CN105296002B - Coal tar cleaning puies forward the method and system that phenol back end hydrogenation produces fuel oil - Google Patents
Coal tar cleaning puies forward the method and system that phenol back end hydrogenation produces fuel oil Download PDFInfo
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- CN105296002B CN105296002B CN201510790846.4A CN201510790846A CN105296002B CN 105296002 B CN105296002 B CN 105296002B CN 201510790846 A CN201510790846 A CN 201510790846A CN 105296002 B CN105296002 B CN 105296002B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011280 coal tar Substances 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004140 cleaning Methods 0.000 title claims abstract description 31
- 239000000295 fuel oil Substances 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 239000003921 oil Substances 0.000 claims abstract description 64
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000002283 diesel fuel Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 13
- 238000004073 vulcanization Methods 0.000 claims description 9
- 239000010742 number 1 fuel oil Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 25
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 239000003502 gasoline Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000002989 phenols Chemical class 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- -1 furfuran compound Chemical class 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000036642 wellbeing Effects 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The method and system that phenol back end hydrogenation produces fuel oil are put forward the present invention relates to a kind of cleaning of coal tar.Coal tar feeding destilling tower is isolated rich phenol cut and other cuts by technical scheme, rich phenol cut cleaning carries the oil of the dephenolize after phenol as solvent naphtha and catalyst, vulcanizing agent, which is mixed and vulcanized, is made catalyst pulp, other cuts mix feeding slurry bed system hydrocracking reactor with catalyst pulp and carry out hydrocracking reaction, it is re-fed into thermal release system and isolates hydrogen-rich gas, light oil and the tail oil containing catalyst, light oil feeding fixed bed hydrogenation reactor carries out hydrofining reaction, obtained reactant feeding fractionating column isolates gaseous hydrocarbon, gasoline fraction, diesel oil distillate.Present invention process is simple, raw material availability is high, and environmentally friendly, production cost and operating cost are low, it is simple to safeguard, it is high to improve catalyst service life, product yield.
Description
Technical field
The present invention relates to a kind of production method of fuel oil and system, specifically a kind of coal tar cleaning is carried after phenol
The method and system of hydrogenation production fuel oil.
Background technology
With rapid economic development, market is growing day by day for the demand of light-end products, and coal tar hydrogenating is its lightweight
The effective way changed and cleaned, is also the main probing direction that coal tar processing is utilized.Coal tar is that coal coking, destructive distillation are gentle
The accessory substance of change.Full fraction of coal tar is different from crude oil or heavy oil, and it constitutes complicated, aromatic hydrocarbons, resin and asphalt content phase
To height, particularly oxygen content is in 8wt% or so.Wherein oxygen is main exists in the form of phenols and furfuran compound, and phenols
Compound is one of base stock of chemical industry, and added value is higher.Traditional coal tar processing route mainly has two kinds, being of one kind
Work route, although recovery rate can reach more than 95%, but often handling 1 ton of raw material containing phenol needs the alkali of nearly 0.2 ton of consumption, together
When produce a large amount of reluctant phenol wastewater.And another route is hydrogenation route, coal tar is after hydrogenation except can be with
Hetero atoms (such as metal, sulphur, nitrogen and oxygen) most in coal tar are removed outside, it also occur that macromolecular in hydrogenation process
Cracking, aromatic hydrocarbons open loop saturation, alkene saturation etc. are reacted, and may finally produce the light-end products of cleaning.For hydrogenation route
Speech, also form kinds of processes and supporting catalyst at present.
