CN104277878B - A kind of two-stage slurry state bed hydroprocessing technique of high temperature coal-tar - Google Patents
A kind of two-stage slurry state bed hydroprocessing technique of high temperature coal-tar Download PDFInfo
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- CN104277878B CN104277878B CN201310282769.2A CN201310282769A CN104277878B CN 104277878 B CN104277878 B CN 104277878B CN 201310282769 A CN201310282769 A CN 201310282769A CN 104277878 B CN104277878 B CN 104277878B
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- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
Abstract
The two-stage slurry state bed hydroprocessing technique that the invention provides a kind of high temperature coal-tar, belongs to technical field of coal chemical industry. Above-mentioned technique comprises the steps: that (1) carry out purified treatment to high temperature coal-tar; (2) high temperature coal-tar after purified treatment in the described step (1) is reduced pressure or air-distillation, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >; (3) heavy oil fraction of 350 DEG C of the > in described step (2) is mixed with hydrocracking catalyst, H2, after mixing, enter successively one-level slurry state bed, secondary slurry state bed carries out two-stage hydrocracking reaction, and the hydrocracking product preparing is carried out to fractionation processing. The liquid fuel that adopts the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar of the present invention to prepare has advantages of that hydrogen consumption is low, product yield is high.
Description
Technical field
The two-stage slurry state bed hydroprocessing technique that the present invention relates to a kind of high temperature coal-tar, belongs to coalificationWork technical field.
Background technology
Liquid fuel occupies very consequence in the various energy. Various automobiles, boats and ships,The means of transport such as aircraft, engineering machinery all uses liquid fuel in a large number. Liquid fuel mainly comesCome from from underground mining oil out. And in recent years, along with world petroleum resource day by dayThe continuous intensification of exhaustion and China's energy crisis, finds reasonable, economic alternative energy source, changesBecome energy consumption structure, become the task of top priority that China faces.
In prior art, along with the fast development of China's iron and steel and Coal Chemical Industry industry, coal tarOutput increasing, effective utilization of coal tar also becomes more and more important. And with coal tarOil is raw material, under the effect of catalyst, carries out hydrofinishing or hydrocracking and prepares liquidThe technology of fuel also just receives much concern as the substitute products of petrochemical industry, and it not only can replaceSupplement the deficiency of domestic petroleum resource for petrochemical industry, and for ensureing energy strategy safety,There is reality and long-range strategic importance.
According to the difference of pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into low conventionallyWarm, middle gentle high temperature coal-tar, its composition difference is larger. At present, coal tar hydrogenating technologyCan roughly be summarized as according to its technical characterstic: coal tar hydrorefining technology, delayed coking-The fixed bed hydrogenation cracking technology of hydrocracking process integration technology, coal tar and coal tarSlurry state bed hydroprocessing cracking technology. Such as Chinese patent literature, CN103059973A discloses oneSlurry state bed and the fixed bed coupling process of planting coal tar hydrogenation of total effluent, the method mainly comprisesFollowing steps: (1) coal tar full distillate oil through dehydration, udst separation pretreatment after, withHydrocracking catalyst mixes, and enters slurry state bed hydroprocessing cracking unit through preheating; (2)In slurry state bed hydroprocessing cracking unit, described coal tar full distillate oil is done at hydrocracking catalystWith under carry out hydrocracking, this process is continuous feed, first hydrogenated products enter fractionation unit;(3) at fractionation unit, described just hydrogenated products through fractionation operation wherein light components enter solidFixed bed hydrofinishing unit, midbarrel loops back paste state bed reactor together with catalyst,After the heavy component coke that remove portion catalyst and cracking process produce after filtration, still loop backStep (1); (4) at fixed bed hydrogenation refined unit, the described just lightweight group of hydrogenated productsPoint under Hydrobon catalyst effect, carry out that hydrogenation is saturated, desulfurization, holder folk prescription speech, obtainHydrogenated products; (5) at product rectification cell, hydrogenated products enter rectifying column, carry out cutCutting obtains final products vapour, diesel oil.
