CN112705123B - Hydrogenation reactor and hydrogenation method - Google Patents
Hydrogenation reactor and hydrogenation method Download PDFInfo
- Publication number
- CN112705123B CN112705123B CN201911020911.XA CN201911020911A CN112705123B CN 112705123 B CN112705123 B CN 112705123B CN 201911020911 A CN201911020911 A CN 201911020911A CN 112705123 B CN112705123 B CN 112705123B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- hydrogenation
- reactor
- reaction
- inner cylinder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 201
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 claims abstract description 156
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 156
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 239000003054 catalyst Substances 0.000 claims abstract description 109
- 239000000463 material Substances 0.000 claims abstract description 46
- 230000000694 effects Effects 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 230000005764 inhibitory process Effects 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 61
- 239000000919 ceramic Substances 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 30
- 150000002431 hydrogen Chemical class 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 22
- 238000004939 coking Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 230000002829 reductive effect Effects 0.000 claims description 15
- 239000013589 supplement Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 230000009469 supplementation Effects 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 7
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 12
- 239000003921 oil Substances 0.000 description 43
- 235000019198 oils Nutrition 0.000 description 40
- 239000007791 liquid phase Substances 0.000 description 16
- 239000010724 circulating oil Substances 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 aldehyde compound Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000005315 distribution function Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrogenation reactor and a hydrogenation method. The hydrogenation reactor comprises an inner cylinder and a reactor shell, wherein the inner cylinder is conical, and an annular space is formed between the inner cylinder and the reactor shell; the top and the bottom of the inner cylinder are open, and the edge of the bottom is hermetically connected with the inner wall of the reactor; the inner cylinder is filled with a hydrogenation catalyst I, the annular space is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is higher than that of the hydrogenation catalyst II; a hydrogen replenishing component is horizontally arranged in the middle of the reactor; the reactor raw material inlet is communicated with the bottom of the inner cylinder, and the reactor product outlet is communicated with the lower part of the annular space; the material flows from bottom to top in the inner cylinder; the material flows from top to bottom in the annular space. The invention can effectively control the contact time of the materials and the catalysts with different activities in different temperature sections of the hydrogenation reaction, realize the purposes of quick reaction in low and medium temperature sections and inhibition of side reaction in high temperature section, and improve the hydrogenation reaction rate and reaction depth.
Description
Technical Field
The invention belongs to the field of chemical and petrochemical industry, and particularly relates to a hydrogenation reactor and a hydrogenation method.
Background
Hydrogenation is a reaction process in which hydrogen interacts with compounds, usually in the presence of a catalyst. Hydrogenation processes have been one of the most important reaction processes in the chemical industry and petroleum refining industry. The hydrogenation reaction is reversible, exothermic and the number of molecules is reduced, and the chemical equilibrium is favorably shifted to the direction of the hydrogenation reaction at low temperature and high pressure. The temperature required for the hydrogenation process depends on the activity of the catalyst used, and temperatures at which the activity is high may be lower. For the hydrogenation reaction with a small equilibrium constant under the reaction temperature condition, the reaction process needs to be carried out under high pressure in order to increase the equilibrium conversion rate, and is also favorable for increasing the reaction speed. In addition, excessive hydrogen is adopted, so that the reaction speed can be accelerated, the conversion rate of hydrogenated substances can be improved, and the reaction heat can be led out. The excess hydrogen can be recycled.
Hydrogenation reactors are classified into various types, such as fixed bed hydrogenation reactors, suspended bed hydrogenation reactors, ebullated bed hydrogenation reactors, and the like, and the fixed bed hydrogenation reactor is most widely applied. The upflow fixed bed reactor can treat various types of oil products, and has unique advantages in the oil product hydrogenation process, such as poor oil product residual oil and coal liquefied oil, which are easily poisoned by hydrogenation catalysts or quickly inactivated by catalyst pore channel blockage due to high impurity content, and the impurities may block the bed layer to quickly raise the pressure drop to cause the working condition of the reactor to be worsened, even the normal operation cannot be realized, if the upflow hydrogenation process is adopted to cause the gas-liquid cocurrent upward movement to cause the expansion of the catalyst bed layer, the void ratio of the bed layer can be increased, and the blockage of the catalyst bed layer is avoided. In the hydrogenation process, compared with the traditional fixed bed gas/liquid/solid three-phase hydrogenation process, the liquid phase hydrogenation process 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, so that the up-flow liquid phase hydrogenation process integrates the advantages of an up-flow hydrogenation reactor and the advantages of a liquid phase hydrogenation process, and has certain advantages when being applied to the hydrogenation process. However, the following problems still exist in the conventional upflow liquid phase hydrogenation reactor and reaction process: (1) The contact between the reaction materials and the catalyst is more sufficient, the reaction rate is high, the reaction efficiency is high, and the problems of long reaction residence time, side reaction or severe cracking and catalyst coking still exist; (2) Especially in the section with high reaction temperature in the final stage, because the contact between the materials and the catalyst is sufficient, the side reaction or the cracking reaction is serious and far exceeds the positive reaction, a large amount of undesired reactions occur in the final stage of the reaction, and the yield and the production efficiency are reduced; (3) Along with the flow of materials in the hydrogenation reactor and the consumption of hydrogen in the reaction process, the dissolution and dispersion state of hydrogen in oil products is gradually changed, so that hydrogen bubbles dissolved around oil product molecules are reacted, and the bubbles which do not react are gradually agglomerated into large bubbles, so that the hydrogen can not be continuously provided in the hydrogenation reaction process of the oil products, and side reactions or cracking reactions can also be increased; (4) At the end of the reaction, some hydrogenation reactions have an inhibitory effect on the positive reaction of the product or one or more components in the product, making it difficult to achieve the desired depth of hydrogenation reaction. Therefore, for the conventional upflow liquid phase hydrogenation reaction process, effective means such as development of a new hydrogenation method and a new reactor form are adopted, the hydrogenation reaction rate and the reaction depth are improved, and the side reaction or the cracking reaction at a high temperature section is inhibited, so that the method has important significance.
