—Details
- B01J2208/024—Particulate material
- B01J2208/025—Two or more types of catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a liquid phase hydrogenation reactor and a hydrogenation method. The liquid phase hydrogenation reactor comprises an inner cylinder and a reactor shell, wherein the inner cylinder is conical, an annular cavity is formed between the inner cylinder and the reactor shell, and the cross section area of the annular cavity is gradually increased from bottom to top; the top of the inner cylinder penetrates through the upper end enclosure and is communicated with a raw material inlet at the top of the reactor, and the bottom of the inner cylinder is communicated with the bottom of the annular cavity; a ceramic membrane nano/micron component is horizontally arranged in the middle of the reactor and is communicated with external hydrogen; the inner cylinder is filled with a hydrogenation catalyst I, the annular cavity is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is lower than that of the hydrogenation catalyst II; the flowing mode of the materials in the inner cylinder is from top to bottom; the material flows from bottom to top in the annular cavity. The method can effectively control the initial activity of the liquid phase hydrogenation reaction and improve the conversion rate in the later reaction period through the internal structure of the reactor, the material flow mode and the catalyst gradation.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a liquid-phase hydrogenation reactor and a hydrogenation method.
Background
The liquid phase hydrogenation technology is a novel hydrogenation technology, hydrogen is dissolved in raw oil in advance, hydrogen required by hydrogenation reaction is met through liquid phase large-amount circulation, the influence of hydrogen diffusion mass transfer in conventional trickle bed hydrogenation reaction is overcome, and the hydrogenation reaction is carried out in a dynamics control area, so that compared with the traditional fixed bed gas/liquid/solid three-phase hydrogenation technology, the liquid phase hydrogenation technology has the advantages of high hydrogenation reaction rate, high reaction efficiency, low energy consumption, low investment and the like, and is widely accepted and applied. The liquid phase hydrogenation reactor is mainly divided into an up-flow fixed bed hydrogenation reactor and a down-flow fixed bed hydrogenation reactor, wherein the down-flow fixed bed reactor can effectively reduce the coking of the catalyst on the surface of the catalyst and can take away the heat in time due to the fact that the reaction materials can react on the surface of the catalyst and leave quickly, and therefore the application is common. However, the following problems still exist in the conventional downflow liquid phase hydrogenation reactor and reaction process: (1) the reactant concentration in the fresh material at the early stage of the reaction is high, the hydrogen content is high, the driving force in the reaction process is large, the initial activity of the catalyst is also high, and the material and the catalyst are in full contact in the liquid phase hydrogenation process, so that the problems of violent reaction heat release, large temperature rise and difficulty in controlling the process exist; (2) in the later stage of the reaction, due to high reaction temperature, if the hydrogenation reaction still occurs on the high-activity catalyst, the problems of high reaction rate and serious side reaction and cracking reaction are caused; (3) because the reaction later stage is still the liquid phase hydrogenation reaction process, the gas product generated by the reaction is still dissolved in the liquid material, namely the gas product is difficult to separate in the liquid phase hydrogenation reaction process by adopting the steam stripping mode of a conventional reactor, a larger steam stripping surface area is needed, and if the gas generated by the reaction is not removed by the steam stripping in time, the reaction conversion rate in the reaction later stage can be reduced, so that the ideal hydrogenation reaction depth can not be achieved; (4) along with the flowing of materials in the hydrogenation reactor and the consumption of hydrogen in the reaction process, the dissolving and dispersing state of hydrogen in oil products is gradually changed, so that hydrogen bubbles dissolved around oil product molecules are reacted, and the unreacted bubbles are gradually agglomerated into large bubbles, so that the oil products can not continuously provide hydrogen in the hydrogenation reaction process, and side reactions or cracking reactions can also be increased. Therefore, for the conventional downflow liquid phase hydrogenation reaction process, effective means such as development of a new hydrogenation method and a new reactor form and control of the activity of reaction materials and the contact mode of the materials and the catalyst are adopted, so that the problems of concentrated heat release at the early stage of the reaction and low reaction conversion rate at the later stage can be controlled, the hydrogenation reaction rate and the reaction depth can be ensured, and the method has important significance.
CN203389622U proposes a liquid phase hydrogenation reactor, which comprises at least one liquid phase enhanced reactor, a static mixer disposed outside the liquid phase enhanced reactor, and a hydrogen gas supplementing device. The object of this patent is to improve the existing method of arranging internals of complex structure in a reactor to the use of static mixers and to arrange the static mixers outside the reactor.