First above-mentioned technology is starching the cracking of state bed hydroprocessing to the full cut of coal tar after pretreatmentUnit carries out hydrocracking, and the first hydrogenated products that obtain are again through fractionation, and light components enters solidFixed bed hydrofinishing unit carries out hydrofinishing, and midbarrel is circulated to paste state bed reactor and entersRow hydrocracking, heavy component is circulated to pretreatment unit and carries out pretreatment after processing after filtration.The petrol and diesel oil target product preparing through above-mentioned technology is to meet the petrol and diesel oil that GB requires.But because above-mentioned technology is directly starched the cracking of state bed hydroprocessing to the full cut of coal tar, and coalIn the full cut of tar, not only contain heavy end, also contain midbarrel and light ends, andLight ends is in the time starching the cracking of state bed hydroprocessing, and light ends forms dilution to heavy endEffect, has reduced reactant concentration, can cause like this starching hydrogen consumption in state bed hydroprocessing cracking processIncrease, cause the wasting of resources, also can affect the receipts of coal tar hydrogenating prepare liquid fuel simultaneouslyRate. .
In prior art, also have first full coal tar cut is reduced pressure or air-distillation after,Cut into light oil distillate and heavy oil fraction, then light oil distillate and heavy oil fraction are urged respectivelyChange the report of hydrogenation prepare liquid fuel. Such as Chinese patent literature CN101864327A public affairsOpened a kind of coal tar hydrogenation modification method, the method mainly comprises the steps: first coalTar is cut into 205 DEG C of the light oil distillate of 205 DEG C of < and >'s through air-distillation or decompression distillationHeavy oil fraction; Again the light oil distillate of 205 DEG C of < is carried out to one section of fixed bed hydrogenation and refine, to thisHydrotreated product carries out alkylated reaction, obtains gasoline products; To the mink cell focus of 205 DEG C of >By weight adding for 1:1, flux oil mixes afterwards cut and hydrogen is mixed into two ends admittedlyFixed bed hydrogenation reactor carries out deep hydrofinishing, after fractionation is processed, obtains diesel oil distillate.Although above-mentioned technology has first been carried out decompression or air-distillation to the full cut of coal tar, then to obtainingLight ends and heavy end carry out respectively hydrofinishing, but above-mentioned technology in, counterweightWhen matter distillate carries out catalytic hydrogenation, adopt again flux oil first to dilute heavy distillate,The hydrofinishing that adopts fixed bed to carry out to the heavy distillate after dilution again, and flux oilExist and can cause equally hydrogen consumption in unifining process to increase, cause the wasting of resources, also simultaneouslyCan affect the quality of coal tar hydrogenating prepare liquid fuel.
That is to say, in prior art the heavy distillate in coal tar is starched to state bedOr fixed bed hydrogenation when reaction, be all to adopt light ends or flux oil to carry out heavy endAfter dilution, carry out again hydrogenation reaction, and the inventor finds by research, light ends mistakeBe present in heavy end more, while jointly carrying out hydrogenation reaction with heavy end, have hydrogen consumptionHeight, the while also causes the low problem of yield of coal tar hydrogenating prepare liquid fuel. But thisInventor also further studies and finds that the existence of light ends is not also definitely harmful, outstandingIt is for low temperature, middle temperature, high temperature coal-tar, selects the lightweight of Sq separatelyCut mixes with heavy end, can, in not affecting hydrogen consumption, obviously play raisingThe quality of the product of heavy end hydrocracking, and this point is prior art art technologyPersonnel do not recognize.
Summary of the invention
Technical problem to be solved by this invention is in prior art, coal tar to be carried out to catalysis to addWhen hydrogen, carry out again after need to first adopting light ends or diluent to dilute heavy endHydrogenation, can reduce reactant concentration like this, causes hydrogen consumption in catalytic hydrogenation process to increase, andThe yield of liquid fuel is low, and then provides a kind of by high temperature coal-tar is carried out to suitable fractionationAfter, different fractions is fixed respectively to bed hydroprocessing the hydrogen refining and cracking of slurry state bed hydroprocessing and consumesThe Unionfining technique low, liquid fuel yield is high.