CN202063881U discloses a liquid phase hydrogenation reactor, wherein a mixer is arranged in a top head of the reactor, the mixer is provided with a mixed oil feeding hole and a hydrogen inlet, a dissolved hydrogen mixture outlet and a gas outlet, and the mixture dissolved hydrogen mixture outlet is inserted into the liquid phase of the reactor. The purpose of this patent is through the structure of hydrogen mixer in the reactor, to increase the gas-liquid phase contact area, make hydrogen dissolve in the miscella, improve hydrogenation efficiency.
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 reactor containing at least two stages of catalysts from top to bottom in sequence with a hydrogen distributor at the lower part of each stage of catalyst, and the product is led out of 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.
CN200810117101.1 proposes an upflow reactor and application thereof, the upflow reactor comprises an initial distributor positioned at the bottom of the reactor and a middle distributor positioned above the initial distributor, the initial distributor consists of a conical baffle plate and a sieve plate positioned above the conical baffle plate; the intermediate distributor is composed of an open-pore sieve plate and a sieve plate string structure, and the upflow reactor provided by the invention aims to realize uniform distribution of gas, thereby improving the utilization rate of the catalyst. CN201110353672.7 provides a gas-liquid distributor of an upflow reactor and application thereof, and the gas-liquid distributor comprises a distribution disc tower plate and a cap type gas collection distributor. CN201510697566.9 proposes an upflow distributor and an upflow reactor, and the purpose of the invention is that the fluid can be uniformly distributed and uniformly mixed after passing through the upflow distributor by the technical scheme.
In summary, in the upflow hydrogenation reactor and the liquid phase hydrogenation reactor in the prior art, hydrogen dissolution is generally performed by a hydrogen dissolution method or a hydrogen dissolution component, and the reaction efficiency is improved by a hydrogen supplementation method, so that the problems of high catalytic activity in the early stage and the middle stage of the reaction, low reaction rate in the final stage, serious side reaction and cracking reaction of the upflow liquid phase hydrogenation reactor, inhibition of reaction products on reaction raw materials, and the like are not solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation reactor and a hydrogenation method, wherein the inner cylinder with a conical structure is arranged in the upflow hydrogenation reactor, so that the contact time of materials and different active catalysts in different temperature sections of the hydrogenation reaction can be effectively controlled, the purposes of realizing rapid reaction in low and medium temperature sections and inhibiting side reaction in a high temperature section are realized, and the hydrogenation reaction rate and the reaction depth are improved.
The hydrogenation reactor comprises an inner cylinder and a reactor shell, wherein the inner cylinder is conical, and an annular space with a gradually reduced cross-sectional area is formed between the inner cylinder and the reactor shell from top to bottom; the top and the bottom of the inner cylinder are open, and the edge of the bottom is hermetically connected with the inner wall of the reactor; the inner cylinder is filled with a hydrogenation catalyst I, the annular space is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is higher than that of the hydrogenation catalyst II; the middle part of the reactor is horizontally provided with a hydrogen replenishing component, the hydrogen replenishing component penetrates through the annular space and the cross section where the inner cylinder is located, and the hydrogen replenishing component is communicated with external hydrogen; the reactor raw material inlet is communicated with the bottom of the inner cylinder, and the reactor product outlet is communicated with the lower part of the annular space; the material flows from bottom to top in the inner cylinder; the material flows from top to bottom in the annular space.
The ratio of the diameter of the top plane of the inner cylinder to the diameter of the reactor is (1.05-1), preferably (1.5-1).
The hydrogenation reactor comprises a hydrogen supplementing assembly and a hydrogen distribution or gas-liquid mixing assembly, wherein the hydrogen supplementing assembly comprises a pipeline communicated with external hydrogen and the hydrogen distribution or gas-liquid mixing assembly. The component with the gas distribution function, such as a distribution pipe, a distribution plate and the like, can also be equipment with the gas-liquid mixing function, such as a static mixer filled with any one of a spiral plate, a corrugated plate, a rotating blade, a flat blade, a bent blade or a porous plate, or a microporous plate nano/micron hydrogen dispersion component, a ceramic membrane nano/micron hydrogen dispersion component and the like. And the hydrogen replenishing assembly of the inner barrel part and the hydrogen replenishing assembly of the annular space part are respectively communicated with an external hydrogen pipeline.