CN203389623U proposes a liquid phase hydrogenation reaction system, which includes a raw oil buffer tank, a reaction feed heating furnace, a gas-liquid mixer, a liquid phase hydrogenation reactor, a pressure reduction device and a low-pressure separator, wherein an outlet of the liquid phase hydrogenation reactor is connected to the low-pressure separator through the pressure reduction device, so as to flash-vaporize most hydrogen sulfide and ammonia in a reaction product.
CN105713659A proposes a continuous liquid phase hydrogenation process for hydrocarbons, in which hydrocarbon raw materials and hydrogen are fully mixed by a gas-liquid mixer to form a liquid phase material flow saturated with dissolved hydrogen, hydrogen is injected into a hydrogen distributor at the lower part of each stage of catalyst from top to bottom in a reactor containing at least two stages of catalysts, and the product is led out from the reactor for subsequent treatment. The aim of the method is to reduce the amount of fresh hydrogen in the catalyst bed, i.e. to increase the reaction efficiency.
In summary, most of the ideas of the liquid phase hydrogenation reactor in the prior art are to dissolve hydrogen by a hydrogen dissolving method or a hydrogen dissolving component, to improve the reaction efficiency by a hydrogen supplementing method, and to flash-evaporate the reaction product to the outside stripping facility to obtain hydrogen sulfide and ammonia, which are gases generated by the reaction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a liquid phase hydrogenation reactor and a hydrogenation method, which effectively control the initial activity of a catalyst in the early stage of hydrogenation reaction, improve the reaction conversion rate in the later stage of reaction, solve the problems of violent heat release in the early stage of reaction and reaction product inhibition reaction conversion rate in the later stage of reaction, and simultaneously realize higher hydrogenation reaction rate and reaction conversion rate in the early stage and the later stage of reaction through the internal structure of the reactor, the material flow mode and the catalyst grading method. The terms "upper" and "lower" in the present invention refer to the axial direction of the reactor.
The liquid phase hydrogenation reactor comprises an inner cylinder and a reactor shell, wherein the top of the reactor shell is an upper end enclosure, the bottom of the reactor shell is a lower end enclosure, the inner cylinder is conical, an annular cavity is formed between the inner cylinder and the reactor shell, and the cross section area of the annular cavity is gradually increased from bottom to top; the top of the inner cylinder penetrates through the upper end enclosure and is communicated with a raw material inlet at the top of the reactor, a catalyst support is arranged below the bottom of the inner cylinder, and the bottom of the inner cylinder is communicated with the bottom of the annular cavity; a ceramic membrane nano/micron component is horizontally arranged in the middle of the reactor, penetrates through the cross section where the annular cavity and the inner cylinder are located, and is communicated with external hydrogen; the upper part of the annular cavity is provided with a product outlet; the inner cylinder is filled with a hydrogenation catalyst I, the annular cavity is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is lower than that of the hydrogenation catalyst II; the flowing mode of the materials in the inner cylinder is from top to bottom; the material flows from bottom to top in the annular cavity.
In the liquid phase hydrogenation reactor, the cone is actually a truncated cone, the upper end surface and the lower end surface of the cone inner cylinder are respectively positioned at the upper end socket and the lower end socket of the reactor, and the top of the inner cylinder is not communicated with the annular cavity; the ratio of the upper end surface to the lower end surface of the conical inner cylinder is 1: 1.05-1: 30, preferably 1: 1.5-1: 15, and the ratio of the lower end surface to the reactor is 1: 1.01-1: 20, preferably 1: 1.05-1: 10. According to the hydrogenation reaction system, the conical inner cylinder part of the hydrogenation reactor is gradually increased in cross sectional area along the material flowing direction, so that the material is gradually contacted with the catalyst in a progressive manner, a local hot point caused by a violent reaction when the concentration of the hydrogenation raw material is higher in the early stage of the reaction is prevented, the reaction rate can be ensured, and the activity in the early stage of the reaction can be effectively controlled; the annular cavity part is also gradually increased in cross section area along the material flowing direction, the materials are gradually contacted with the catalyst in a progressive mode, reactants and reaction gases in products in the later stage of reaction are stripped out in a mode of gradually increasing the stripping surface area and improving the stripping effect while the reaction rate of the high-temperature area is controlled, and the reaction rate and the conversion rate in the later stage of reaction are improved.
In the liquid phase hydrogenation reactor, the ceramic membrane nano/micron component is of an integrated tube shell structure and generally comprises a plurality of ceramic membrane tubes and a shell, wherein the ceramic membrane tubes are perpendicular to the cross section of the reactor; the ceramic membrane nano/micron component of the inner cylinder part is characterized in that a membrane tube is communicated with materials flowing upwards in the inner cylinder, and a cavity outside the membrane tube is communicated with an external hydrogen pipeline; the ceramic membrane nano/micron component is arranged at the annular cavity part, the membrane tube is communicated with an external hydrogen pipeline, and the cavity at the outer side of the membrane tube is communicated with materials flowing downwards in the annular cavity; the size of the nano/micron bubbles which can be formed by the ceramic membrane nano/micron component is generally 10-1000 nm, and preferably 50-500 nm.