In order to solve the problems of the technologies described above, the invention provides a kind of two-stage slurry of high temperature coal-tarState bed hydroprocessing technique, comprises the steps:
(1) high temperature coal-tar is carried out to purified treatment;
(2) high temperature coal-tar after purified treatment in the described step (1) is reduced pressure orAir-distillation, cuts into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) by the heavy oil fraction of 350 DEG C of the > in described step (2) and hydrocracking catalysisAgent, H2Mix, after mixing, enter successively one-level slurry state bed, secondary slurry state bed carries out twoLevel hydrocracking reaction, carries out fractionation processing to the hydrocracking product preparing, by <The product of 350 DEG C distillates, and the cut of the > 500-550 of 3～20wt% DEG C is arranged outward, and all the other loop backSecondary paste state bed reactor, the product that wherein said < is 350 DEG C is through further obtaining stone after fractionationCerebrol and diesel product.
By in the light oil distillate of 350 DEG C of the < in described step (2) and described step (3)Product that < is 350 DEG C mixes, then with H2Mix, after mixing, enter single-stage or two-stageFixed bed hydrogenation reactor carries out hydrofining reaction under Hydrobon catalyst effect.
Described Hydrobon catalyst is Co-Mo system, Ni-Mo system, Co-W system, Ni-WAny one or a few in system.
The condition of described fixed bed hydrogenation reaction is: be that 220～450 DEG C, pressure are in temperature12.0～20.0MPa, volume space velocity are 0.5～2.0h-1, hydrogen to oil volume ratio is 500～3000.
In the high temperature coal-tar in described step (1), add in middle coalite tar, residual oilOne or more, wherein said residual oil can be selected the heavy residual oil of high-sulfur, the heavy slag of high bitumen contentAny one or a few in the heavy residual oil of oily, high content of beary metal.
Described hydrocracking catalyst is for containing hydrogenation activity component Fe, Co, Ni, Mo, WIn any one or a few nanometer materials.
Described nanometer materials are oil-soluble nanometer materials.
The heavy oil fraction that > in described step (3) is 350 DEG C first after the pre-heat treatment, then with addHydrogen Cracking catalyst, H2Mix.
Described preheat temperature is 100～250 DEG C.
Described one-level slurry reactor temperature is 350～580 DEG C, and secondary slurry reactor temperature is350～580 DEG C, other reaction condition of one-level slurry state bed and secondary slurry state bed is: pressure is10.0～23.0MPa, volume space velocity are 0.5～2.0h-1, hydrogen to oil volume ratio is 1200～5000.
The present invention compared with prior art tool has the following advantages:
(1) two-stage of high temperature coal-tar of the present invention slurry state bed hydroprocessing technique, first rightHigh temperature coal-tar carries out purified treatment, and the object of purified treatment is to remove in high temperature coal-tar to containSome solid impurities, water etc.; And then the high temperature coal-tar after purified treatment is subtractedPress or air-distillation, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >,Taking 350 DEG C as cut point, be suitable because of containing in the heavy oil fraction on this cut pointAmount light oil distillate, and the existence of this part light oil distillate to heavy oil fraction in follow-up two-stageIn the cracking of slurry state bed hydroprocessing, have collaborative facilitation, it can improve this part heavy oil greatlyThe quality of the hydrogenated products of cut, after tested, the method for the invention reduces naphtha and bavinSulfur content in oil, nitrogen content, and greatly improved the Cetane number in diesel oil.
(2) two-stage of high temperature coal-tar of the present invention slurry state bed hydroprocessing technique, further350 DEG C of the < that ground obtains by the light oil distillate of 350 DEG C of < with after the cracking of two-stage slurry state bed hydroprocessingCut be mixed into fixed bed and carry out hydrofinishing, can further improve of the present inventionThe conversion ratio of high temperature coal-tar. Adopt the two-stage slurry state bed of high temperature coal-tar of the present invention to addThe liquid fuel that hydrogen technique prepares has that hydrogen consumption is low, product quality can further be carriedHigh.