CN1351130A discloses in a kind of method of producing diesel by utilizing coal tar, the patent to be less than 370 in coal tar
DEG C light fraction be refining to obtain diesel product by fixed bed hydrogenation for raw material, catalyst used for Hydrobon catalyst with
Dearomatization catalyst.The light fraction being primarily adapted for use in coal tar of the technique, can not handle full fraction of coal tar, particularly
Heavy distillat.Full fraction of coal tar or heavy distillat resin and asphalt content are high, and fixed bed reactors are difficult to；Secondly evaporate entirely
Point or heavy distillat in contain micron-sized coal dust, these micron-sized coal dusts once entrance fixed bed reactors after will soon
Cause the obstruction of beds.In addition, into phenols is rich in the light fraction of fixed bed, phenols is directly entered hydrofinishing section
Water will be produced after hydrogenation reaction, water is all adversely affected for the life-span of hydrogenation catalyst and activity, and is added
Hydrogen consumes.CN101240191A discloses a kind of method of producing lightweight fuel oil by coal tar heavy fractioning hydrogenation, and this method is using solid
Fixed bed hydrofinishing-be hydrocracked-hydro-upgrading group technology.Although the technique can handle the heavy distillat in coal tar,
It is that technological process is complicated, in addition to needing the reactor and catalyst of three kinds of difference in functionalitys, in addition it is also necessary to increase after hydrofining reaction
If the water that piece-rate system is formed with discharging in hydrogenation process, to avoid adversely affecting hydrocracking catalyst.The above two
Plant technique and use fixed-bed process, therefore also there are corresponding requirements for coal tar raw material, raw material has to pass through multiple pretreatment
The solid impurity (such as coal dust, ash grades) gone afterwards could be fed.CN1766058A, which discloses a kind of coal tar and evaporates suspension bed entirely, to be added
Hydrogen process, its catalyst is water-soluble homogeneous catalyst.Compared to fixed bed hydrogenation, suspension bed hydrogenation process, which can be handled, to be contained
There is the inferior raw material of impurity, and can maximized utilization raw material production light-end products.But full fraction of coal tar hydrogenation can be by
The phenolic compound of high added value is changed into hydro carbons and water in tar, on the one hand reduces added value；On the other hand increase hydrogen consumes,
The presence of water simultaneously can also reduce the activity of catalyst and the corrosion of life-span and increase equipment and pipeline.In addition, the technique makes
Water-soluble phosphorus nikel molybdate is used, the dispersed sulfur system of this kind of catalyst is huge, equipment is complicated, high energy consumption.
The content of the invention
The invention aims to solve above-mentioned technical problem there is provided a kind of technique is simple, raw material availability is high, to ring
Border is friendly, production cost and operating cost are low, it is simple to safeguard, improves catalyst service life, product yield height, ensure that system is long
The coal tar cleaning of phase stable operation puies forward the method that phenol back end hydrogenation produces fuel oil.
The present invention also provides a kind of coal tar low for simple system, the reliable, equipment investment cost of the above method and added
The system that hydrogen produces fuel oil.
The inventive method comprises the following steps：
(1) coal tar feeding destilling tower normal pressure is isolated into rich phenol cut and other cuts, the rich phenol cut enters clear
The clean phenol system that carries carries out cleaning and carries phenol obtaining dephenolize oil of the phenol content less than 3.5wt%, and dephenolize oil feeding catalyst slurry batch can is made
Catalyst pulp is made with catalyst and vulcanizing agent mixing vulcanization for solvent naphtha；
(2) vulcanized after catalyst raw material, solvent and vulcanizing agent mixing, the condition of vulcanization is：Hydrogen to oil volume ratio (mark condition
Under)：400-600,230 DEG C of temperature vulcanizes and vulcanizes 3-5h at 3-5h, 320 DEG C, hydrogen pressure 3-6MPa, and vulcanizing agent is DMDS
Ether.Catalyst pulp after the completion of vulcanization mixes feeding slurry bed system hydrocracking reaction with the other cuts obtained in step (1)
Hydrocracking reaction is carried out in device in the presence of hydrogen, obtained reactant feeding thermal release system isolates hydrogen-rich gas, lightweight
Oil and the tail oil containing catalyst；
(3) light oil obtained in step (2) feeding fixed bed hydrogenation reactor is subjected to hydrofining reaction, obtained
Reactant feeding fractionating column isolates naphtha and diesel oil.In the step (1), the vulcanizing agent catalyst, urge vulcanizing agent and
The mixing quality ratio of dephenolize oil is 1:(2-5):(4-7).