In the liquid phase hydrogenation reactor, the ceramic membrane nano/micron component at the inner cylinder part and the ceramic membrane nano/micron component positioned in the inner cylinder mainly have the functions of hydrogen supplement and hydrogen re-dissolution, so that the driving force of the hydrogenation reaction process at low and medium temperature sections is enhanced to maintain higher reaction rate; the ceramic membrane nano/micron component with the annular cavity has the main functions of hydrogen supplement and steam stripping, and the material is subjected to steam stripping through the outer diffusion of hydrogen, so that hydrogen can be supplemented in the last stage of reaction, the surface coking of the catalyst in the high-temperature stage in the last stage is inhibited, and simultaneously a surface coking precursor and the generated gas of the reactor are inhibited to be timely stripped and separated, and the enhanced reaction depth is improved. The ceramic membrane nano/micron modules can be arranged in one or more groups along the radial direction of the reactor.
In the liquid phase hydrogenation reactor, the top of the reactor is provided with a gas space, and the highest point of a head at the top of the reactor is provided with a gas outlet for continuously or discontinuously discharging reaction gas extracted in the reaction process.
In the liquid phase hydrogenation reactor, the upper part of the reactor discharges materials through the liquid level control annular cavity, so that the hydrogenation reaction process is ensured to be full liquid phase hydrogenation.
The liquid phase hydrogenation method comprises the following steps: the raw material containing hydrogen enters a conical inner cylinder of the hydrogenation reactor through a feed inlet at the top of the reactor, is subjected to hydrogenation reaction with a hydrogenation catalyst I filled in the inner cylinder, is subjected to hydrogen supplementation and hydrogen re-dissolution through a ceramic membrane nano/micron component, flows out of the bottom of the inner cylinder, passes through the bottom of the reactor, enters an annular cavity from bottom to top, is subjected to further hydrogenation reaction with a hydrogenation catalyst II filled in the annular cavity, flows are subjected to hydrogen supplementation and steam stripping through the ceramic membrane nano/micron component, and the final reaction product is discharged from a discharge outlet at the upper part of the reactor.
In the method, the raw material containing hydrogen is generally obtained by mixing through hydrogen-oil mixing equipment, such as equipment with a gas-liquid mixing function, including a static mixer, a dissolved air pump, a colloid mill, a microporous plate nano/micron hydrogen dispersion component, a ceramic membrane nano/micron hydrogen dispersion component and the like; the hydrogen content of the hydrogen-containing feedstock is generally from 0.01wt% to 20wt%, preferably from 0.05wt% to 3.0wt%, based on the weight of the heavy oil feedstock.
In the method, the hydrogen supplement amounts of the inner cylinder and the annular cavity are adjusted according to the needs of the reaction process, and the ratio of the hydrogen supplement amount of the inner cylinder to the hydrogen supplement amount of the annular cavity is 50: 1-1: 50, preferably 1: 1-1: 10.
In the method, the retention time ratio of the materials in the inner cylinder and the annular cavity is 1: 0.5-1: 100, preferably 1: 2-1: 10.
In the method, the material on the upper part of the inner cylinder enters the membrane tube of the ceramic membrane nano/micron component, and hydrogen permeates and diffuses from the outside of the tube to the inside of the tube through an external hydrogen pipeline and is mixed with the material in the inner cylinder to be dissolved into the material containing the hydrogen and flows out of the membrane tube; the lower material of the annular cavity flows from bottom to top outside the membrane tube, hydrogen enters the membrane tube through an external hydrogen pipeline, permeates and diffuses from inside to outside of the membrane tube, is mixed with the material outside the membrane tube and is dissolved into the material containing the hydrogen, and simultaneously, the material is stripped through the external diffusion of the hydrogen.