(3) two-stage of high temperature coal-tar of the present invention slurry state bed hydroprocessing technique, furtherGround can also add a kind of or several in middle coalite tar, residual oil in high temperature coal-tarPlant and form mixture, then adopt above-mentioned steps to carry out catalytic hydrogenation to this mixture, due to rightThis mixture is provided with the cut point of 350 DEG C equally, and in mixture on this cut pointIn heavy oil fraction, can contain the light oil distillate of Sq, and existing of this part light oil distillate is rightHeavy oil fraction in mixture has collaborative promotion in follow-up secondary slurry state bed hydroprocessing crackingEffect, it can improve the hydrogenation conversion of the heavy oil fraction in this part mixture greatly.Therefore, adopt the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar of the present invention, not only canSo that high temperature coal-tar is carried out to catalytic hydrogenation, all right centering coalite tar, residual oil and heightThe miscella that temperature coal tar forms carries out catalytic hydrogenation, and the liquid fuel preparing is sameThere is low, the excellent product performance of hydrogen consumption.
(4) two-stage of high temperature coal-tar of the present invention slurry state bed hydroprocessing technique, furtherGround, can also select the heavy oil fraction of 350 DEG C of > to carry out the pre-heat treatment, then with hydrocrackingCatalyst, H2Mix, can make like this heavy oil fraction of 350 DEG C of > and catalyst, H2MixedThat closes is more even, so that further improve its hydrogenation catalyst efficiency.
Brief description of the drawings
Fig. 1 is the process flow of the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar of the present inventionCheng Tu;
Reference numeral is as follows:
1. high temperature coal-tar raw material; 2. purified treatment; 3. normal pressure or vacuum distillation tower; 4. 350 DEG C of >Cut; 5. the cut of 350 DEG C of <; The cut of 500～540 DEG C 7. one-level slurries of 6.3～20wt%State bed reaction device; 8. secondary slurry reactor device; 9. fixed-bed reactor; All the otherCut
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
Embodiment 1
(1) in purification apparatus to high temperature coal-tar dewater, purification place of removal of impuritiesReason, the high temperature coal-tar water content after dehydration is less than 0.5wt%;
(2) high temperature coal-tar after purified treatment in described step (1) is carried out to normal pressure steamingHeat up in a steamer, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) by the heavy oil fraction of 350 DEG C of the > in described step (2) and hydrocracking catalysisAgent, H2Mix, wherein, described hydrocracking catalyst is nanometer materials, and it consists of50wt% alpha-feooh, surplus is γ-Al2O3, after mixing, enter successively one-level slurry state bed,Secondary slurry state bed carries out two-stage hydrocracking reaction, and the condition of hydrocracking reaction is as follows: described inOne-level slurry reactor temperature is 350 DEG C, and secondary slurry reactor temperature is 350 DEG C, one-levelOther reaction condition of slurry state bed and secondary slurry state bed is: pressure is 23.0MPa, volume space velocityFor 0.5h-1, hydrogen to oil volume ratio is 1200; The hydrocracking product preparing is carried out to fractionationProcess, the product of 350 DEG C of < is distillated, the cut of the > 500-550 of 3～20wt% DEG C is arranged outward,All the other loop back secondary paste state bed reactor, and the product that wherein said < is 350 DEG C is through further dividingAfter heating up in a steamer, obtain naphtha and diesel product.