In the hydrogenation reactor, the hydrogen supplement component is preferably a ceramic membrane nano/micron dispersion component which 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, two ends of each membrane tube are fixed on a tube plate, and the shell is fixed on the inner surface of the reactor; the ceramic membrane nano/micron dispersion component of the inner cylinder part, the membrane tube is communicated with the material flowing upwards in the inner cylinder, and the cavity outside the membrane tube is communicated with an external hydrogen pipeline; a ceramic membrane nano/micron dispersion component in the annular space, wherein a membrane tube is communicated with an external hydrogen pipeline, and a cavity outside the membrane tube is communicated with a material flowing downwards in the annular space; the ceramic membrane nano/micro hydrogen dispersion module is capable of forming nano/micro bubble hydrogen with a size of generally 10 to 1000nm, preferably 50 to 500nm.
According to the hydrogenation reactor, the ceramic membrane nano/micron dispersion assembly at the inner cylinder part and the ceramic membrane nano/micron hydrogen dispersion assembly positioned at the inner cylinder mainly have the functions of hydrogen supplement and hydrogen re-dissolution, materials at the lower part of the inner cylinder enter the inside of the membrane tube, hydrogen enters the outside of the membrane tube through an external hydrogen pipeline, the hydrogen permeates and diffuses into the inside of the tube through the outside of the membrane tube and is mixed and dissolved with the materials in the inner cylinder to be hydrogen-containing materials, and the hydrogen flows out of the membrane tube, 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 hydrogen dispersion assembly in the annular space has the main functions of hydrogen supplement and stripping, materials flowing downwards in the upper part of the annular space enter the outside of the membrane tube, hydrogen enters the inside of the membrane tube through an external hydrogen pipeline, and in the process that the hydrogen permeates and diffuses to the outside of the membrane tube through the outside of the tube, the materials are mixed and dissolved with the materials outside the membrane tube to form the materials containing the hydrogen, and the stripping effect is performed on the materials through the external diffusion of the hydrogen, so that the hydrogen can be supplemented in the final reaction stage, the coking of the surface of a catalyst in the high-temperature section in the final reaction stage is inhibited, and meanwhile, a surface coking precursor and the generated gas in a reactor can be timely stripped and separated, and the reaction depth is improved.
In the hydrogenation reactor, the top is a reactor upper end enclosure, the bottom is a reactor lower end enclosure, and a material distributor is preferably arranged at a raw material inlet and used for uniformly distributing materials to enter the inner cylinder.
The hydrogenation method comprises the following steps: the raw material containing hydrogen enters the conical inner cylinder through a feed inlet at the bottom of the reactor, and is subjected to hydrogenation reaction with the hydrogenation catalyst I filled in the inner cylinder, the material is subjected to hydrogen supplementation and hydrogen re-dissolution through the hydrogen supplementation component, flows out from the top of the inner cylinder, passes through the top of the reactor, enters the annular space from top to bottom, is subjected to further hydrogenation reaction with the hydrogenation catalyst II filled in the annular space, the material flow is subjected to hydrogen supplementation and steam stripping through the hydrogen supplementation component, and the final reaction product is discharged from a discharge outlet at the bottom of the reactor.
In the method, the hydrogen replenishing amount of the inner cylinder and the annular space is regulated according to the requirement of the reaction process, and the ratio of the hydrogen replenishing amount of the inner cylinder to the hydrogen replenishing amount of the annular space is (1-1), preferably (1).
In the method, the retention time ratio of the materials in the inner cylinder and the annular space is 100 to 1, preferably 30.
In the method, the top of the reactor is provided with a gas space, and the highest point of the head at the top of the reactor is provided with a gas outlet for continuously or discontinuously discharging the reaction gas stripped in the reaction process.
In the method, the upper part of the reactor is discharged by liquid level control, so that the hydrogenation reaction process is ensured to be full liquid phase hydrogenation.
In the method, the hydrogenation reaction conditions of the inner cylinder are as follows: the reaction temperature is 60-360 ℃, preferably 180-340 ℃; the reaction pressure is 0.5MPa to 20.0MPa, preferably 2.0MPa to 6.0MPa; fresh feed liquid hourly space velocity of 0.5h -1 ～10.0h -1 Preferably 1.0h -1 ～6.0h -1 。
In the method of the invention, the hydrogenation reaction conditions of the annular space are as follows: the reaction temperature is 120-400 ℃, preferably 220-380 ℃; the reaction pressure is 0.5MPa to 20.0MPa, preferably 2.0MPa to 6.0MPa; fresh feed liquid hourly space velocity of 0.5h -1 ～15.0h -1 Preferably 3.0h -1 ～10.0h -1
The 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 reactions such as 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 performed 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.
