CN111298722B - Hydrogenation reactor and hydrogenation method for hydrocarbon raw material - Google Patents
Hydrogenation reactor and hydrogenation method for hydrocarbon raw material Download PDFInfo
- Publication number
- CN111298722B CN111298722B CN201811513990.3A CN201811513990A CN111298722B CN 111298722 B CN111298722 B CN 111298722B CN 201811513990 A CN201811513990 A CN 201811513990A CN 111298722 B CN111298722 B CN 111298722B
- Authority
- CN
- China
- Prior art keywords
- section
- hydrogenation
- hydrogenation reaction
- reactor
- homogenizing
- 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 287
- 239000002994 raw material Substances 0.000 title claims abstract description 66
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 59
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 59
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000007791 liquid phase Substances 0.000 claims description 78
- 239000001257 hydrogen Substances 0.000 claims description 68
- 229910052739 hydrogen Inorganic materials 0.000 claims description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000265 homogenisation Methods 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 13
- 239000002101 nanobubble Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 206010013496 Disturbance in attention Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 etc. Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
-
- 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
- B01J8/0242—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 flow within the bed being predominantly vertical
-
- 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
- B01J8/0278—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
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
-
- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
- B01J8/065—Feeding reactive fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
-
- 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
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
-
- 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
- B01J2208/00008—Controlling the process
- B01J2208/00539—Pressure
Abstract
The invention discloses a hydrogenation reactor and a hydrogenation method for hydrocarbon raw materials, wherein the reactor is a 'n' -shaped tubular reactor and comprises a front homogenizing section, an up-flow type hydrogenation reaction section, an arc-shaped flow guide section, a down-flow type hydrogenation reaction section and a rear homogenizing section, and all the sections are communicated in sequence; the front homogenizing section and the rear homogenizing section are of horizontal tube structures, the upflow hydrogenation reaction section and the downflow hydrogenation reaction section are of vertical tube structures, and the arc-shaped flow guide section is of an arc structure communicating the upflow hydrogenation reaction section and the downflow hydrogenation reaction section; the front homogenizing section is provided with a reaction material inlet, and the rear homogenizing section is provided with a reaction material outlet. The invention can realize the uniform hydrogenation of light/heavy components in hydrocarbon raw materials, is beneficial to controlling the reaction conversion rate, reducing the radial temperature difference, reducing local hot spots, relieving carbon deposition and coking on the surface of the catalyst, and prolonging the service life of the catalyst and the start-up period of the device.
Description
Technical Field
The invention belongs to the field of petroleum processing, and particularly relates to a hydrogenation reactor and a hydrogenation method for a hydrocarbon raw material, which can be widely applied to a hydrogenation reaction process in the field of petrochemical industry.
Background
The liquid phase hydrogenation technology of oil products is a new type of hydrogenation technology, compared with the conventional trickle bed gas \ liquid \ solid three-phase hydrogenation process, the liquid phase hydrogenation technology eliminates the influence of hydrogen diffusion mass transfer, so that the hydrogenation reaction is carried out in a dynamic control area, and the pure liquid phase reaction is carried out in a reactor, thereby eliminating the influence of mass transfer of hydrogen from a gas phase to a liquid phase.
CN201510697566.9 discloses an upflow distributor and an upflow reactor, the upflow distributor comprises a shell, the lower part of which is provided with an opening. The invention provides a first distribution hole on a shell of an up-flow distributor, and the axes of a plurality of the first distribution holes are arranged to extend outwards and divergently from the shell. Through the technical scheme, the aim is to enable the fluid to flow out of the shell of the upflow distributor in a divergent mode through the first distribution holes, so that the fluid can be uniformly distributed after passing through the upflow distributor, and gas and liquid in the mixed fluid can be more uniformly mixed in the fluid distribution process. The method aims to mix the reaction gas and the liquid more uniformly, and does not solve the problems of poor concentration of light and heavy components and non-uniform reaction in the flowing process of materials. For an up-flow reactor, the movement rate of heavy components is slow, the retention time is long, the cracking reaction is easy to occur under the condition of hydrogen deficiency to cause the coking of the catalyst, particularly, the temperature at the final stage of the reaction is higher, the residual amount of hydrogen is small, and the coking reaction is easy to occur on a catalyst bed layer; although the reaction feed is fully contacted with the surface of the catalyst, a certain hydrotreating effect can be achieved, the coking materials generated at the later stage of the hydrogenation reaction at a high temperature are easy to adhere to the surface of the catalyst, so that the problem that the bed layer is blocked by the coking of the catalyst is caused.
CN201380060228.3 relates to a multilayer bed downflow reactor comprising vertically spaced beds of solid contact material, and a mixing device arranged in the interbed space between adjacent beds. In one aspect, the mixing device comprises a ring of first nozzles distributed around a vertical axis and arranged for injecting fluid into said inter-bed space in a first injection direction; in another aspect, the mixing device comprises a ring of second nozzles distributed around a vertical axis and arranged for injecting fluid into the inter-bed space in a second injection direction. The purpose of the method of the invention is to make the distribution of the fluid more uniform before entering the reactor or in the adjacent lower layer, so as to make the temperature of the fluid more uniform, but still not solve the problems of poor concentration of light and heavy components and uneven reaction generated in the material flowing process. In the case of the downflow reactor, the heavy component has a high moving rate and a short residence time, and thus there is a problem that the contact with the catalyst surface is insufficient, and some impurities such as sulfide, nitride, metal oxide, etc. are present in the heavy component, so that the desired effect of hydrotreating is not achieved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation reactor and a hydrogenation method for hydrocarbon raw materials. The invention can realize the uniform hydrogenation of light/heavy components in hydrocarbon raw materials, is beneficial to controlling the reaction conversion rate, reducing the radial temperature difference, reducing local hot spots, relieving carbon deposition and coking on the surface of the catalyst, and prolonging the service life of the catalyst and the start-up period of the device.