In above-described embodiment, the total conversion of high temperature coal-tar is 94.7%, diesel oil total recovery74.2%。
Embodiment 2
(1) in purification apparatus to high temperature coal-tar dewater, purification place of removal of impuritiesReason, the high temperature coal-tar water content after dehydration is less than 0.5wt%;
(2) high temperature coal-tar after purified treatment in the described step (1) is reduced pressure steamingHeat up in a steamer, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) by the heavy oil fraction of 350 DEG C of the > in described step (2) and hydrocracking catalysisAgent, H2Mix, wherein, described hydrocracking catalyst is oil solubility nanometer level material, itsConsist of 25wt%MoO3, 5wt%NiO, surplus be oil-soluble γ-Al2O3Carrier, mixesEvenly, enter successively one-level slurry state bed, secondary slurry state bed carries out two-stage hydrocracking reaction, addThe condition of hydrogen cracking reaction is as follows: described one-level slurry reactor temperature is 400 DEG C, secondary slurryState bed reaction temperature is 400 DEG C, and other reaction condition of one-level slurry state bed and secondary slurry state bed is:Pressure is that 19.0MPa, volume space velocity are 1.5h-1, hydrogen to oil volume ratio is 3000; To being prepared intoTo hydrocracking product carry out fractionation processing, the product of 350 DEG C of < is distillated to 3～20wt%The cut of > 500-550 DEG C arrange outward, all the other loop back secondary paste state bed reactor;
(4) by the light oil distillate of 350 DEG C of the < in described step (2) and described step (3)In product and the H of 350 DEG C of <2Mix, after mixing, enter successively two stage fixed-bed hydrogenationReactor, the condition of described two stage fixed-bed hydrogenation reaction is: be 220 DEG C, press in temperaturePower is that 20.0MPa, volume space velocity are 0.5h-1, hydrogen to oil volume ratio is 500; In hydrofinishingUnder catalyst action, carry out hydrofining reaction, the composition of wherein said Hydrobon catalyst asUnder: 7wt%NiO, 20wt%MoO3, surplus is ZSM-5 molecular sieve, to hydrorefinedProduct carries out fractionation, obtains naphtha and diesel oil.
In above-described embodiment, the total conversion of high temperature coal-tar is 97.1%, diesel oil total recovery77.3%。
Embodiment 3
(1) in purification apparatus, high temperature coal-tar, high-sulfur are weighed to residual oil, high heavy metalThe mixture of the heavy residual oil of content dewaters, the purified treatment of removal of impurities, wherein said high temperature coal tarThe mass ratio of oil, the heavy residual oil of high-sulfur, the heavy residual oil of high content of beary metal is 5:0.5:0.5, through dehydrationAfter mixture water content be less than 0.5wt%;
(2) high temperature coal-tar after purified treatment in described step (1) is carried out to normal pressure steamingHeat up in a steamer, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) heavy oil fraction of 350 DEG C of the > in described step (2) is carried out at 100 DEG CThe pre-heat treatment, and then with hydrocracking catalyst, H2Mix, wherein, described hydrogenation splitsChange catalyst is nanometer materials, and it consists of 5wt%NiO, 30wt%WO3Surplus is skySo zeolite molecular sieve, enters one-level slurry state bed, secondary slurry state bed carries out two successively after mixingLevel hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperatureDegree is 455 DEG C, and secondary slurry reactor temperature is 455 DEG C, one-level slurry state bed and secondary slurry stateOther reaction condition of bed is: pressure is that 16.0MPa, volume space velocity are 0.5h-1, hydrogen oil bodyLong-pending ratio is 2000; The hydrocracking product preparing is carried out to fractionation processing, by 350 DEG C of <Product distillate, the cut of the > 500-550 of 3～20wt% DEG C is arranged outward, all the other loop back secondaryPaste state bed reactor;
(4) by the light oil distillate of 350 DEG C of the < in described step (2) and described step (3)In product and the H of 350 DEG C of <2Mix, after mixing, enter single slage fixed bed hydrogenation reactionDevice, the condition of described fixed bed hydrogenation reaction is: temperature be 360 DEG C, pressure be 12MPa,Volume space velocity is 1.0h-1, hydrogen to oil volume ratio is 1000; Under Hydrobon catalyst effect, enterRow hydrofining reaction, wherein said Hydrobon catalyst composed as follows: 7wt%NiO,35wt%CoO, surplus are ZSM-5 molecular sieve, and hydrorefined product is carried out to fractionation,To naphtha and diesel oil.