In the step (2), the mixing quality ratio of catalyst (being counted using active component oxide) and other cuts is 0.5-
5:100, more preferably 1-3:100.
In the step (2), the reaction temperature for controlling the slurry hydrocracking reactor is 330-480 DEG C, reaction pressure
Power：12-20MPa, volume space velocity is 0.1-3.0h-1, hydrogen to oil volume ratio (mark condition under) is：1000-2000.
In the step (3), the hydrogen-rich gas isolated can be hydrocracked instead as hydrogen feeding slurry bed system is filled into
Answer in device.
In the step (2), the tail oil containing catalyst is recycled back to slurry bed system hydrocracking reactor in whole or in part
Participate in reaction.
In the step (3), 300-400 DEG C of the reaction temperature of the fixed bed hydrogenation reactor, reaction pressure 6- are controlled
12MPa, volume space velocity：0.1-3.0h-1, hydrogen to oil volume ratio is 400-1200.
Present system includes the destilling tower being sequentially connected, slurry bed system hydrocracking reactor, thermal release system, fixed bed
Hydrogenation reactor and fractionating column, wherein, the cleaned phenol system that carries of the destilling tower top exit connects with catalyst slurry batch can entrance
Connect, the catalyst slurry batch can outlet is connected with the entrance of slurry bed system hydrocracking reactor.
The outlet at bottom of the thermal release system is respectively with the entrance of slurry bed system hydrocracking reactor and being out-of-bounds connected.
The problem of for being deposited in background technology, inventor be considered as destilling tower will by distillation cut out rich phenol cut and
Other cuts, cutting temperature can be adjusted according to raw material actual conditions between 150-300 DEG C, and cutting temperature temperature preferably is
170-260 DEG C, the rich phenol composition isolated carries by cleaning and dephenolize oil is obtained after phenol system isolates crude phenols, carries out cleaning and carries phenol
Can extract to greatest extent added value in coal tar it is higher contain phenolic compounds, while being greatly lowered in technique useless containing phenol
The discharge of water, reduces environmental pollution, and crude phenols can further obtain crude phenols byproduct, be refining to obtain smart phenolic product.For cleaning
The dephenolize oil obtained after phenol is carried, inventor has found, when phenol content is less than 3.5wt% in dephenolize oil, can be added as solvent naphtha
Carry out being mixed and made into catalyst mixed slurry with catalyst, vulcanizing agent in catalyst slurry batch can, dephenolize oil is substituted into the molten of routine
Agent oil, which prepares catalyst mixed slurry, some following benefit：(1) because dephenolize oil is inherently derived from coal tar raw material, do not deposit
In the compatibility issues of oil product, therefore the catalyst mixed slurry prepared using it as raw material other can evaporate with what distillation be partitioned into
Divide preferably mixing, preferably promotion catalyst disperseing in other cuts.(2) due to the phenols in dephenolize oil substantially
It is removed, dephenolize oil will not be adversely affected to the activity of catalyst or life-span.(3) phenol technique is carried by cleaning, makes to take off
Carbolic oil substitutes solvent naphtha and enters system, saves production cost, farthest using raw material, is carried by distilling segmentation and cleaning
Phenol, the phenol in coal tar is removed in advance, and being greatly decreased for phenol content can reduce hydrogenation process in subsequent technique material
The generation of middle waste water, is adversely affected so as to avoid to catalyst in fixed bed hydrogenation reactor, is solved secondary in technique
Reaction produces the various problems that water is brought, and also reduces the consumption of hydrogen.(4) added value of phenol products in itself is high, particularly
The high middle coalite tar containing phenols, can improve the economic well-being of workers and staff of whole technique；Simultaneously because the extraction of phenols, after reducing
The hydrogen consumption of continuous hydrogenation system.
The method that the cleaning carries phenol can put forward phenol technology, such as patent using existing environment amenable various coal tar
Number be CN201410080517.6, entitled " separation method of phenolic compound and nitrogen-containing compound in coal tar " it is clear
Clean to put forward phenol technique, its technique is simple, environmentally friendly, do not produce phenol wastewater, energy Fast synchronization removes phenols chemical combination and nitrogenous
Compound, removal effect are good.