In the method of the present invention, the activity of the hydrogenation catalyst I is higher 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 1.05 to 10. The level of activity is expressed by the amount of reactants converted into raw materials per unit volume (or mass) of the catalyst in unit time, and can be selected or regulated in the preparation process through the specific surface area of the catalyst carrier, the nature of active centers on the surface, the amount of active centers 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 space can be filled with a hydrogenation catalyst with activity which is wholly or partially lower than that of the 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 a conventional hydrogenation reaction process, firstly, most of the hydrogenation reaction processes are exothermic reactions, that is, the temperature is gradually increased along with the reaction, although the higher the temperature is, the faster the reaction rate is, when the temperature is higher, the material is more prone to coking on the surface of the catalyst, so that a cracking reaction occurs or the activity of the catalyst is reduced, therefore, along with the increase of the hydrogenation reaction temperature, the contact time of the raw material and the high-efficiency catalyst should be gradually shortened, and the coking on the surface of the catalyst is slowed or controlled while the higher reaction is maintained; in the second aspect, in the later stage of the hydrogenation reaction, the reaction temperature is high, the high-activity catalyst is more prone to coking under the condition of high temperature, and the cracking reaction is more serious, so that a catalyst with proper activity or even slightly low activity is filled in the last stage of the reaction, the hydrogenation reaction rate is controlled as much as possible, the high reaction rate in the later stage of the reaction is inhibited, and in the later stage of the reaction, along with the increase of the hydrogenation reaction temperature, the retention time of the raw material on the surface of the catalyst is gradually shortened to control the coking on the surface of the catalyst; in the third aspect, some byproduct reaction gases have a certain inhibiting effect on hydrogenation reaction, and the byproduct reaction gases cannot be removed out of the system in time and are not beneficial to deep hydrogenation reaction, so that in-situ stripping in the reaction process plays an important role in realizing deep hydrogenation; in the fourth aspect, in the low and medium temperature stages, the hydrogenation reaction rate is high, the hydrogen consumption is high, the dissolution dispersion state of the hydrogen in the raw material has been gradually changed, so that the hydrogen bubbles dissolved around the oil molecules have been reacted, and those bubbles which have not reacted gradually coalesce 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, and the reaction rate is reduced, therefore, the dissolved hydrogen in the high dispersion state needs to be timely supplemented in the low and medium temperature stages of the reaction.
According to the invention, through a special hydrogenation reactor structure and a hydrogenation reaction method, the contact time of materials and different active catalysts in different temperature sections of the hydrogenation reaction is effectively controlled, the purposes of quick reaction in low and medium temperature sections and inhibition of side reaction in a high temperature section are realized, and the hydrogenation reaction rate and the reaction depth are improved. The hydrogenation reactor comprises a conical inner cylinder, an annular space with the cross sectional area gradually reduced from bottom to top and a hydrogen replenishing assembly penetrating through the inner cylinder and the annular space, wherein the material flows from bottom to top in the conical inner cylinder, and the contact time of the raw material and the high-activity catalyst is controlled to be gradually shortened along with the rise of the reaction temperature by utilizing the characteristic that the cross sectional area of a conical structure is gradually reduced from bottom to top, so that the coking on the surface of the catalyst is slowed or controlled while the high reaction is kept, and the side reaction is reduced; the flowing mode of the material in the annular space is from top to bottom, and the characteristic that the sectional area of the annular space is gradually reduced from top to bottom is utilized, so that the contact time of the control raw material and the catalyst with low activity is gradually shortened when the temperature at the final stage of reaction is higher, and the high-temperature coking on the surface of the catalyst can be further inhibited and slowed or controlled, and the side reaction is reduced. In addition, a high-activity catalyst is adopted at the low and medium temperature reaction stages of the conical inner cylinder, rapid hydrogenation reaction occurs, hydrogen is supplemented through a hydrogen supplementing component in the reaction process, when high hydrogen consumption in the reaction process is achieved, high-dispersion hydrogen is supplemented in time, the driving force of the hydrogenation reaction process is increased, and the medium and low temperature hydrogenation reaction rates are further improved; and a catalyst with slightly low activity is filled in the annular space at a high temperature stage to perform a slow hydrogenation reaction, and hydrogen is supplemented through the hydrogen supplementing component in the reaction process to play roles of supplementing hydrogen and stripping, so that the coking of the catalyst at the high temperature reaction stage is inhibited, and the reaction gas for inhibiting the hydrogenation reaction is stripped to achieve a deep hydrogenation reaction.
Drawings
FIG. 1 is a schematic diagram of a hydrogenation reactor and hydrogenation process of the present invention.
Fig. 2 is a schematic of a ceramic membrane nano/micro hydrogen dispersion module of the present invention.