In above-described embodiment, the total conversion of coal oil mixture is 94.4%, diesel oil total recovery75.3%。
Embodiment 4
(1) in purification apparatus, high temperature coal-tar, high bitumen content are weighed to residual oil and heavyThe mixture of oil dewaters, the purified treatment of removal of impurities, wherein said high temperature coal-tar, residual oilWith the mass ratio of heavy oil be 5:1:1, through dehydration after mixture water content be less than 0.5wt%;
(2) high temperature coal-tar after purified treatment in described step (1) is carried out to normal pressure steamingHeat up in a steamer, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) heavy oil fraction of 350 DEG C of the > in described step (2) is carried out at 170 DEG CThe pre-heat treatment, and then with hydrocracking catalyst, H2Mix, wherein, described hydrogenation splitsChange catalyst is nanometer materials, and it consists of 5wt%CoO, 35wt%MoO3Surplus is skySo zeolite molecular sieve, enters one-level slurry state bed, secondary slurry state bed carries out two successively after mixingLevel hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactor temperatureDegree is 500 DEG C, and secondary slurry reactor temperature is 500 DEG C, one-level slurry state bed and secondary slurry stateOther reaction condition of bed is: pressure is that 10.0MPa, volume space velocity are 2.0h-1, hydrogen oil bodyLong-pending ratio is 4000; The hydrocracking product preparing is carried out to fractionation processing, by 350 DEG C of <Product distillate, the cut of the > 500-550 of 3～20wt% DEG C is arranged outward, all the other loop back secondaryPaste state bed reactor;
(4) by the light oil distillate of 350 DEG C of the < in described step (2) and described step (3)In product and the H of 350 DEG C of <2Mix, after mixing, enter single slage fixed bed hydrogenation reactionDevice, the condition of described fixed bed hydrogenation reaction is: temperature be 400 DEG C, pressure be 18MPa,Volume space velocity is 2.0h-1, hydrogen to oil volume ratio is 2500; Under Hydrobon catalyst effect, enterRow hydrofining reaction, wherein said Hydrobon catalyst composed as follows: 27wt%WO3、10wt%CoO, surplus are ZSM-5 molecular sieve, and hydrorefined product is carried out to fractionation,To naphtha and diesel oil;
In above-described embodiment, the total conversion of coal oil mixture is 95.1%, diesel oil total recovery78.4%。
Embodiment 5
(1) mixture to high temperature coal-tar and middle coalite tar in purification apparatusDewater, the purified treatment of removal of impurities, wherein, described high temperature coal-tar and middle coalite tarMass ratio be 3:1, through dehydration after mixture water content be less than 0.5wt%;
(2) high temperature coal-tar after purified treatment in described step (1) is carried out to normal pressure steamingHeat up in a steamer, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) heavy oil fraction of 350 DEG C of the > in described step (2) is carried out at 250 DEG CThe pre-heat treatment, and then with hydrocracking catalyst, H2Mix, wherein, described hydrogenation splitsChange catalyst is nanometer materials, and it consists of 5wt%Fe2O3、35wt%WO3, surplus isNatural zeolite molecular sieve, enters one-level slurry state bed, secondary slurry state bed carries out successively after mixingTwo-stage hydrocracking reaction, the condition of hydrocracking reaction is as follows: described one-level slurry reactorTemperature is 580 DEG C, and secondary slurry reactor temperature is 580 DEG C, one-level slurry state bed and secondary slurryOther reaction condition of state bed is: pressure is that 10.0MPa, volume space velocity are 1.0h-1, hydrogen oilVolume ratio is 1800; The hydrocracking product preparing is carried out to fractionation processing, by 350 DEG C of <Product distillate, the cut of the > 500-550 of 3～20wt% DEG C is arranged outward, all the other loop back secondaryPaste state bed reactor;
(4) by the light oil distillate of 350 DEG C of the < in described step (2) and described step (3)In product and the H of 350 DEG C of <2Mix, after mixing, enter single slage fixed bed hydrogenation reactionDevice, the condition of described fixed bed hydrogenation reaction is: temperature be 450 DEG C, pressure be 12MPa,Volume space velocity is 1.5h-1, hydrogen to oil volume ratio is 3000; Under Hydrobon catalyst effect, enterRow hydrofining reaction, wherein said Hydrobon catalyst composed as follows: 7wt%NiO,35wt%CoO, surplus are ZSM-5 molecular sieve, and hydrorefined product is carried out to fractionation,To naphtha and diesel oil;
In above-described embodiment, the total conversion of coal oil mixture is 96.4%, diesel oil total recovery76.7%。
In addition, the present invention also provide high temperature coal-tar used in above-mentioned all embodiment, in lowTemperature coal tar, slag oil properties, as shown in table 1, and the stone preparing is further providedCerebrol and bavin oil properties, as shown in table 2.