The hydrogenation reactor of the hydrocarbon raw material is a 'n' -shaped tubular reactor and comprises a front homogenizing section, an up-flow hydrogenation reaction section, an arc-shaped flow guide section, a down-flow hydrogenation reaction section and a rear homogenizing section, wherein all the sections are communicated in sequence; the front homogenizing section and the rear homogenizing section are of horizontal tube structures, the upflow hydrogenation reaction section and the downflow hydrogenation reaction section are of vertical tube structures, and the arc-shaped flow guide section is of an arc structure communicating the upflow hydrogenation reaction section and the downflow hydrogenation reaction section; the front homogenizing section is provided with a reaction material inlet, and the rear homogenizing section is provided with a reaction material outlet.
The front homogenizing section of the 'n' -shaped tubular reactor comprises a shell, an annular disperser and a central channel, wherein the shell of the annular disperser is fixed on the inner wall of the circular shell, membrane tube bundles are uniformly distributed on the annular disperser, and the shearing force of nano/micron hydrogen bubbles released by the membrane tube bundles is utilized to push and gather working liquid components from outside to inside and from the periphery to the central channel, so that a microscopically uniform hydrogen-dissolved material with light and heavy components enters an up-flow hydrogenation reaction section to carry out hydrogenation reaction; the length-diameter ratio of the front homogenizing section is 50: 1-1: 1, preferably 5: 1-15: 1; the liquid phase residence time of the front homogenizing section is 0.5-10 minutes, preferably 1.5-3.0 minutes. The upflow type hydrogenation reaction section of the tube-shaped reactor is communicated with the tail end of the front homogenizing section and is used for performing upflow type liquid phase hydrogenation reaction on the microscopically uniform hydrogen dissolving materials of light and heavy components formed by the front homogenizing section; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 0.5-1: 15, preferably 1: 1-1: 5.
The arc-shaped guide plate is arranged in the arc-shaped guide section of the n-shaped tubular reactor and is used for uniformly distributing and guiding the material flowing out of the upflow hydrogenation reaction section; the arc guide plates are preferably a plurality of groups of arc guide uniform distribution plates which are distributed at equal intervals, the guide uniform distribution plates can be in a shutter type, and the surface of the shutter can be appropriately provided with holes; the central angle of the arc is 0-360 degrees, preferably 180-270 degrees.
The downflow type hydrogenation reaction section of the tube-shaped reactor is connected with the front end of the rear homogenizing section and is used for carrying out downflow type liquid phase hydrogenation reaction on the material flowing out of the upflow type hydrogenation reaction section; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 0.5-1: 15, preferably 1: 1-1: 5.
In the tube-type reactor, the diameter of the upflow hydrogenation reaction section and the diameter of the downflow hydrogenation reaction section are the same or different, and the average flow velocity of the material in the upflow hydrogenation reaction section is lower, while the average flow velocity of the material in the downflow hydrogenation reaction section is higher, so as to ensure the reaction uniformity of the upflow and downflow, the diameter of the upflow hydrogenation reaction section is preferably smaller than or equal to that of the downflow hydrogenation reaction section, and the diameter ratio is generally 1: 10-1: 1.
The top and the bottom of the upflow hydrogenation reaction section and the top and the bottom of the downflow hydrogenation reaction section of the "n" shaped tubular reactor can be positioned at the same height or different heights, and are preferably positioned at a uniform height.
The structure of the rear homogenizing section of the 'n' -shaped tubular reactor is the same as that of the front homogenizing section, and the rear homogenizing section is used for re-dissolving hydrogen and homogenizing light and heavy components in the raw material for discharging of the downstream liquid phase hydrogenation reaction section, on one hand, dissolving hydrogen in the reaction material, and on the other hand, forcibly and uniformly mixing the light components in the reaction product in the heavy components to form hydrogen-dissolved material flow with uniformly micro-mixed hydrogen, light components and heavy components; the residence time of the liquid phase material in the post-homogenization section is 0.1-5.0 minutes, preferably 0.1-2.0 minutes.
The diameter ratio of the upflow hydrogenation reaction section to the front homogenizing section of the 'n' -shaped tubular reactor can be 15: 1-1: 5, preferably 5: 1-1: 1; the ratio of the downflow hydrogenation reaction zone to the post-homogenization zone may be 15:1 to 1:15, preferably 2:1 to 150: 1.
The tubular reactor is characterized in that the annular disperser of the front homogenizing section (the rear homogenizing section) is of a ceramic membrane tube bundle structure, one or more membrane tubes can be contained in the tube bundle, hydrogen is introduced into the tube, and the hydrogen is pushed by pressure difference to permeate and diffuse through nano/micron pore channels on the tube wall to form nano/micron bubbles which enter the shell space outside the tube and are dispersed into the liquid phase of the shell space to form a liquid phase raw material carrying the nano/micron bubble hydrogen. The size of the nano/micron bubble hydrogen is generally 10nm to 1000nm, preferably 50nm to 500 nm.
The 'n' -shaped tubular reactor, the upflow hydrogenation reaction section and the downflow hydrogenation reaction section can be filled with the same or different catalysts, the filled catalysts can use proper hydrogenation catalysts according to the reaction requirements to realize different hydrogenation purposes, such as hydrofining catalysts, pre-hydrogenation refined catalysts, hydrogenation modified catalysts, selective hydrogenation catalysts, hydrotreating catalysts, hydrocracking catalysts, supplementary hydrogenation catalysts 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.
The invention also provides a liquid phase hydrogenation reaction system, which comprises a plurality of 'n' -shaped tubular reactors connected in series, wherein the rear homogenizing section of the former reactor is communicated with the front homogenizing section of the latter reactor, and the number of the reactors is generally 2-10, preferably 2-5.