The device comprises a raw material oil 1, a hydrogen 2, a hydrogen-oil mixer 3, a hydrogenation reactor feeding 4, a hydrogenation reactor 5, a reaction product 6, a discharge gas 7, a reaction product discharge valve 8, an exhaust control valve 9, a catalyst gland grating 10, a catalyst support grating 11, a conical inner cylinder 12, a hydrogenation catalyst I13, an annular space 14, a hydrogenation catalyst II15, a hydrogen supplement component (ceramic membrane nano/micron dispersion component) 16, a hydrogen pipeline communicated with the annular space 17, a ceramic membrane pipe of the conical inner cylinder 18, a ceramic membrane pipe of the annular space 19 and a hydrogen pipeline communicated with the conical inner cylinder 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 hydrogenation reactor and hydrogenation process of the present invention are illustrated in FIG. 1:
raw oil 1 and hydrogen 2 are mixed by a hydrogen-oil mixer 3, and then enter a hydrogenation reactor 5 from the bottom of the hydrogenation reactor 5 as a hydrogenation reactor feed 4, firstly enter a conical inner cylinder 12 of the hydrogenation reactor 5, sequentially pass through a hydrogenation catalyst I from bottom to top for hydrogenation reaction, enter a region where the top of the reactor is communicated with the inner cylinder, and carry out hydrogen supplementation and hydrogen re-dissolution by a hydrogen supplementation component (ceramic membrane nano/micron hydrogen dispersion component) 16 in the reaction process of the conical inner cylinder 12; the material leaving the conical inner cylinder 12 enters an annular space 14, and is subjected to further hydrogenation reaction with a hydrogenation catalyst II15 in the annular space from top to bottom, and in the reaction process, hydrogen supplement and stripping reaction gas are performed through a hydrogen supplement component (ceramic membrane nano/micron hydrogen dispersion component) 16, so that the reaction gas in the reaction product is stripped while the coking of the high-temperature catalyst is prevented; the final reaction product 6 leaves the hydrogenation reactor 5 under the control of a reaction product discharge valve 8; the reaction gas stripped from the annular space 14 is discharged as an exhaust gas 7 by the reactor top exhaust control valve 9. The hydrogen supplement component (ceramic membrane nano/micron dispersion component) 16 is an integrated tube shell structure and generally comprises a plurality of ceramic membrane tubes and a shell, wherein the ceramic membrane tubes generally comprise a plurality of ceramic membranes perpendicular to the cross section of the reactor, two ends of each membrane tube are fixed on a tube plate, and the shell is fixed on the inner surface of the reactor; a ceramic membrane nano/micron dispersion component 16 at the inner cylinder part, a membrane tube 16 is communicated with materials flowing upwards in the inner cylinder, and a cavity at the outer side of the membrane tube is communicated with an external hydrogen pipeline 20; a ceramic membrane nano/micron dispersion component 16 at the annular space part, a membrane tube 19 is communicated with an external hydrogen pipeline 17, and a cavity at the outer side of the membrane tube is communicated with a material flowing downwards in the annular space; in the hydrogenation reaction process, the ceramic membrane nano/micron dispersion component 16 at the inner cylinder part is a material from the lower part of the inner cylinder enters the membrane tube, hydrogen enters the outside of the membrane tube through an external hydrogen pipeline, and the hydrogen permeates and diffuses into the tube through the outside of the tube and is mixed with the material in the inner cylinder to be dissolved into a material containing the hydrogen and flows out of the membrane tube and flows downwards to generate the hydrogenation reaction; the ceramic membrane nanometer/micrometer dispersion assembly 16 of the annular space is that the supplies from the annular space enter the outside of the tube of membrane tube, hydrogen enters the tube of the tube 19 of membrane tube through the outside hydrogen pipeline 17, in the course that the hydrogen permeates and diffuses outside the tube through the tube, mix and dissolve with the supplies outside the tube as the supplies comprising hydrogen, carry on the stripping action to the supplies through the outer diffusion of hydrogen, can supplement hydrogen for the reaction later stage, inhibit the catalyst surface coking of high-temperature section of later stage from coking, can separate surface coking precursor and inhibit the timely stripping of the reactor forming gas at the same time, improve and strengthen the depth of reaction.
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 0.63% by mass of the feed oil (sum of fresh feed oil and cycle oil). The hydrogenation reactor adopts a catalyst FHUDS-5 of the comforting petrochemical research institute.
The fixed bed hydrogenation reaction conditions were as follows: the reaction temperature is 340-388 ℃, the reaction pressure is 6.5MPaG, the liquid hourly space velocity is 3.0h < -1 >, and the circulation ratio is 1.5-2.0.
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
By adopting the method shown in the attached figure 1, the catalyst adopted by the conical inner cylinder of the hydrogenation reactor is FHUDS-5 of the comforting petrochemical research institute, and the catalyst adopted by the annular space is FH-40C; the hydrogen contained in the feeding material of the hydrogenation reactor is 0.31 percent 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 0.24 percent 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 space is 0.05 percent 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 300-340 ℃, the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 5.0h -1 (ii) a The reaction conditions of the annular space are as follows: the reaction temperature is 330-358 ℃, the reaction pressure is 5.9MPaG, and the liquid hourly space velocity is 6.0h -1 . The ratio of the top plane diameter of the inner tapered cylinder in the reactor to the diameter of the reactor was 1.