Catalyst in the catalyst mixed slurry can use molybdenum base, iron-based, Ni-based or complex class catalyst,
The vulcanizing agent can be used in the one or more in sulphur, carbon disulfide, dimethyl sulfide, the present invention, due to using de-
Carbolic oil reduces the compatibility issues of different oil products as solvent naphtha, makes the dispersiveness of catalyst more preferable, and then improves catalysis effect
Fruit and catalyst service life, therefore vulcanizing agent catalyst, urge vulcanizing agent and dephenolize oil mixing quality ratio be 1:(2-5):
The mixing quality ratio of (4-7), catalyst (being counted using active component oxide) and other cuts is 0.5-5:100, more preferably
1-3:100。
Beneficial effect：
1) introduce cleaning and put forward phenol technique, what the added value in extraction coal tar was higher to greatest extent contains phenolic compounds, together
When the discharge of phenol wastewater is greatly lowered, reduce environmental pollution.Further, since the extraction containing phenolic compounds, after can reducing
Hydrogen consumes in phase hydrogenation process, while can also reduce influence of the water produced after phenols hydrogenation to catalyst activity and life-span.It is de-
Carbolic oil, which belongs to light oil raw material, to be used directly as solvent naphtha into system, reduce production cost.
2) oil of the dephenolize after phenol is carried as the solvent naphtha for preparing catalyst pulp using cleaning, due to the oily inherently source of dephenolize
From in coal tar raw material, in the absence of the compatibility issues of oil product, therefore it is referred to as after slurry with catalyst preparation mixed with coal tar
Conjunction can preferably promote catalyst to disperse in coal tar.Again due to the phenols in dephenolize oil has been removed substantially, will not
The activity of catalyst or life-span are adversely affected.
3) using slurry bed system be hydrocracked with fixed bed hydrogenation group technology, substantially increase the adaptability of raw material, also carry
The high flexibility of operation.Slurry bed system, which is hydrocracked, can also process that solid content is higher and the higher coal tar of carbon residue, and urge
Agent can with online supplement and get rid of outside, so as to ensure that reactor can be with long-term operation.Meanwhile, using tail oil circulation technology,
Improve the utilization rate of raw material.And fixed bed hydrogenation can both slough the miscellaneous originals such as most of sulphur, nitrogen, oxygen and the metal in raw material
Son, improves the quality of oil product；16 values of diesel oil distillate can be improved with hydrogenation aromatics-removing again, the oil product of high-quality is obtained.
4) present invention process is simple, raw material availability is high, and environmentally friendly, production cost and operating cost are low, safeguard letter
Single, raising catalyst service life, guarantee system are run steadily in the long term, and environmentally friendly, simple system is reliable, easy maintenance,
Product and byproduct high income, with wide market application foreground.
Brief description of the drawings
Fig. 1 is present invention process flow chart and system diagram.
Wherein, 1- catalyst raw material；2- catalyst premixings and vulcanizing tank；3- coal tar；4- destilling towers；5- slurry bed hydroprocessings
Cracker；6- cleanings put forward phenol system；7- thermal release systems；8- fixed bed hydrogenation reactors；9- fractionating columns；10- gaseous hydrocarbons；
11- gasoline fractions；12- diesel oil distillates；13- residual oil；The outer whipping oil of 14-；15- crude phenols；16- hydrogen.
Embodiment
System embodiment：
The entrance that the top exit of destilling tower 4 puies forward phenol system 6 with cleaning is connected, and the oil phase that the cleaning puies forward phenol system 6 goes out
Mouthful be connected with the entrance of catalyst slurry batch can 2, the outlet of the outlet at bottom and catalyst slurry batch can 2 of the destilling tower 4 with slurry
The entrance connection of state bed hydroprocessing cracker 5, the outlet connection thermal release system of the slurry bed system hydrocracking reactor 5,
Gas vent is arranged at the top of thermal release system 7, and there is oil phase outlet at middle part, and tail oil outlet is arranged at bottom, and the oil phase outlet is successively
Be connected bed hydroprocessing reactor 8 and fractionating column 9, and the tail oil outlet of the thermal release system 7 is hydrocracked with slurry bed system respectively
The entrance of reactor and out-of-bounds connect.