The invention also provides a liquid phase hydrogenation reaction system, which comprises a plurality of groups of 'n' -shaped tubular reactors and fixed bed reactors, wherein the 'n' -shaped tubular reactors are connected in series with the fixed bed reactors, a discharge hole of a rear homogenizing section of each 'n' -shaped tubular reactor is communicated with a feed hole of the fixed bed reactor, and the groups of reactors can be connected in parallel or in series.
The invention also provides a hydrogenation method of hydrocarbon raw materials, which adopts the 'n' -shaped tubular reactor and comprises the following contents:
(1) introducing hydrocarbon raw materials and hydrogen into a front homogenizing section of a 'n' -shaped tubular reactor, wherein the hydrocarbon raw materials enter a central channel in the front homogenizing section, the hydrogen enters an annular disperser in the front homogenizing section, the hydrogen is dispersed into micro/nano bubbles by the annular disperser, the micro/nano bubbles are dispersed and dissolved in the hydrocarbon raw materials in the central channel, and the hydrocarbon raw materials are mixed and homogenized under the action of the micro/nano bubbles to form homogenized materials;
(2) the homogenized material enters an upflow hydrogenation reaction section, contacts with a hydrogenation catalyst to carry out hydrogenation reaction to obtain a hydrogenation reaction product A, and the hydrogenation reaction product A is introduced into a downflow hydrogenation reaction section through an arc transition section to contact with the hydrogenation catalyst for further hydrogenation to obtain a hydrogenation reaction product B;
(3) the hydrogenation reaction product B enters a central channel in the post-homogenizing section, supplementary hydrogen is introduced into an annular disperser in the post-homogenizing section, and a gas phase and a liquid phase are mixed and homogenized to obtain a homogenized material which enters the next hydrogenation process.
In the method of the present invention, the hydrocarbon raw material in step (1) is generally a hydrocarbon raw material with any distillation range within 130 to 550 ℃, and may be selected from one or more of naphtha, reformed oil, aviation kerosene, diesel oil, wax oil, lubricating oil, atmospheric residue oil, deasphalted oil, biodiesel, animal oil or vegetable oil, and the like, preferably straight-run diesel oil, catalytic diesel oil or coker diesel oil.
In the process of the present invention, the mass ratio of hydrogen to hydrocarbon feedstock in the front homogenization section is generally from 0.001% to 15%, preferably from 0.1% to 8%, and the mass ratio of hydrogen to hydrocarbon feedstock in the rear homogenization section is generally from 0.001% to 5%, preferably from 0.01% to 1.0%.
In the method of the present invention, the liquid phase hydrogenation reaction process conditions are generally determined by those skilled in the art according to the raw material properties and the quality requirements of the final product. In the upflow hydrogenation reaction section, the process conditions are generally as follows: the reaction temperature is 150-450 ℃, the reaction pressure is 1-18 MPaG, and the liquid hourly space velocity is 10-150 h-1(ii) a The process conditions for the downflow hydrogenation reaction zone are generally: the reaction temperature is 150-450 ℃, the reaction pressure is 1-18 MPaG, and the liquid hourly space velocity is 50-500 h-1。
In the method, in the step (1), the retention time of the liquid phase material in the front homogenization section is 0.5-10 minutes, preferably 1.0-3.0 minutes, the uniform dissolution of hydrogen and the homogenization of light molecules and heavy molecules cannot be achieved by excessively short retention time, and nano/micron hydrogen bubbles can be aggregated and grow into large bubbles by excessively long retention time. The residence time of the liquid phase material in the rear homogenizing section is 0.1-5.0 minutes, preferably 0.1-2.0 minutes, and the residence time of the material in the rear homogenizing section can be shorter than that in the front homogenizing section, because the material in the rear homogenizing section passes through the homogenizing of the front homogenizing section and the up-flow/down-flow hydrogenation reaction section, the material existence device is relatively uniform, and the uniform mixing of hydrogen, light weight separation and heavy weight molecules can be achieved through the shorter residence time.
In the method of the present invention, the hydrogenation catalyst used can be a suitable hydrogenation catalyst according to the reaction requirements, such as a hydrorefining catalyst, a prehydrogenation refining catalyst, a hydroupgrading catalyst, a selective hydrogenation catalyst, a hydrotreating catalyst, a hydrocracking catalyst, a supplementary hydrogenation catalyst, etc., and various catalysts can be commercial catalysts or can be prepared according to the prior art. The catalytic reaction can remove the impurities of 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 carry out reactions of hydrocarbon molecule isomerization, alkylation, cyclization, aromatization, cracking and the like.
In the method of the invention, the next hydrogenation process in the step (3) can be a hydrogenation reaction of the homogenized material in a fixed bed liquid phase hydrogenation reactor or a hydrogenation reaction in a serial-connected 'n' -shaped tubular reactor; if left as a reaction product, step (3) does not require hydrogen make-up.