In the method, the hydrogenation reaction conditions of the conical inner cylinder are as follows: the reaction temperature is 60-340 ℃, and preferably 180-300 ℃; the reaction pressure is 0.5-20.0 MPa, preferably 2.0-6.0 MPa; fresh feeding liquid hourly space velocity of 0.5-10.0 h-1Preferably 1.0 to 6.0 hours-1。
In the method, the hydrogenation reaction conditions of the annular cavity are as follows: the reaction temperature is 120-380 ℃, and preferably 220-360 ℃; the reaction pressure is 0.5-20.0 MPa, preferably 2.0-6.0 MPa; fresh feeding liquid hourly space velocity of 0.5-15.0 h-1Preferably 3.0 to 10.0 hours-1。
The liquid phase hydrogenation reactor can be used for various raw materials which can be subjected to hydrogenation reaction with hydrogen in the field of petrochemical industry, and can be crude oil and secondary processing oil such as crude oil, gasoline, kerosene, diesel oil, residual oil, heavy oil, wax oil, lubricating oil, deasphalted oil, biodiesel, animal oil or vegetable oil, coal tar, anthracene oil and the like, wherein the reactions of hydrogenation conversion of sulfur/nitrogen/oxygen/metal and the like, olefin and diene hydrogenation saturation, aromatic hydrocarbon partial hydrogenation saturation, hydrocracking and the like are carried out in the hydrogenation process; the catalyst can also be various raw materials capable of undergoing hydrogenation reaction in the chemical field, and can be raw materials containing carbon-carbon double bonds, carbon-carbon triple bonds and organic functional groups, such as olefin hydrogenation, alkyne hydrogenation, aldehyde compound hydrogenation, ketone compound hydrogenation, ester compound hydrogenation, nitro compound hydrogenation, nitrile compound hydrogenation and the like. The liquid phase hydrogenation reactor is particularly suitable for reaction processes with high reaction activity in the early stage, intense heat release and low reaction rate in the later stage, such as olefin hydrogenation, alkyne hydrogenation, ketone compound hydrogenation, diesel oil hydrodesulfurization and the like, effectively controls the uniform heat release in the early stage of the reaction, ensures the high activity in the early stage of the reaction, and improves the reaction rate and the conversion rate in the later stage of the reaction.
In the method of the present invention, the activity of the hydrogenation catalyst I is lower than that of the hydrogenation catalyst II, and preferably, the ratio of the activity of the hydrogenation catalyst I to the activity of the hydrogenation catalyst II is 1: 10-1: 1.05. The activity is expressed by the amount of raw material reactant converted in unit time per unit volume (or mass) of the catalyst, and can be selected or regulated in the preparation process through the specific surface area of the catalyst carrier, the property of the active center on the surface, the amount of the active center on the unit surface area and the like.
The catalyst activity was evaluated as follows: under the same raw material composition and reaction conditions, the same volume of catalyst is subjected to hydrogenation reaction on the same set of device, the product composition data is determined after the same retention time, and the conversion rate is calculated and compared to be used as the basis for judging the activity.
In the method of the invention, the catalyst adopted by the hydrogenation reactor can use proper hydrogenation catalyst according to the reaction requirement to realize different hydrogenation purposes, such as hydrofining catalyst, prehydrogenation refining catalyst, hydrogenation modification catalyst, selective hydrogenation catalyst, hydrotreating catalyst, hydrocracking catalyst, supplementary hydrogenation catalyst and the like, and various catalysts can be selected from commercial catalysts and can also be prepared according to the prior art. The catalytic reaction can remove the impurities such as sulfur, nitrogen, oxygen, arsenic, metal, carbon residue and the like in part or all of the hydrocarbon raw materials, or saturated/partially saturated olefin, aromatic hydrocarbon and diene, or the reactions such as hydrocarbon molecular isomerization, alkylation, cyclization, aromatization, cracking and the like; the catalyst active component includes but is not limited to one or more combinations of noble metals, Co, Mo, Ni, W, Mg, Zn, rare earth elements and the like.
In the method, the annular cavity can be filled with a hydrogenation catalyst with the activity wholly or partially higher than that of the conical inner cylinder, and the catalyst can be a commercially available product or prepared according to conventional knowledge in the field; for example, a catalyst with high hydrodesulfurization activity can be used, which generally uses alumina or silicon-containing alumina as a carrier and Mo and Co as hydrogenation active components. Based on the weight of the catalyst, the content of the metal Mo is 6-20 wt% calculated by oxide, and the content of the metal Co is 1-12 wt% calculated by oxide.