Process example：
(1) raw material coal tar 3 is sent into destilling tower 4 and isolates rich phenol cut and other cuts, vapo(u)rizing temperature is 150-300
DEG C, pressure is normal pressure.The rich phenol cut puies forward phenol system 6 into cleaning, and (system uses Patent No.
CN201410080517.6 process is carried out) carry out cleaning and carry phenol obtaining dephenolize oil and crude phenols 15, dephenolize oil feeding catalysis
Agent slurry tank 2 is mixed and made into catalyst pulp as solvent naphtha and catalyst and vulcanizing agent, the vulcanizing agent catalyst, urges vulcanization
The mixing quality ratio of agent and dephenolize oil is 1:(2-5):(4-7).
(2) carry out vulcanization after catalyst raw material, solvent and vulcanizing agent mixing and prepare catalyst pulp, the condition of vulcanization is：
Hydrogen to oil volume ratio (under mark condition)：400-600,230 DEG C of temperature vulcanizes and vulcanizes 3-5h at 3-5h, 320 DEG C, hydrogen pressure 3-6MPa, vulcanization
Agent is dimethyl disulfide.The catalyst pulp that vulcanization completes to obtain mixes feeding slurry with the other cuts obtained in step (1)
Hydrocracking reaction, catalyst are carried out in state bed hydroprocessing cracker 5 in the presence of hydrogen 16 (in terms of active component oxide)
Mixing quality ratio with other cuts is 0.5-5:100, more preferably 1-3:100.The slurry is controlled to be hydrocracked instead
The reaction temperature for answering device 5 is 330-480 DEG C, reaction pressure：12-20MPa, volume space velocity is 0.1-2.0h-1, hydrogen to oil volume ratio
For：1000-2000, (operating pressure scope is obtained reactant feeding thermal release system 7：Normal pressure -25MPa, operation temperature model
Enclose for：200-480 DEG C) hydrogen-rich gas, light oil and the tail oil containing catalyst are isolated, hydrogen-rich gas can be sent into as hydrogen
In slurry bed system hydrocracking reactor 5 and catalyst premixing and vulcanizing tank 2, the tail oil part containing catalyst is recycled back to slurry bed system
Hydrocracking reactor 5 participates in reaction, and remainder is outer whipping oil 14.
(3) it is the light oil obtained in step (2) the feeding progress hydrofining reaction of fixed bed hydrogenation reactor 8 is further
Arene removal, removes the hetero atoms such as sulphur, nitrogen, oxygen and metal, controls the reaction temperature 300- of the fixed bed hydrogenation reactor 8
400 DEG C, reaction pressure 6-12MPa, volume space velocity 0.1-3.0h-1, hydrogen to oil volume ratio is 400-1200.Obtained reactant feeding
Fractionating column 9 isolates gaseous hydrocarbon 10, gasoline fraction 11, diesel oil distillate 12 and residual oil 13.
Below from a kind of typical middle coalite tar as test raw material, by dewatering and desalting and except mechanical admixture etc.