The invention has the following technical advantages: (1) based on the opposite change trends of the movement rate and the concentration distribution of light and heavy components in the hydrocarbon raw material in the hydrogenation reaction process, the special structure of the n-shaped reactor is utilized, so that the component distribution and the concentration gradient formed in the movement process of the hydrocarbon raw material can be kept in the whole hydrogenation reaction process, and the distribution of the light and heavy components and the hydrogenation reaction degree can be controlled; (2) because the solubility of hydrogen in light and heavy components is different in the hydrogenation reaction process, and the component concentration difference exists in the reaction process of the light and heavy components, a front homogenizing section is arranged before the reaction, on one hand, the uniform dissolution and dispersion of the hydrogen in the hydrocarbon raw material are completed, and simultaneously the uniform mixing between the light and heavy components is realized, so that the uniform hydrogenation reaction can be maintained within a longer retention time in the upflow type hydrogenation reaction process; (3) in the liquid phase hydrogenation reaction process, although the reaction material is in full contact with the catalyst in the upflow reaction process, the high-temperature coking of heavy molecules and the adhesion of coking substances on the surface of the catalyst can be increased in the upflow hydrogenation reaction mode due to the high temperature of the heavy components in the later reaction stage, so that the reaction material is introduced into the downflow hydrogenation reaction section, the high-temperature coking of the heavy molecules can be reduced or avoided by utilizing the principles that the gravity of the heavy components is large and the downflow movement rate is high, the formed coking substances are timely washed away on the surface of the catalyst, the adhesion of the coking substances on the surface of the catalyst is reduced, and the service life of the catalyst is prolonged.
Drawings
FIG. 1 is a schematic diagram of a hydrogenation reactor and reaction process for a hydrocarbon feedstock according to the present invention.
Figure 2 is a schematic representation of a series of several "n" shaped "hydrogenation reactors.
FIG. 3 is a schematic diagram of a "n" shaped hydrogenation reactor and a fixed bed hydrogenation reactor.
The reactor comprises a hydrocarbon raw material 1, a 'n' -shaped tubular reactor 2, hydrogen 3, hydrogen 4 and hydrogen 5, a front homogenizing section 6, an annular disperser 7, a ceramic membrane tube 8, a central channel 9, an up-flow hydrogenation reaction section 10, an up-flow hydrogenation reaction section 11, an up-flow hydrogenation reaction section catalyst bed 12, an arc flow guide section 13, an arc flow guide plate 14, a down-flow hydrogenation reaction section 15, a down-flow hydrogenation reaction section catalyst bed 15, a rear homogenizing section 16, an annular disperser 17, a ceramic membrane tube 18, a central channel 19, a reaction discharge material of the 'n' -shaped tubular reactor 20, a fixed bed reactor 21, a fixed bed reactor catalyst bed 22 and a fixed bed reactor discharge material 23.
Detailed Description
The invention is explained in more detail below with reference to the drawing description and the examples, without thereby restricting the invention.
The hydrogenation process of the hydrocarbon feedstock of the present invention is illustrated by way of example in the accompanying FIG. 1:
the hydrocarbon raw material 1 is introduced into a 'several' type tubular reactor 2, and the tubular reactor 2 is divided into a front homogenizing section 6, an up-flow type hydrogenation reaction section 10, a down-flow type hydrogenation reaction section 14 and a rear homogenizing section 16. Hydrocarbon raw materials firstly enter a central channel 9 of a front homogenizing section 6, hydrogen enters a ceramic membrane tube 8 in an annular disperser 7, the hydrogen forms micro/nano bubbles and is uniformly dispersed in the hydrocarbon raw materials under the pushing of the pressure difference between the inside and the outside of the membrane tube, and meanwhile, the hydrocarbon raw materials are gathered and mixed from the periphery to the central channel 9 to complete the dissolution of the hydrogen and the homogenization of light molecules and heavy molecules; introducing the material formed in the front homogenizing section 6 into an upflow hydrogenation reaction section catalyst bed layer 11 of an upflow hydrogenation reaction section 10 to perform an upflow hydrogenation reaction, so that light molecules and heavy molecules are subjected to uniform hydrogenation reaction; the material which finishes the upflow hydrogenation reaction enters the downflow hydrogenation reaction section 14 under the action of the arc-shaped guide plate 13 in the arc-shaped guide 12, and the downflow hydrogenation reaction is carried out in the catalyst bed layer 15 of the downflow hydrogenation reaction section; the reaction material finally enters a rear homogenizing section 17 of a rear homogenizing section, similar to the front homogenizing section, hydrogen forms micro/nano bubbles through a ceramic membrane tube 18 in an annular disperser 17 and is uniformly dispersed in the reaction material, meanwhile, the reaction material is gathered and mixed from the periphery to a central channel 19 to complete the dissolution of the hydrogen and the homogenization of light molecules and heavy molecules, a homogenizing product is used as a reaction material 20 and can leave a hydrogenation reaction device or enter a subsequent fixed bed reactor 21, the hydrogenation reaction is continuously carried out under the action of a fixed bed catalyst bed layer 22, and a discharged material 23 after the reaction leaves the hydrogenation reaction device as a hydrogenation reaction product
The raw oils used in the examples and comparative examples of the present invention were normal straight-run kerosene (raw oil 1) and normal straight-run diesel oil (raw oil 2) from an atmospheric and vacuum distillation unit of a certain plant, and specific properties are shown in table 1. The protecting agent/catalyst used in the examples is FBN-03B01/FH-40A and FHUDS-5 hydrofining catalyst of the comforting petrochemical research institute.
TABLE 1 Properties of the stock oils
Comparative example 1
A conventional fixed bed liquid phase hydrogenation reactor is adopted, wherein the height-diameter ratio of the liquid phase hydrogenation reactor is 2.5.
The hydrogenation reaction conditions were as follows: the reaction temperature is 245-280 ℃, the reaction pressure is 4.0MPaG, and the liquid hourly space velocity is 4.0h-1(ii) a FBN-03B01/FH-
A40A hydrogenation catalyst.
The feeding of the fixed bed liquid phase hydrogenation reactor is hydrogen-containing raw oil, wherein the mass fraction of hydrogen in the raw oil is 0.242%.
The normal straight-run kerosene in table 1 was used as a raw material, and a reaction product was obtained after liquid phase hydrogenation in a conventional fixed bed, and the product properties are shown in table 2.
Comparative example 2
A conventional fixed bed liquid phase hydrogenation reactor is adopted, wherein the height-diameter ratio of the liquid phase hydrogenation reactor is 2.5.