Table 1 raw material oil properties
| Feedstock oil | High temperature coal-tar | Middle coalite tar | Residual oil |
| Density g/cm3 | 1.18 | 1.002 | 0.94 |
| S，wt% | 0.3 | 0.3 | 2.1 |
| O，wt% | - | 6.5 | - |
| N，wt% | 0.8 | - | - |
| Ash content, wt% | - | - | 0.045 |
| Ni+V，ppm | - | - | 110 |
| C7 insoluble matter, wt% | ＜9 | 4.5 | - |
The naphtha that table 2 prepares and bavin oil properties
Comparative example
The present invention adopts the embodiment providing in documents CN103059973A as thisBright described comparative example, it is taking the full cut of high temperature coal-tar as raw material, wherein, density is 1.18,Sulfur content is 0.3wt%, and nitrogen content is 0.8wt%, and C7 insoluble matter is < 9wt%, adopt asLower technique prepare liquid fuel:
Water and the mechanical admixture in raw material removed in pretreatment, mixes with hydrocracking catalystEnter paste state bed reactor, hydrocracking catalyst is 35%WO3、10%NiO、3%P2O5、Surplus is USY molecular sieve, and hydrocracking condition is as follows: 150 DEG C of preheat temperatures, reaction pressureSplit 12MPa, reaction temperature is 390 DEG C, volume space velocity 0.5h-1, hydrogen to oil volume ratio is 1600,Head product after hydrocracking enters fractionating column, and light fraction enters back segment fixed bed reactors and entersRow hydrofinishing, this part cut accounts for 15wt%, the about 65wt% circulation of midbarrel overfallState bed reactor continues hydrocracking, the remove portion catalysis after filtration of the heavy end of about 20wt%After the coke producing in agent and course of reaction, enter raw material storage tank, the cyclic utilization rate of catalyst approximatelyBe 80%, wherein light ends fixed bed hydrogenation refining reaction condition is as follows: reaction pressure8MPa, 375 DEG C of reaction temperatures, volume space velocity 0.5h-1, hydrogen to oil volume ratio 1600; Fixed bedProduct after refining obtains gasoline and diesel oil through fractionation;
Adopt the performance of the gasoline that above-mentioned technology prepares as follows: density 0.7995g/cm-3、Sulfur content < 50ppm, nitrogen content < 50ppm, octane number 91.5, the diesel oil preparing heats up in a steamerThe performance of dividing is as follows: density 0.7995g/cm-3, sulfur content < 50ppm, nitrogen content < 50ppm,Cetane number 35.6.
From above-mentioned comparative example, the naphtha, the bavin that adopt the method for the invention to prepareSulfur content, the nitrogen content of oil reduce greatly, and the Cetane number of diesel oil also improves greatly.
Obviously, above-described embodiment is only for example is clearly described, and not rightThe restriction of embodiment. For those of ordinary skill in the field, in above-mentioned explanationBasis on can also make other changes in different forms. Here without also cannotAll embodiments are given exhaustive, and the apparent variation of being extended out thus orVariation is still among the protection domain in the invention claim.