For the conventional hydrogenation reaction process, firstly, most of the hydrogenation reaction process belongs to exothermic reaction, reactant concentration in a fresh material at the early stage of the reaction is high, hydrogen content is also high, the driving force of the reaction process is large, and the raw material and a catalyst are fully contacted in the liquid phase hydrogenation process, so that the problems of violent reaction heat release, uneven heat release, large temperature rise, difficulty in controlling the process and the like exist, and the problem of concentrated heat release at the early stage of the reaction needs to be solved; in the later stage of the reaction, due to high reaction temperature, if the hydrogenation reaction still occurs on the high-activity catalyst, the problems of high side reaction rate and serious cracking reaction are caused, so that a catalyst with proper activity is adopted in the later stage of the reaction to control the reaction rate and improve the reaction yield, and the hydrogenation reaction depth is improved from the viewpoint of solving the inhibition effect of a reaction product on the hydrogenation reaction; thirdly, because the later stage of the reaction is still the liquid phase hydrogenation reaction process, the gas product generated by the reaction is still dissolved in the liquid material, namely, the gas product is difficult to separate in the liquid phase hydrogenation reaction process by adopting a conventional reactor stripping mode, the stripping efficiency is gradually increased along with the improvement of the reaction conversion rate, and if the stripping effect is not ideal, the reaction conversion rate in the later stage of the reaction is reduced, so that the ideal hydrogenation reaction depth is not reached; in the fourth aspect, no matter in the early stage and the later stage of the reaction, the hydrogenation reaction consumes hydrogen, the dispersion state of the hydrogen dissolved in the raw material is gradually changed along with the reaction, so that hydrogen bubbles dissolved around oil molecules are reacted, and the bubbles which are not reacted are gradually agglomerated into large bubbles, so that the oil cannot continuously provide hydrogen in the hydrogenation reaction process, the continuous driving force of the reaction hydrogen is reduced, the reaction rate is reduced, and the dissolved hydrogen in a high dispersion state needs to be timely supplemented in the reaction process.
According to the invention, through the special liquid-phase hydrogenation reactor and the hydrogenation method, the initial activity of the catalyst at the early stage of the hydrogenation reaction is effectively controlled, the reaction conversion rate at the later stage of the reaction is improved, the problems of violent heat release at the early stage of the reaction and reaction conversion rate inhibition of reaction products at the later stage of the reaction are solved, and simultaneously, the higher hydrogenation reaction rate and reaction conversion rate at the early stage and the later stage of the reaction are achieved. The hydrogenation reactor comprises a conical inner cylinder, an annular cavity and a ceramic membrane nano/micron component penetrating through the inner cylinder and the annular cavity, the flow mode of materials in the conical inner cylinder is from top to bottom, the characteristic that the sectional area of a conical structure is gradually increased from top to bottom is utilized, the sectional area of the inner cylinder is gradually increased along with the progress of reaction, the materials and a catalyst are in progressive contact, the problem of uneven heat release caused by violent reaction when the concentration of hydrogenation raw materials is higher in the early stage of reaction is solved, the reaction rate can be ensured, and the activity in the early stage of reaction can be effectively controlled; the material flows from bottom to top in the annular cavity, and the characteristic that the sectional area of the annular cavity is gradually increased from bottom to top is also utilized to realize gradual progressive contact between the material and the catalyst in the later reaction period, so that reactants and reaction gas in the products in the later reaction period are stripped by gradually increasing the stripping surface area and improving the stripping effect while controlling the reaction rate in the high-temperature region, and the reaction rate and the conversion rate in the later reaction period are improved. In addition, in the early stage of the reaction of the conical inner cylinder, because the concentration of reaction raw materials is high and the reaction driving force is large, a proper catalyst with low activity is adopted in the early stage of the reaction, the reaction rate in the early stage of the reaction is controlled, the heat release is more uniform, hydrogen is supplemented through the ceramic membrane nano/micron hydrogen dispersion assembly in the hydrogenation reaction process, the hydrogen consumed in the reaction process is supplemented in time, the driving force in the hydrogenation reaction process is increased, and the high hydrogenation reaction rate in the early stage of the reaction is kept; in the later reaction stage in the annular cavity, because the reaction concentration is low and the reaction driving force is small, the catalyst with the activity higher than that of the inner cylinder is adopted, the reaction rate in the later reaction stage is improved, hydrogen is supplemented through the ceramic membrane nano/micron hydrogen dispersion assembly in the reaction process, the effects of supplementing hydrogen and stripping are achieved, and the purpose of improving the hydrogenation reaction depth is achieved through a mode of gradually increasing the stripping surface area and improving the stripping effect.
Drawings
FIG. 1 is a schematic diagram of a liquid phase hydrogenation reactor and hydrogenation process of the present invention.
Fig. 2 is a schematic diagram of a ceramic membrane nano/micro module of the present invention.
The device comprises a hydrogen gas 1, a raw oil 2, a hydrogen-oil mixer 3, a liquid phase hydrogenation reactor 4, a liquid phase hydrogenation reactor 5, a hydrogenation reaction product 6, an exhaust gas 7, a reaction product discharge valve 8, an exhaust control valve 9, an annular cavity catalyst gland grating 10, a catalyst support grating 11, a conical inner cylinder 12, a catalyst I13, an annular cavity 14, a catalyst II 15, a ceramic membrane nano/micron component 16, an annular cavity hydrogen feeding pipeline 17, a ceramic membrane nano/micron component of the conical inner cylinder 18, a ceramic membrane nano/micron component of the annular cavity 19 and a conical inner cylinder hydrogen feeding pipeline 20.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but the invention is not limited thereby.