The hydrogenation reaction conditions were as follows: the reaction temperature is 340-365 ℃, the reaction pressure is 6.0MPaG, and the liquid hourly space velocity is 4.0h-1(ii) a FHUDS-5 hydrogenation catalyst of the petrochemical research institute is filled in the hydrogenation reactor.
The feeding of the fixed bed liquid phase hydrogenation reactor is hydrogen-containing raw oil, wherein the mass fraction of hydrogen in the raw oil is 0.357%.
The normal second-line straight-run diesel oil in the table 1 is used as a raw material, and a reaction product is obtained after the normal fixed bed liquid phase hydrogenation, and the product properties are shown in the table 2.
Example 1
The liquid phase hydrogenation reactor and the reaction method which are shown in the attached figure 1 are adopted, the liquid phase hydrogenation reactor contains 1 n-shaped tubular reactor, wherein the n-shaped tubular reactor comprises a front homogenizing section, an up-flow type hydrogenation reaction section, an arc-shaped flow guide section, a down-flow type hydrogenation reaction section and a rear homogenizing section.
Wherein the length-diameter ratio of the front homogenizing section is 10:1, and the liquid phase retention time is 3.0 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 5: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow type hydrogenation reaction section is 1: 3; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 5: 1; the residence time of the liquid phase material in the post-homogenization section was 1.5 minutes.
The feeding of the 'n' -shaped tubular reactor is hydrogen-containing raw oil, wherein the mass ratio of hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.205%, and the mass ratio of hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.021%.
The hydrogenation reaction conditions were as follows: the reaction temperature is 238-255 ℃; the reaction pressure was 4.0 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly space velocity of the downflow hydrogenation reaction section is 80h-1。
The normal straight-run kerosene in table 1 was used as a raw material, and a reaction product was obtained by liquid phase hydrogenation in several "type tubular reactors, and the product properties are shown in table 2.
Example 2
By adopting the liquid phase hydrogenation reactor and the reaction method shown in the attached figure 2, the liquid phase hydrogenation reactor comprises 3 n-shaped tubular reactors connected in series, and each n-shaped tubular reactor comprises a front homogenizing section, an upflow type hydrogenation reaction section, an arc-shaped flow guide section, a downflow type hydrogenation reaction section and a rear homogenizing section.
In the first 'n' -shaped tubular reactor, the length-diameter ratio of the front homogenizing section is 10:1, and the liquid phase retention time is 2.5 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 2; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 5: 1; the residence time of the liquid phase material in the post-homogenization section was 1.5 minutes. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.115%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.066%.
In the second 'n' -shaped tubular reactor, the length-diameter ratio of the front homogenizing section is 8:1, and the liquid phase retention time is 1.0 minute; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 5; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 30: 1; the residence time of the liquid phase material in the post-homogenization section was 1.0 minute. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.066%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.042%.
In the third 'several' type tubular reactor, the length-diameter ratio of the front homogenizing section is 5:1, and the liquid phase retention time is 0.5 min; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 1: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 5; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 50: 1; the residence time of the liquid phase material in the post-homogenization section was 0.5 minutes. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.042%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.012%.
The hydrogenation reaction conditions were as follows: the reaction temperature is 245-265 ℃; the reaction pressure was 4.0 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly space velocity of the downflow hydrogenation reaction section is 80h-1。
The reaction product is obtained by using the normal straight-run kerosene in table 1 as a raw material and carrying out liquid phase hydrogenation through three sets of tubular reactors connected in series, and the product properties are shown in table 2.
Example 3
The liquid phase hydrogenation reactor and the reaction method which are shown in the attached figure 3 are adopted, the liquid phase hydrogenation reactor comprises 1 n-shaped tubular reactor and a fixed bed reactor, the n-shaped tubular reactor and the fixed bed reactor are connected in series, and the n-shaped tubular reactor comprises a front homogenizing section, an up-flow type hydrogenation reaction section, an arc-shaped flow guide section, a down-flow type hydrogenation reaction section and a rear homogenizing section.
In a 'n' -shaped tubular reactor, the length-diameter ratio of a front homogenizing section is 8:1, and the liquid phase retention time is 2.0 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 3; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 10: 1; the residence time of the liquid phase material in the post-homogenization section was 1.0 minute. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.175%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.068%.
The hydrogenation reaction conditions were as follows: the reaction temperature is 245-265 ℃; the reaction pressure was 4.0 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly volume space velocity of the downflow type hydrogenation reaction section is 80h-1。
The feeding of the fixed bed reactor is a 'several' type tubular reactor, and the height-diameter ratio of the fixed bed reactor is 2.5.
The normal straight-run kerosene in table 1 was used as a raw material, and liquid phase hydrogenation was carried out in series with a set of several "type tubular reactors and a fixed bed reactor to obtain a reaction product, and the product properties are shown in table 2.
Example 4
The liquid phase hydrogenation reactor and the reaction method which are shown in the attached figure 1 are adopted, the liquid phase hydrogenation reactor contains 1 n-shaped tubular reactor, wherein the n-shaped tubular reactor comprises a front homogenizing section, an up-flow type hydrogenation reaction section, an arc-shaped flow guide section, a down-flow type hydrogenation reaction section and a rear homogenizing section.
Wherein the length-diameter ratio of the front homogenizing section is 10:1, and the liquid phase retention time is 3.0 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 5: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow type hydrogenation reaction section is 1: 3; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 5: 1; the residence time of the liquid phase material in the post-homogenization section was 1.5 minutes.
The feeding of the 'n' -shaped tubular reactor is hydrogen-containing raw oil, wherein the mass ratio of hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.205%, and the mass ratio of hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.021%.