Claims (9)
1. the two-stage of a high temperature coal-tar slurry state bed hydroprocessing technique, comprises the steps:
(1) mixture of high temperature coal-tar or high temperature coal-tar and middle coalite tar and/or residual oil is carried out to purified treatment;
(2) high temperature coal-tar after purified treatment in the described step (1) is reduced pressure or air-distillation, cut into the heavy oil fraction of 350 DEG C of the light oil distillate of 350 DEG C of < and >;
(3) by the heavy oil fraction of 350 DEG C of the > in described step (2) and hydrocracking catalyst, H2Mix, after mixing, enter successively one-level slurry state bed, secondary slurry state bed carries out two-stage hydrocracking reaction, the hydrocracking product preparing is carried out to fractionation processing, the product of 350 DEG C of < is distillated, after the further fractionation of product that the < that distillates is 350 DEG C, obtain naphtha and diesel product, the cut of the > 500-550 of 3～20wt% DEG C is arranged outward, and all the other loop back secondary paste state bed reactor.
2. the two-stage of high temperature coal-tar is starched state bed hydroprocessing technique according to claim 1, it is characterized in that, after the product distillating of 350 DEG C of < in the light oil distillate of 350 DEG C of < in described step (2) and described step (3) is mixed, then with H2Mix, after mixing, enter single-stage or two stage fixed-bed hydrogenation reactor, under Hydrobon catalyst effect, carry out hydrofining reaction, hydrorefined product is carried out to fractionation, obtain naphtha and diesel oil.
3. the two-stage of high temperature coal-tar is starched state bed hydroprocessing technique according to claim 2, it is characterized in that, described Hydrobon catalyst is any one or a few in Co-Mo system, Ni-Mo system, Co-W system, Ni-W system.
4. the two-stage of high temperature coal-tar slurry state bed hydroprocessing technique according to claim 2, is characterized in that, the condition of described fixed bed hydrogenation reaction is: temperature is that 220～450 DEG C, pressure are that 12.0～20.0MPa, volume space velocity are 0.5～2.0h-1, hydrogen to oil volume ratio is 500～3000.
5. according to the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar described in claim 1～4 any one, it is characterized in that, described hydrocracking catalyst is any one or a few nanometer materials that contain in hydrogenation activity component Fe, Co, Ni, Mo, W.
6. the two-stage of high temperature coal-tar is starched state bed hydroprocessing technique according to claim 5, it is characterized in that, described nanometer materials are oil-soluble nanometer materials.
7. according to the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar described in claim 1-4 any one, it is characterized in that, the heavy oil fraction that > in described step (3) is 350 DEG C first after the pre-heat treatment, then with hydrocracking catalyst, H2Mix.
8. the two-stage of high temperature coal-tar is starched state bed hydroprocessing technique according to claim 7, it is characterized in that, described preheat temperature is 100～250 DEG C.
9. according to the two-stage slurry state bed hydroprocessing technique of high temperature coal-tar described in claim 1,2,3,4,6 or 8, it is characterized in that, described one-level slurry reactor temperature is 350～580 DEG C, secondary slurry reactor temperature is 350～580 DEG C, and other reaction condition of one-level slurry state bed and secondary slurry state bed is: pressure is that 10.0～23.0MPa, volume space velocity are 0.5～2.0h-1, hydrogen to oil volume ratio is 1200～5000.
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Citations (3)
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|---|---|---|---|---|
| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| CN101629103A (en) * | 2008-10-15 | 2010-01-20 | 何巨堂 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
| CN102796559A (en) * | 2012-08-13 | 2012-11-28 | 煤炭科学研究总院 | Method and apparatus for producing fuel oil by hydrocracking |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| CN101629103A (en) * | 2008-10-15 | 2010-01-20 | 何巨堂 | Hydro-conversion combination method for coal tar fraction with different boiling ranges |
| CN102796559A (en) * | 2012-08-13 | 2012-11-28 | 煤炭科学研究总院 | Method and apparatus for producing fuel oil by hydrocracking |
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