The liquid phase hydrogenation reactor and the hydrogenation method of the invention comprise the following steps: hydrogen 1 raw oil 2 is mixed with hydrogen oil by a hydrogen-oil mixer 3, enters a liquid phase hydrogenation reactor 5 as a liquid phase hydrogenation reactor feed 4 from the top of the liquid phase hydrogenation reactor 5, firstly enters a conical inner cylinder 12 of the liquid phase hydrogenation reactor 5, sequentially passes through a catalyst I from top to bottom, enters a region where the bottom of the reactor is communicated with an annular cavity 14, and is subjected to hydrogen supplement and hydrogen re-dissolution by a ceramic membrane nano/micron component 16 in the hydrogenation reaction process of the conical inner cylinder 12; the material leaving the conical inner cylinder 12 enters the annular cavity 14, passes through the catalyst II 15 of the annular cavity from bottom to top to perform further hydrogenation reaction, and in the reaction process, the ceramic membrane nano/micron component 16 is used for hydrogen supplement and reaction gas stripping, so that the reaction gas in the reaction product is stripped while the coking of the high-temperature catalyst is prevented; the final hydrogenation reaction product 6 leaves the liquid phase hydrogenation reactor 5 under the control of a reaction product discharge valve 8; the reaction gas stripped from the annular cavity 14 is discharged as exhaust gas 7 by the top exhaust control valve 9 of the annular cavity. The ceramic membrane nano/micron component 16 is divided into a conical inner cylinder part 18 and an annular cavity part 19, in the ceramic membrane nano/micron component 18 of the conical inner cylinder, a material from the upper part of the conical inner cylinder 18 enters a membrane tube, hydrogen enters the outside of the membrane tube through an external hydrogen pipeline 20, the hydrogen permeates and diffuses into the tube through the outside of the tube and is mixed and dissolved with the material of the inner cylinder to form a material containing the hydrogen, the material flows out of the membrane tube, in the ceramic membrane nano/micron component 19 of the annular cavity, the material flowing upwards from the lower part of the annular cavity 14 is outside the membrane tube, the hydrogen enters the inside of the membrane tube through an external hydrogen pipeline 17, and the hydrogen is mixed and dissolved with the material outside the tube to form the material containing the hydrogen in the process of permeating and diffusing to the outside of the tube through.
The raw oil used in the comparative example and the example of the invention is straight-run diesel oil and catalytic diesel oil from a certain plant, and the specific properties are shown in Table 1.
TABLE 1 Properties of the raw materials
Comparative example 1
A conventional fixed bed hydrogenation reactor and a hydrogenation method are adopted, and a static mixer is adopted as hydrogen-oil mixing equipment, wherein the model is as follows: SX-2.3-10.0-500; the hydrogen feed in the reactor feed was 0.68% (straight run diesel feedstock) and 2.45% (catalytic diesel feedstock) of the feedstock (sum of fresh feedstock and cycle oil) mass. The hydrogenation reactor adopts catalysts FHUDS-3 and FHUDS-5 of the comforting petrochemical research institute, and the ratio of the two catalysts is 1: 2.
The fixed bed (straight-run diesel) hydrogenation reaction conditions were as follows: the reaction temperature is 310-378 ℃, the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 3.0h-1The circulation ratio is 1.5 to 2.0.
The fixed bed (catalytic diesel) hydrogenation reaction conditions were as follows: the reaction temperature is 306-387 ℃, the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 3.0h-1The circulation ratio is 1.5 to 2.0.
The straight-run diesel oil and the catalytic diesel oil in the table 1 are respectively used as raw materials, and reaction products are obtained after fixed bed liquid phase hydrogenation, and the reaction conditions and the product properties are shown in tables 2 and 3.
Example 1
Using the method described in figure 1According to the method, a catalyst adopted by a conical inner cylinder of a hydrogenation reactor is FH-40C of a comforting petrochemical research institute, and a catalyst adopted by an annular cavity space is FHUDS-2; the hydrogen contained in the feed of the hydrogenation reactor is 0.23 percent (straight-run diesel raw material) and 0.23 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil), the hydrogen supplement amount in the conical inner cylinder of the hydrogenation reactor is 0.25 percent (straight-run diesel raw material) and 1.15 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil), and the hydrogen supply amount in the annular cavity is 0.13 percent (straight-run diesel raw material) and 0.62 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil). The reaction conditions of the conical inner cylinder of the hydrogenation reactor are as follows: the reaction temperature is 300-325 ℃ (straight-run diesel raw material), 300-344 ℃ (catalytic diesel raw material), the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 4.0h-1(ii) a The reaction conditions of the annular cavity were as follows: the reaction temperature is 325-352 ℃ (straight-run diesel raw material), the reaction pressure is 5.9MPaG (catalytic diesel raw material), and the liquid hourly space velocity is 6.0h-1. The ratio of the top plane diameter to the bottom surface diameter of the inner conical cylinder in the reactor is 1:2, and the ratio of the bottom surface diameter to the reactor diameter of the inner conical cylinder is 1: 1.1.