The hydrogenation reaction conditions were as follows: the reaction temperature is 338-355 ℃; the reaction pressure was 6.0 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly space velocity of the downflow hydrogenation reaction section is 80h-1(ii) a The hydrogenation reactor is filled with FHUDS-5 hydrogenation catalyst of the petroleum chemical research institute.
The normal second-line straight-run diesel oil in the table 1 is used as a raw material, and a reaction product is obtained after liquid phase hydrogenation of a pipe type reactor, and the product properties are shown in the table 2.
Example 5
By adopting the liquid phase hydrogenation reactor and the reaction method shown in the attached figure 2, the liquid phase hydrogenation reactor comprises 3 n-shaped tubular reactors connected in series, and each n-shaped tubular reactor comprises a front homogenizing section, an upflow type hydrogenation reaction section, an arc-shaped flow guide section, a downflow type hydrogenation reaction section and a rear homogenizing section.
In the first 'n' -shaped tubular reactor, the length-diameter ratio of the front homogenizing section is 10:1, and the liquid phase retention time is 2.5 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 2; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 5: 1; the residence time of the liquid phase material in the post-homogenization section was 1.5 minutes. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.115%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.066%.
In the second 'n' -shaped tubular reactor, the length-diameter ratio of the front homogenizing section is 8:1, and the liquid phase retention time is 1.0 minute; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 5; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 30: 1; the residence time of the liquid phase material in the post-homogenization section was 1.0 minute. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.066%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.042%.
In the third 'n' -shaped tubular reactor, the length-diameter ratio of the front homogenizing section is 5:1, and the liquid phase retention time is 0.5 min; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 1: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 5; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 50: 1; the residence time of the liquid phase material in the post-homogenization section was 0.5 minutes. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.042%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.012%.
The hydrogenation reaction conditions were as follows: the reaction temperature is 330-355 ℃; the reaction pressure was 6.0 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly space velocity of the downflow hydrogenation reaction section is 80h-1(ii) a FHUDS-5 hydrogenation catalyst of the petrochemical research institute is filled in the hydrogenation reactor.
The normal second-line straight-run diesel oil in the table 1 is used as a raw material, and a reaction product is obtained after liquid phase hydrogenation is carried out through the series connection of three groups of pipe type reactors, and the product properties are shown in the table 2.
Example 6
The liquid phase hydrogenation reactor and the reaction method which are shown in the attached figure 3 are adopted, the liquid phase hydrogenation reactor comprises 1 n-shaped tubular reactor and a fixed bed reactor, the n-shaped tubular reactor and the fixed bed reactor are connected in series, and the n-shaped tubular reactor comprises a front homogenizing section, an up-flow type hydrogenation reaction section, an arc-shaped flow guide section, a down-flow type hydrogenation reaction section and a rear homogenizing section.
In a 'n' -shaped tubular reactor, the length-diameter ratio of a front homogenizing section is 8:1, and the liquid phase retention time is 2.0 minutes; the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 3: 1; the height-diameter ratio of the upflow hydrogenation reaction section is 1: 1; the height-diameter ratio of the downflow hydrogenation reaction section is 1: 3; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 10: 1; the residence time of the liquid phase material in the post-homogenization section was 1.0 minute. Wherein the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.175%, and the mass ratio of the hydrogen to the hydrocarbon raw material in the rear homogenizing section is 0.068%.
The hydrogenation reaction conditions in the "n" type tubular reactor were as follows: the reaction temperature is 330-350 ℃; the reaction pressure was 60 MPaG; the liquid hourly volume space velocity of the upflow hydrogenation reaction section is 40h-1The liquid hourly space velocity of the downflow hydrogenation reaction section is 80h-1。
The hydrogenation reaction conditions in the fixed bed reactor were as follows: the reaction temperature is 345-355 ℃; the reaction pressure was 5.5 MPaG; the liquid hourly space velocity is 6.0h-1。
The feeding of the fixed bed reactor is a 'several' type tubular reactor, and the height-diameter ratio of the fixed bed reactor is 2.5. The normal second-line straight-run diesel oil in the table 1 is taken as raw material and passes through a group of several-shaped tubular reactors and a fixed bed reactor
The reactors are connected in series to carry out liquid phase hydrogenation to obtain a reaction product, and the properties of the product are shown in Table 2.
TABLE 2 Properties of the products
As can be seen from the hydrogenation effects of the present embodiment and the comparative example, the liquid phase hydrogenation reactor and the hydrogenation method of the present invention have the following advantages: (1) compared with the traditional fixed bed liquid phase hydrogenation reaction process, the single 'n' -shaped tubular reactor has more ideal hydrogenation reaction effect, lower reaction temperature, higher average airspeed, smaller total volume of the reactor and more uniform hydrogenation reaction; (2) hydrogenation reaction is carried out through a plurality of 'n' -shaped tubular reactors connected in series, the total volume of the reactors is further reduced, and deep desulfurization and denitrification can be realized under the same reaction condition under the more moderate condition; (3) the 'n' -shaped tubular reactor and the fixed bed reactor are connected in series to generate a liquid phase hydrogenation reaction, the 'n' -shaped tubular reactor generates a small part of hydrogenation reaction, and the fixed bed reactor generates a large part of hydrogenation reaction, so that the volume of the total reactor is reduced, and deep desulfurization and denitrification are realized under a slightly mild condition under the condition that the hydrogenation reaction system is not greatly changed. According to the embodiment of the invention, the 'n' -shaped tubular reactor is arranged, so that the light/heavy components of the raw material are uniformly hydrogenated, the reaction conversion rate is favorably controlled, the radial temperature difference is reduced, local hot spots are reduced, carbon deposition and coking on the surface of the catalyst are relieved, the service life of the catalyst is prolonged, and the start-up period of the device is prolonged.