The straight-run diesel oil and catalytic diesel oil in table 1 are 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 2
The method shown in the attached figure 1 is adopted, wherein a catalyst adopted by the conical inner cylinder of the hydrogenation reactor is FHUDS-2 of the comforting petrochemical research institute, and a catalyst adopted by the annular space is FH-40C; the hydrogen contained in the feeding material of the hydrogenation reactor is 0.26 percent 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 0.28 percent 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 space is 0.06 percent 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 315-352 ℃, the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 4.5h -1 (ii) a The reaction conditions of the annular space are as follows: the reaction temperature is 340-372 ℃, the reaction pressure is 5.9MPaG, and the liquid hourly space velocity is 7.5h -1 . The ratio of the top plane diameter of the inner tapered cylinder in the reactor to the diameter of the reactor was 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 fixed bed liquid phase hydrogenation, and the reaction conditions and the product properties are shown in 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-5 of the comforting petrochemical research institute, and the catalyst adopted by the annular space is FHUDS-2; the hydrogen contained in the feeding of the hydrogenation reactor is 0.22 percent 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 0.31 percent 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 space is 0.07 percent 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 318-348 ℃, the reaction pressure is 5.5MPaG,the liquid hourly space velocity is 5.0h -1 (ii) a The reaction conditions of the annular space are as follows: the reaction temperature is 338-375 ℃, the reaction pressure is 5.4MPaG, and the liquid hourly space velocity is 9.0h -1 . The ratio of the top plane diameter of the inner tapered cylinder in the reactor to the diameter of the reactor was 1.5.
TABLE 2 reaction conditions and product Properties (straight run diesel feedstock)
TABLE 3 reaction conditions and product Properties (catalytic Diesel feedstock)
As can be seen from the hydrogenation reaction effects of the examples and the comparative examples, the hydrogenation reactor and the hydrogenation method can realize rapid reaction at low and medium temperature sections, inhibit side reaction at high temperature section, and improve hydrogenation reaction rate and reaction depth. The method is mainly characterized in that the characteristic that the sectional area of a conical structure in the reactor is gradually reduced from bottom to top is utilized, the contact time of the raw material and the catalyst is controlled to be gradually shortened along with the rise of the reaction temperature, the coking on the surface of the catalyst is slowed down or controlled while the high-activity catalyst shows higher reaction rate, the flowing mode of the material in an annular space is from top to bottom, the characteristic that the sectional area of the annular space is gradually reduced from top to bottom is utilized, the contact time of the raw material and the catalyst is controlled to be gradually shortened when the temperature at the later stage of reaction is higher, the high-temperature coking on the surface of the catalyst can be further inhibited and slowed down or controlled during the reaction on the surface of the catalyst with slightly lower activity, and side reactions are reduced; the hydrogen is supplemented through the hydrogen supplementing component in the reaction process of the conical inner barrel, when the high consumption hydrogen in the reaction process is reached, the high dispersion hydrogen is timely supplemented, the driving force in the hydrogenation reaction process is increased, the medium and low temperature hydrogenation reaction rates are further improved, the hydrogen is supplemented through the hydrogen supplementing component in the annular space, the effects of hydrogen supplementation and steam stripping are achieved, reaction gas for inhibiting the hydrogenation reaction is stripped, and the deep hydrogenation reaction is achieved.
Claims (16)
1. A hydrogenation reactor characterized by: the reactor comprises an inner cylinder and a reactor shell, wherein the inner cylinder is conical, and an annular space with a cross-sectional area gradually reduced from top to bottom is formed between the inner cylinder and the reactor shell; the top and the bottom of the inner cylinder are open, and the edge of the bottom is hermetically connected with the inner wall of the reactor; the inner cylinder is filled with a hydrogenation catalyst I, the annular space is filled with a hydrogenation catalyst II, and the activity of the hydrogenation catalyst I is higher than that of the hydrogenation catalyst II; the middle part of the reactor is horizontally provided with a hydrogen replenishing component, the hydrogen replenishing component penetrates through the annular space and the cross section where the inner cylinder is located, and the hydrogen replenishing component is communicated with external hydrogen; the raw material inlet of the reactor is communicated with the bottom of the inner cylinder, and the product outlet of the reactor is communicated with the lower part of the annular space; the material flows from bottom to top in the inner cylinder; the material flows from top to bottom in the annular space; the hydrogen replenishing assembly is a ceramic membrane nano/micron hydrogen dispersing assembly which is of an integrated tube shell structure and comprises a plurality of ceramic membrane tubes and a shell, the ceramic membrane tubes are perpendicular to the cross section direction of the reactor, two ends of each membrane tube are fixed on a tube plate, and the shell is fixed on the inner surface of the reactor; a ceramic membrane nano/micron hydrogen dispersion component at the inner cylinder part, wherein a membrane tube is communicated with materials flowing upwards in the inner cylinder, and a cavity at the outer side of the membrane tube is communicated with an external hydrogen pipeline; the ceramic membrane nano/micron hydrogen dispersion assembly is arranged in the annular space, the membrane tube is communicated with an external hydrogen pipeline, and a cavity outside the membrane tube is communicated with materials flowing downwards in the annular space; the size of the nano/micron bubbles formed by the ceramic membrane nano/micron hydrogen dispersion component is 10-1000 nm.