The straight-run diesel oil and the catalytic diesel oil in the table 1 are used as raw materials, and reaction products are obtained after the liquid phase hydrogenation of the invention, and the reaction conditions and the product properties are shown in the tables 2 and 3.
Example 2
The method shown in the attached figure 1 is adopted, the catalyst adopted by the conical inner cylinder of the hydrogenation reactor is FH-40C of the comforting petrochemical research institute, and the catalyst adopted by the annular cavity is FHUDS-5; hydrogen contained in the feed of the hydrogenation reactor is 0.22 percent (straight-run diesel raw material) and 0.25 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of fresh raw oil and circulating oil), the hydrogen supplement amount in the conical inner cylinder of the hydrogenation reactor is 0.26 percent (straight-run diesel raw material) and 1.08 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of fresh raw oil and circulating oil), and the hydrogen supply amount in the annular cavity space is 0.12 percent (straight-run diesel raw material) and 0.12 percent (straight-run diesel raw material) of the mass of the raw oil (the sum of fresh raw oil and circulating oil0.65% (catalytic diesel feedstock). The reaction conditions of the conical inner cylinder of the hydrogenation reactor are as follows: the reaction temperature is 305-332 ℃ (straight-run diesel raw material), 300-346 ℃ (catalytic diesel raw material), the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 3.0h-1(ii) a The reaction conditions of the annular cavity were as follows: the reaction temperature is 332-355 ℃ (straight-run diesel raw material), 346-368 ℃ (catalytic diesel raw material), the reaction pressure is 5.9MPaG, and the liquid hourly space velocity is 6.5h-1. The ratio of the top plane diameter to the bottom surface diameter of the inner conical cylinder in the reactor is 1:5, and the ratio of the bottom surface diameter to the reactor diameter of the inner conical cylinder is 1: 1.5.
The straight-run diesel oil and the catalytic diesel oil in the table 1 are used as raw materials, and reaction products are obtained after the liquid phase hydrogenation of the invention, and the reaction conditions and the product properties are shown in the tables 2 and 3.
Example 3
Adopting the method shown in the attached figure 1, the catalyst adopted by the conical inner cylinder of the hydrogenation reactor is FHUDS-2 of the comforting petrochemical research institute, and the catalyst adopted by the annular cavity is FHUDS-5; the hydrogen contained in the feed of the hydrogenation reactor is 0.21 percent (straight-run diesel raw material) and 0.23 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil), the hydrogen supplement amount in the conical inner cylinder of the hydrogenation reactor is 0.22 percent (straight-run diesel raw material) and 1.14 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil), and the hydrogen supply amount in the annular cavity is 0.17 percent (straight-run diesel raw material) and 0.58 percent (catalytic diesel raw material) of the mass of the raw oil (the sum of the fresh raw oil and the circulating oil). The reaction conditions of the conical inner cylinder of the hydrogenation reactor are as follows: the reaction temperature is 308-338 ℃ (straight-run diesel raw material), 310-355 ℃ (catalytic diesel raw material), the reaction pressure is 5.0MPaG, and the liquid hourly space velocity is 5.5h-1(ii) a The reaction conditions of the annular cavity were as follows: the reaction temperature is 338-362 ℃ (straight-run diesel raw material), 355-376 ℃ (catalytic diesel raw material), the reaction pressure is 4.9MPaG, and the liquid hourly space velocity is 7.0h-1. The ratio of the top plane diameter to the bottom surface diameter of the inner conical cylinder in the reactor is 1:3, and the ratio of the bottom surface diameter to the reactor diameter of the inner conical cylinder is 1: 1.5.
TABLE 2 reaction conditions and product Properties (straight run Diesel feedstock)
TABLE 3 reaction conditions and product Properties (catalytic Diesel feedstock)
Claims (12)
1. A liquid phase hydrogenation reactor, characterized by: the reactor comprises an inner cylinder and a reactor shell, wherein the top of the reactor shell is provided with an upper seal head, the bottom of the reactor shell is provided with a lower seal head, the inner cylinder is conical, an annular cavity is formed between the inner cylinder and the reactor shell, the cross section area of the annular cavity is gradually increased from bottom to top, and the upper part of the annular cavity is provided with a product outlet; the top of the inner cylinder penetrates through the upper end enclosure and is communicated with a raw material inlet at the top of the reactor, a catalyst support is arranged below the bottom of the inner cylinder, and the bottom of the inner cylinder is communicated with the bottom of the annular cavity; a ceramic membrane nano/micron component is horizontally arranged in the middle of the reactor, penetrates through the cross section where the annular cavity and the inner cylinder are located, and is communicated with external hydrogen; the inner cylinder is filled with a hydrogenation catalyst I, the annular cavity is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is lower than that of the hydrogenation catalyst II; the flowing mode of the materials in the inner cylinder is from top to bottom; the material flows from bottom to top in the annular cavity.