Claims (20)
1. A hydrogenation reactor for a hydrocarbon feedstock characterized by: the hydrogenation reactor is a 'U' -shaped tubular reactor with a 'U' -shaped structure, and comprises a front homogenizing section, an up-flow hydrogenation reaction section, an arc-shaped flow guide section, a down-flow hydrogenation reaction section and a rear homogenizing section, and all the sections are communicated in sequence; the front homogenizing section and the rear homogenizing section are of horizontal tube structures, the upflow hydrogenation reaction section and the downflow hydrogenation reaction section are of vertical tube structures, and the arc-shaped flow guide section is of an arc structure communicating the upflow hydrogenation reaction section and the downflow hydrogenation reaction section; the front homogenizing section is provided with a reaction material inlet, and the rear homogenizing section is provided with a reaction material outlet; the front homogenizing section comprises a shell, an annular disperser and a central channel, the shell of the annular disperser is fixed on the inner wall of the circular shell, and the membrane tube bundles are uniformly distributed on the annular disperser; the upflow type hydrogenation reaction section is communicated with the tail end of the front homogenizing section and is used for carrying out upflow type liquid phase hydrogenation reaction on the light and heavy component microcosmically uniform dissolved hydrogen material formed by the front homogenizing section; the arc-shaped guide plates are arranged in the arc-shaped guide section and are used for uniformly distributing and guiding the material flowing out of the upflow hydrogenation reaction section; the downflow type hydrogenation reaction section is connected with the front end of the rear homogenizing section and is used for carrying out downflow type liquid phase hydrogenation reaction on the material flowing out of the upflow type hydrogenation reaction section; the post-homogenizing section comprises a shell, an annular disperser and a central channel, wherein the shell of the annular disperser is fixed on the inner wall of the circular shell, and the tube bundles of the membrane tubes are uniformly distributed on the annular disperser; used for re-dissolving hydrogen and homogenizing light and heavy components in the raw material for the discharge of the downflow liquid phase hydrogenation reaction section.
2. The hydrogenation reactor of claim 1, wherein: the length-diameter ratio of the front homogenizing section is 50: 1-1: 1.
3. The hydrogenation reactor of claim 1, wherein: the height-diameter ratio of the upflow hydrogenation reaction section is 1: 0.5-1: 15.
4. The hydrogenation reactor of claim 1, wherein: the central angle of the arc-shaped flow guide section is 180-270 degrees.
5. The hydrogenation reactor of claim 1, wherein: the height-diameter ratio of the downflow hydrogenation reaction section is 1: 0.5-1: 15.
6. The hydrogenation reactor of claim 1, wherein: the diameter ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the downflow hydrogenation reaction section is 1: 10-1: 1.
7. The hydrogenation reactor of claim 1, wherein: the ratio of the diameter of the upflow hydrogenation reaction section to the diameter of the front homogenizing section is 15: 1-1: 5; the ratio of the diameter of the downflow hydrogenation reaction section to the diameter of the after-homogenizing section is 15: 1-1: 15.
8. The hydrogenation reactor of claim 1, wherein: the annular disperser is a ceramic membrane tube bundle structure, the tube bundle comprises one or more membrane tubes, hydrogen is introduced into the tubes, and the hydrogen is pushed by pressure difference to permeate and diffuse through nano/micron pore channels on the tube wall to form nano/micron bubbles which enter the shell space outside the tubes and are dispersed into the liquid phase in the shell space to form a liquid phase raw material carrying the nano/micron bubble hydrogen; the size of the nano/micron bubble hydrogen is 10-1000 nm.
9. A liquid phase hydrogenation reaction system, characterized by: the system comprises a plurality of hydrogenation reactors according to any one of claims 1 to 8 connected in series, wherein the rear homogenizing section of the former reactor is communicated with the front homogenizing section of the latter reactor.
10. A liquid phase hydrogenation reaction system, characterized by: the system comprises a plurality of groups of hydrogenation reactors and fixed bed reactors as claimed in any one of claims 1 to 8, wherein a plurality of tube-type reactors and the fixed bed reactors are connected in series, a discharge port of a post homogenization section of the tube-type reactor is communicated with a feed port of the fixed bed reactor, and the reactors of each group are connected in parallel or in series.
11. A process for the hydrogenation of a hydrocarbonaceous feedstock, characterized in that: the method adopts the hydrogenation reactor as defined in any one of claims 1 to 8.
12. The method of claim 11, comprising: (1) introducing hydrocarbon raw materials and hydrogen into a front homogenizing section of a 'n' -shaped tubular reactor, wherein the hydrocarbon raw materials enter a central channel in the front homogenizing section, the hydrogen enters an annular disperser in the front homogenizing section, the hydrogen is dispersed into micro/nano bubbles by the annular disperser, the micro/nano bubbles are dispersed and dissolved in the hydrocarbon raw materials in the central channel, and the hydrocarbon raw materials are mixed and homogenized under the action of the micro/nano bubbles to form homogenized materials; (2) the homogenized material enters an upflow hydrogenation reaction section, contacts with a hydrogenation catalyst to carry out hydrogenation reaction to obtain a hydrogenation reaction product A, and the hydrogenation reaction product A is introduced into a downflow hydrogenation reaction section through an arc transition section to contact with the hydrogenation catalyst for further hydrogenation to obtain a hydrogenation reaction product B; (3) the hydrogenation reaction product B enters a central channel in the post-homogenizing section, supplementary hydrogen is introduced into an annular disperser in the post-homogenizing section, and a gas phase and a liquid phase are mixed and homogenized to obtain a homogenized material which enters the next hydrogenation process.
13. The method of claim 11, wherein: the hydrocarbon raw material is any fraction with the distillation range of 130-550 ℃.
14. The method of claim 11, wherein: the mass ratio of the hydrogen to the hydrocarbon raw material in the front homogenizing section is 0.001-15%.
15. The method of claim 11, wherein: the mass ratio of the hydrogen to the hydrocarbon raw material in the post-homogenizing section is 0.001-5%.
16. The method of claim 11, wherein: the process conditions of the upflow hydrogenation reaction section are as follows: the reaction temperature is 150-450 ℃, the reaction pressure is 1-18 MPaG, and the liquid hourly space velocity is 10-150 h-1。
17. The method of claim 11, wherein: the process conditions of the downflow hydrogenation reaction section are as follows: the reaction temperature is 150-450 ℃, the reaction pressure is 1-18 MPaG, and the liquid hourly space velocity is 50-500 h-1。
18. The method of claim 11, wherein: the residence time of the liquid-phase material in the front homogenizing section is 0.5-10 minutes.
19. The method of claim 11, wherein: the residence time of the liquid-phase material in the post-homogenization section is 0.1-5.0 minutes.
20. The method of claim 11, wherein: the hydrogenation catalyst is a hydrofining catalyst, a prehydrogenation refining catalyst, a hydrogenation modification catalyst, a selective hydrogenation catalyst or a hydrocracking catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811513990.3A CN111298722B (en) | 2018-12-12 | 2018-12-12 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811513990.3A CN111298722B (en) | 2018-12-12 | 2018-12-12 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111298722A CN111298722A (en) | 2020-06-19 |
| CN111298722B true CN111298722B (en) | 2022-07-12 |
Family
ID=71161246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811513990.3A Active CN111298722B (en) | 2018-12-12 | 2018-12-12 | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111298722B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871337A (en) * | 2020-07-16 | 2020-11-03 | 南京延长反应技术研究院有限公司 | Micro-interface reaction system and method for diesel hydrogenation |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6554994B1 (en) * | 1999-04-13 | 2003-04-29 | Chevron U.S.A. Inc. | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
| CN101831318B (en) * | 2009-03-09 | 2015-07-22 | 催化蒸馏技术公司 | Use of catalytic distillation for benzene separation and purification |
| CN102443435A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Heavy oil hydrogenation method utilizing partition plate type reactor |
| CN102453529A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Method for processing heavy material by using up-flow reactor system |
| CN103059938B (en) * | 2011-10-21 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of heavy hydrocarbon hydroprocessing method |
| CN103540350B (en) * | 2012-07-12 | 2015-10-28 | 中国石油天然气股份有限公司 | A kind of inferior heavy oil, hydrotreatment combination process |
| CN104927898B (en) * | 2014-03-21 | 2017-02-08 | 中国石油化工股份有限公司 | Hydrocarbon oil hydrotreatment method |
| EP3394218A4 (en) * | 2015-12-21 | 2019-07-24 | Uop Llc | Staged introduction of additives in slurry hydrocracking process |
| CN108018084B (en) * | 2016-11-01 | 2020-10-16 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method for improving catalyst utilization rate |
| RU2681527C1 (en) * | 2016-12-30 | 2019-03-07 | Бейджинг Хуаши Юнайтед Энерджи Технолоджи энд Девелопмент Ко., Лтд. | Light petroleum products from heavy oil production method and device by the hydrogenation in the fluidized bed method |
| CN206872743U (en) * | 2017-01-06 | 2018-01-12 | 中国石油化工股份有限公司 | A kind of hydrocarbon ils pretreatment unit and a kind of hydrocarbon oil hydrogenation processing system |
-
2018
- 2018-12-12 CN CN201811513990.3A patent/CN111298722B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111298722A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111068589A (en) | Liquid-phase hydrogenation system and liquid-phase hydrogenation method | |
| CN102311761B (en) | Low hydrogen-oil ratio hydrotreating method and reactor | |
| CN111298722B (en) | Hydrogenation reactor and hydrogenation method for hydrocarbon raw material | |
| CN109679689B (en) | Liquid-phase hydrogenation reactor, hydrogenation reaction method and reaction system | |
| CN111068587B (en) | Liquid phase hydrogenation reaction device and reaction method | |
| CN111690433B (en) | FCC feedstock liquid phase hydroprocessing system and method | |
| CN112705117B (en) | Liquid phase hydrogenation reactor and hydrogenation process | |
| KR20230093025A (en) | Reaction system and reaction method of multi-phase combination | |
| EP4238636A1 (en) | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method | |
| CN109679684B (en) | Liquid phase hydrogenation reaction system and method | |
| WO2021078186A1 (en) | Liquid phase reactor and application thereof | |
| CN115090221B (en) | Microbubble downflow hydrogenation reactor | |
| JP6395709B2 (en) | Hydrocarbon oil hydrotreating method | |
| RU2704610C1 (en) | Method of increasing output of hydrocarbons from a unit for catalytic reforming | |
| CN112705123B (en) | Hydrogenation reactor and hydrogenation method | |
| CN109722281B (en) | Fluidized bed reactor with multiple catalysts for internal circulation and hydrogenation method thereof | |
| CN114437779B (en) | Heavy oil hydrogenation process | |
| CN114479925B (en) | Heavy oil hydrogenation reaction system and heavy oil hydrogenation method | |
| CN112705122B (en) | Liquid phase hydrogenation reactor and hydrogenation method | |
| CN114479933B (en) | Heavy oil hydrogenation reaction system and hydrogenation method | |
| CN115106023B (en) | Gas-liquid two-phase reactor, application thereof and hydrocarbon oil hydrogenation method | |
| CN112705118B (en) | Heavy oil hydrogenation reactor and hydrogenation process | |
| CN112705119B (en) | Heavy oil hydrogenation reactor and hydrogenation method | |
| CN112705120B (en) | Heavy oil processing device and processing method | |
| CN113563925B (en) | Method for producing jet fuel |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231025 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. |