2. The hydrogenation reactor of claim 1, wherein: the ratio of the diameter of the top plane of the inner cylinder to the diameter of the reactor is 1.05-1.
3. The hydrogenation reactor of claim 1, wherein: the hydrogen supplementing component comprises a pipeline communicated with external hydrogen and a component with hydrogen distribution or gas-liquid mixing functions.
4. The hydrogenation reactor of claim 1, wherein: the hydrogen replenishing assembly of the inner barrel part and the hydrogen replenishing assembly of the annular space part are respectively communicated with an external hydrogen pipeline.
5. The hydrogenation reactor according to claim 3, characterized in that: the component with hydrogen distribution or gas-liquid mixing function is one or more of a distribution pipe, a distribution plate, a static mixer, a microporous plate nano/micron hydrogen dispersion component or a ceramic membrane nano/micron hydrogen dispersion component.
6. A hydrogenation reactor according to claim 3, characterized in that: the ceramic membrane nano/micron hydrogen dispersion component positioned in the inner cylinder mainly has the functions of supplementing hydrogen and dissolving hydrogen again, and enhances the driving force of the hydrogenation reaction process in the low and medium temperature sections so as to maintain higher reaction rate; the ceramic membrane nano/micron hydrogen dispersion assembly located in the annular space has the main functions of hydrogen supplement and steam stripping, hydrogen supplement at the end of reaction is performed, coking on the surface of the catalyst at a high-temperature section at the end is inhibited, and meanwhile, a surface coking precursor and gas generated by the inhibition reactor are stripped and separated in time, so that the enhanced reaction depth is improved.
7. The hydrogenation reactor of claim 1, wherein: the top is reactor upper cover, and the bottom is reactor lower cover, and the raw materials entrance sets up material distributor for evenly distributed material gets into the inner tube.
8. The 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.
9. A hydrogenation method for a hydrogenation reactor as defined in any one of claims 1 to 8, characterized by comprising the following steps: the raw material containing hydrogen enters a conical inner cylinder through a feed inlet at the bottom of the reactor, and is subjected to hydrogenation reaction with a hydrogenation catalyst I filled in the inner cylinder, the material is subjected to hydrogen supplementation and hydrogen re-dissolution through a hydrogen supplementation component, flows out from the top of the inner cylinder, passes through the top of the reactor, enters an annular space from top to bottom, is subjected to further hydrogenation reaction with a hydrogenation catalyst II filled in the annular space, and is subjected to hydrogen supplementation and steam stripping through the hydrogen supplementation component, and the final reaction product is discharged from a discharge outlet at the bottom of the reactor; the activity of the hydrogenation catalyst I is higher than that of the hydrogenation catalyst II.
10. The method of claim 9, wherein: the ratio of the inner cylinder hydrogen supplement amount to the annular space hydrogen supplement amount is (100).
11. The method of claim 9, wherein: the residence time ratio of the materials in the inner barrel to the annular space is (100).
12. The method of claim 9, wherein: the hydrogenation reaction conditions of the inner cylinder are as follows: the reaction temperature is 60-360 ℃, the reaction pressure is 0.5-20.0 MPa, and the hourly space velocity of fresh feed liquid is 0.5h -1 ～10.0h -1 。
13. The method of claim 9, wherein: the hydrogenation reaction conditions of the annular space are as follows: the reaction temperature is 120-400 ℃, the reaction pressure is 0.5-20.0 MPa, and the hourly space velocity of fresh feed liquid is 0.5h -1 ～15.0h -1 。
14. The method of claim 9, wherein: the ratio of the activity of the hydrogenation catalyst I to the activity of the hydrogenation catalyst II is 1.05; wherein the level of activity is expressed as the amount of converted feed reactant per unit volume or mass of catalyst per unit time.
15. The method of claim 9, wherein: the hydrogenation catalyst is one or more of hydrofining catalyst, pre-hydrogenation refined catalyst, hydrogenation modified catalyst, selective hydrogenation catalyst, hydrotreating catalyst, hydrocracking catalyst or supplementary hydrogenation catalyst.