2. The liquid phase hydrogenation reactor of claim 1, wherein: the ratio of the upper end surface to the lower end surface of the conical inner cylinder is 1: 1.05-1: 30, preferably 1: 1.5-1: 15, and the ratio of the lower end surface to the reactor is 1: 1.01-1: 20, preferably 1: 1.05-1: 10.
3. The liquid phase hydrogenation reactor of claim 1, wherein: the ceramic membrane nano/micron component is of an integrated tube shell structure and comprises a plurality of ceramic membrane tubes and a shell, wherein the ceramic membrane tubes are perpendicular to the cross section direction of the reactor; the ceramic membrane nano/micron component of the inner cylinder part is characterized in that a membrane tube is communicated with materials flowing upwards in the inner cylinder, and a cavity outside the membrane tube is communicated with an external hydrogen pipeline; the ceramic membrane nano/micron component is arranged at the annular cavity part, the membrane tube is communicated with an external hydrogen pipeline, and the cavity at the outer side of the membrane tube is communicated with materials flowing downwards in the annular cavity; the size of the nano/micron bubbles which can be formed by the ceramic membrane nano/micron component is 10-1000 nm.
4. The liquid phase hydrogenation reactor of claim 1, wherein: the ceramic membrane nano/micron modules can be arranged in one or more groups along the radial direction of the reactor.
5. The liquid phase hydrogenation reactor of claim 1, wherein: the top of the reactor is provided with a gas space, and the highest point of the top seal head of the reactor is provided with a gas outlet for continuously or discontinuously discharging the reaction gas stripped in the reaction process.
6. A liquid phase hydrogenation process, characterized by comprising: the raw material containing hydrogen enters a conical inner cylinder of the hydrogenation reactor through a feed inlet at the top of the reactor, is subjected to hydrogenation reaction with a hydrogenation catalyst I filled in the inner cylinder, is subjected to hydrogen supplementation and hydrogen re-dissolution through a ceramic membrane nano/micron component, flows out of the bottom of the inner cylinder, passes through the bottom of the reactor, enters an annular cavity from bottom to top, is subjected to further hydrogenation reaction with a hydrogenation catalyst II filled in the annular cavity, flows are subjected to hydrogen supplementation and steam stripping through the ceramic membrane nano/micron component, and the final reaction product is discharged from a discharge outlet at the upper part of the reactor.
7. The method of claim 1, wherein: the ratio of the hydrogen supplement amount of the inner cylinder to the hydrogen supplement amount of the annular cavity is 50: 1-1: 50.
8. The method of claim 1, wherein: the retention time ratio of the materials in the inner cylinder and the annular cavity is 1: 0.5-1: 100.
9. The method of claim 1, wherein: the material on the upper part of the inner cylinder enters a membrane tube of the ceramic membrane nano/micron component, and hydrogen permeates and diffuses from the outside of the tube to the inside of the tube through an external hydrogen pipeline and is mixed with the material in the inner cylinder to be dissolved into a material containing hydrogen and flows out of the membrane tube; the lower material of the annular cavity flows from bottom to top outside the membrane tube, hydrogen enters the membrane tube through an external hydrogen pipeline, permeates and diffuses from inside to outside of the membrane tube, is mixed with the material outside the membrane tube and is dissolved into the material containing the hydrogen, and simultaneously, the material is stripped through the external diffusion of the hydrogen.
10. The method of claim 1, wherein: the hydrogenation reaction conditions of the conical inner cylinder are as follows: the reaction temperature is 60-340 ℃, the reaction pressure is 0.5-20.0 MPa, and the hourly space velocity of fresh feed liquid is 0.5-10.0 h-1。
11. The method of claim 1, wherein: the hydrogenation reaction conditions of the annular cavity are as follows: the reaction temperature is 120-380 ℃, the reaction pressure is 0.5-20.0 MPa, and the hourly space velocity of fresh feed liquid is 0.5-15.0 h-1。
12. The method of claim 1, wherein: the ratio of the activity of the hydrogenation catalyst I to the activity of the hydrogenation catalyst II is 1: 10-1: 1.05.
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