After processing, the property such as table 1 of coal tar raw material：
The property of the coal tar raw material of table 1
As shown in table 2, product distribution is as shown in table 3 for embodiment process conditions.Wherein slurry bed system hydrocracking reactor 5 makes
Catalyst is heterogeneous composite catalyst, wherein aluminum oxide 24wt%, iron oxide 50wt%, nickel oxide 6wt%, oxidation
Molybdenum 20wt%, particle diameter is 5-100 μm；Filling is Hydrobon catalyst in fixed bed hydrogenation reaction 8, and it is constituted and property
For：Molybdenum oxide 20wt%, nickel oxide 8wt%, carrier is gama-alumina.The pore volume of catalyst is 0.5cm3/ g, specific surface area is
180m2/g。
The process conditions of the embodiment 1,2,3,4 of table 2
The products therefrom yield distribution of table 3
Claims (9)
1. a kind of coal tar cleaning puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that comprise the following steps：
(1) coal tar feeding destilling tower normal pressure is isolated into rich phenol cut and other cuts, the rich phenol cut is carried into cleaning
The progress cleaning of phenol system carries phenol and obtains dephenolize oil of the phenol content less than 3.5wt%, and dephenolize oil sends into catalyst slurry batch can as molten
Catalyst pulp is made with catalyst and vulcanizing agent mixing vulcanization in agent oil；
(2) catalyst pulp is mixed into hydrogen in feeding slurry bed system hydrocracking reactor with the other cuts obtained in step (1)
Hydrocracking reaction is carried out in the presence of gas, obtained reactant feeding thermal release system is isolated hydrogen-rich gas, light oil and contained
There is the tail oil of catalyst；
(3) light oil obtained in step (2) feeding fixed bed hydrogenation reactor is subjected to hydrofining reaction, obtained reaction
Thing feeding fractionating column isolates naphtha and diesel oil.
2. coal tar cleaning as claimed in claim 1 puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that described
In step (1), the mixing quality ratio of the vulcanizing agent, catalyst and dephenolize oil is 1:(2-5):(4-7).
3. coal tar cleaning as claimed in claim 1 puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that described
In step (2), in terms of active component oxide, the mixing quality ratio of catalyst and other cuts is 0.5-5:100.
4. the coal tar cleaning as described in claim 1 or 3 puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that
In the step (2), the reaction temperature of the slurry hydrocracking reactor is controlled：330-480 DEG C, reaction pressure：10-
20MPa, volume space velocity is 0.1-3.0h-1, hydrogen to oil volume ratio is：1000-2000.
5. coal tar cleaning as claimed in claim 1 puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that described
In step (2), the hydrogen-rich gas isolated can be sent into slurry bed system hydrocracking reactor as hydrogen is filled into.
6. coal tar cleaning as claimed in claim 1 puies forward the method that phenol back end hydrogenation produces fuel oil, it is characterised in that described
In step (2), the tail oil containing catalyst is recycled back to slurry bed system hydrocracking reactor and participates in reaction in whole or in part.
7. the coal tar cleaning as described in claim 1 or 5 or 6 puies forward the method that phenol back end hydrogenation produces fuel oil, its feature exists
In, in the step (3), 300-400 DEG C of the reaction temperature of the control fixed bed hydrogenation reactor, reaction pressure 6-12MPa,
Volume space velocity：0.1-3.0h-1, hydrogen to oil volume ratio：400-1200.
8. a kind of system of preparing fuel oil with coal oil hydrogenation product, it is characterised in that including destilling tower, the slurry bed system being sequentially connected
Hydrocracking reactor, thermal release system, fixed bed hydrogenation reactor and fractionating column, wherein, the destilling tower top exit warp
Cleaning puies forward phenol system and is connected with catalyst slurry batch can entrance, the catalyst slurry batch can outlet and slurry bed system hydrocracking reactor
Entrance connection.
9. the system of preparing fuel oil with coal oil hydrogenation product as claimed in claim 8, it is characterised in that the thermal release system
Outlet at bottom respectively with the entrance of slurry bed system hydrocracking reactor and being out-of-bounds connected.
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| CN108300511B (en) * | 2018-03-13 | 2023-12-15 | 中国五环工程有限公司 | Two-stage hydrotreating process and system for medium-low temperature coal tar |
| CN113337308A (en) * | 2021-05-26 | 2021-09-03 | 洛阳瑞华新能源技术发展有限公司 | Multi-element dispersant slurry of heavy oil suspension bed hydrogenation catalyst |
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| CN103789026A (en) * | 2014-01-29 | 2014-05-14 | 河南龙成煤高效技术应用有限公司 | Processing method for coal tar fluidized bed hydrogenation of heterogeneous catalyst |
| CN205313469U (en) * | 2015-11-17 | 2016-06-15 | 中国五环工程有限公司 | System for coal tar hydrogenation for production fuel oil |
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