16. The method of claim 9, wherein: the annular space is filled with a hydrogenation catalyst with the activity which is wholly or partially lower than that of the inner cylinder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911020911.XA CN112705123B (en) | 2019-10-25 | 2019-10-25 | Hydrogenation reactor and hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911020911.XA CN112705123B (en) | 2019-10-25 | 2019-10-25 | Hydrogenation reactor and hydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112705123A CN112705123A (en) | 2021-04-27 |
| CN112705123B true CN112705123B (en) | 2022-10-11 |
Family
ID=75540541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911020911.XA Active CN112705123B (en) | 2019-10-25 | 2019-10-25 | Hydrogenation reactor and hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112705123B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116554918A (en) * | 2022-01-29 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst grading filling method for easy-coking oil hydrogenation |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2721291A1 (en) * | 1977-05-09 | 1978-11-23 | Ernst Kirchgaessner | Fuel hydrogasification reactor - with flow channels in inner cylinder wall and bottom carbonisation cone |
| CN1546217A (en) * | 2003-12-12 | 2004-11-17 | 华东理工大学 | Catalytic reforming and catalytic dehydrogenation centrifugal type fixed bed radial reactor |
| CN200949094Y (en) * | 2006-06-16 | 2007-09-19 | 中国石油化工股份有限公司 | Suspending bed hydrogenation reactor |
| CN101942325A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Heavy oil hydroprocessing method and reactor |
| CN102453528A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Multi-section boiling bed residual oil hydrogenation process method |
| CN202823315U (en) * | 2012-09-04 | 2013-03-27 | 山东齐鲁石化工程有限公司 | catalyst section-separating on-line regeneration |
| CN103657539A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工集团公司 | Fluidized bed reactor |
| CN204051631U (en) * | 2014-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | A kind of fluid distributor and fluid predistribution dish |
| CN107760371A (en) * | 2016-08-18 | 2018-03-06 | 北京华石联合能源科技发展有限公司 | A kind of hydrogenation reactor and hydrogenation technique |
| CN207159159U (en) * | 2017-09-11 | 2018-03-30 | 新能能源有限公司 | A kind of hydrogasification stove with semicoke refrigerated separation function |
| CN108014721A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of residual hydrogenation reactor |
-
2019
- 2019-10-25 CN CN201911020911.XA patent/CN112705123B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2721291A1 (en) * | 1977-05-09 | 1978-11-23 | Ernst Kirchgaessner | Fuel hydrogasification reactor - with flow channels in inner cylinder wall and bottom carbonisation cone |
| CN1546217A (en) * | 2003-12-12 | 2004-11-17 | 华东理工大学 | Catalytic reforming and catalytic dehydrogenation centrifugal type fixed bed radial reactor |
| CN200949094Y (en) * | 2006-06-16 | 2007-09-19 | 中国石油化工股份有限公司 | Suspending bed hydrogenation reactor |
| CN101942325A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Heavy oil hydroprocessing method and reactor |
| CN102453528A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Multi-section boiling bed residual oil hydrogenation process method |
| CN202823315U (en) * | 2012-09-04 | 2013-03-27 | 山东齐鲁石化工程有限公司 | catalyst section-separating on-line regeneration |
| CN103657539A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工集团公司 | Fluidized bed reactor |
| CN204051631U (en) * | 2014-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | A kind of fluid distributor and fluid predistribution dish |
| CN107760371A (en) * | 2016-08-18 | 2018-03-06 | 北京华石联合能源科技发展有限公司 | A kind of hydrogenation reactor and hydrogenation technique |
| CN108014721A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of residual hydrogenation reactor |
| CN207159159U (en) * | 2017-09-11 | 2018-03-30 | 新能能源有限公司 | A kind of hydrogasification stove with semicoke refrigerated separation function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112705123A (en) | 2021-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109679690B (en) | Liquid-phase hydrogenation system and liquid-phase hydrogenation method | |
| CN111068589B (en) | Liquid-phase hydrogenation system and liquid-phase hydrogenation method | |
| CN112705117B (en) | Liquid phase hydrogenation reactor and hydrogenation process | |
| CN111068587B (en) | Liquid phase hydrogenation reaction device and reaction method | |
| CN109679689B (en) | Liquid-phase hydrogenation reactor, hydrogenation reaction method and reaction system | |
| CN112705123B (en) | Hydrogenation reactor and hydrogenation method | |
| CN112705120B (en) | Heavy oil processing device and processing method | |
| KR20230093025A (en) | Reaction system and reaction method of multi-phase combination | |
| CN111298722A (en) | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material | |
| CN111068588B (en) | Diesel oil ultra-deep desulfurization device and diesel oil hydrogenation reaction system | |
| CN109679684B (en) | Liquid phase hydrogenation reaction system and method | |
| CN105713659A (en) | Hydrocarbon continuous liquid-phase hydrogenation process | |
| WO2021078186A1 (en) | Liquid phase reactor and application thereof | |
| CN112705122B (en) | Liquid phase hydrogenation reactor and hydrogenation method | |
| CN112705121B (en) | Fixed bed hydrogenation reactor and heavy oil liquid phase hydrogenation process | |
| CN112705119B (en) | Heavy oil hydrogenation reactor and hydrogenation method | |
| CN112705118B (en) | Heavy oil hydrogenation reactor and hydrogenation process | |
| CN114437779B (en) | Heavy oil hydrogenation process | |
| CN110117503A (en) | The combinational processing method of FCC recycle oil | |
| CN216799757U (en) | Liquid phase hydrogenation reaction device and system | |
| CN115785993B (en) | Diesel hydrogenation method and device | |
| CN115466628B (en) | Liquid phase hydrogenation reaction device and system and hydrocarbon oil phase hydrogenation method | |
| CN115703976A (en) | Method for removing olefin by liquid-phase hydrogenation of reformate | |
| CN116064121A (en) | Coal tar hydrotreating method and device | |
| CN109694301B (en) | Method for producing ethylene by using aromatic raffinate oil as raw material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231110 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |