CN104419461B - The slurry bed system of a kind of coal tar and fixed bed serial hydrogenation technique - Google Patents
The slurry bed system of a kind of coal tar and fixed bed serial hydrogenation technique Download PDFInfo
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- CN104419461B CN104419461B CN201310360713.4A CN201310360713A CN104419461B CN 104419461 B CN104419461 B CN 104419461B CN 201310360713 A CN201310360713 A CN 201310360713A CN 104419461 B CN104419461 B CN 104419461B
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The present invention provides slurry bed system and the fixed bed serial hydrogenation technique of a kind of coal tar, comprises the steps: that (1) carries out purified treatment；(2) carry out reducing pressure or air-distillation by the coal tar after described purified treatment, cut into light oil distillate and heavy oil fraction, the cut point of light and heavy fractions 220 ~ 370 DEG C；(3) by described light oil distillate and H2Mixing, enters fixed bed, carries out hydrofinishing, prepare hydrofinishing product under the effect of Hydrobon catalyst after mix homogeneously；(4) by described heavy oil fraction and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, the hydrocracked product prepared is carried out fractional distillation process, wherein arrange outside 540 DEG C of fractions of ＞, 350 DEG C of fractions of ＜ are as the part charging reuse of fixed bed, and remaining component returns one-level slurry bed system entrance.The method of the invention reduces the sulfur content in Petroleum and diesel oil, nitrogen content, and substantially increases the Cetane number in diesel oil.
Description
Technical field
The present invention relates to slurry bed system and the fixed bed Unionfining technique of a kind of coal tar, belong to technical field of coal chemical industry.
Background technology
Liquid fuel occupies highly important status in the various energy.The means of transports such as various automobiles, boats and ships, aircraft, engineering machinery use liquid fuel the most in a large number.Liquid fuel is mainly derived from from underground mining oil out.And in recent years, along with the day by day exhausted of world petroleum resource and the continuous intensification of China's energy crisis, find reasonable, economic alternative energy source, change energy consumption structure, it has also become the task of top priority that China faces.
In prior art, along with China's iron and steel and the fast development of coal chemical industry, the yield of coal tar is increasing, and effective utilization of coal tar also becomes more and more important.And with coal tar as raw material, under the effect of catalyst, carry out hydrofinishing or be hydrocracked the technology preparing liquid fuel and the most just receive much concern as the substitute products of petrochemical industry, it can not only supplement the deficiency of domestic petroleum resource by petroleum replacing chemical industry, and for ensureing energy strategy safety, there is real and long-range strategic importance.
At present, coal tar hydrogenating technology can substantially be summarized as according to its technical characterstic: coal tar hydrorefining technology, delayed coking-be hydrocracked process integration technology, the fixed bed hydrogenation cracking technology of coal tar and the slurry bed system hydrocracking technology of coal tar.Such as Chinese patent literature CN103059973A discloses slurry bed system and the fixed bed coupling process of a kind of full fraction of coal tar hydrogenation, the method mainly comprise the steps: (1) full fraction of coal tar oil through dehydration, udst separation pretreatment after, mix homogeneously with hydrocracking catalyst, preheated entrance slurry bed system Hydrocracking unit；(2) at slurry bed system Hydrocracking unit, described full fraction of coal tar oil is hydrocracked under hydrocracking catalyst effect, and this process is continuous feed, and first hydrogenated products enter fractionation unit；(3) at fractionation unit, described just hydrogenated products are fractionated into operating wherein light components and enter fixed bed hydrogenation refined unit, midbarrel loops back paste state bed reactor together with catalyst, and heavy component still loops back step (1) after the coke that partial catalyst and cracking process produce is removed by filtration；(4) at fixed bed hydrogenation refined unit, the light components of described just hydrogenated products carries out being hydrogenated with saturated, desulfurization, torr folk prescription speech under Hydrobon catalyst effect, obtains hydrogenated products；(5) at product rectification cell, hydrogenated products enter rectifying column, carry out fraction cutting and obtain final products vapour, diesel oil.
First full fraction of coal tar after pretreatment is hydrocracked by above-mentioned technology at slurry bed system Hydrocracking unit, the first hydrogenated products obtained are fractionated into again, light components enters fixed bed hydrogenation refined unit and carries out hydrofinishing, midbarrel is recycled to paste state bed reactor and is hydrocracked, and heavy component carries out pretreatment through filtration treatment Posterior circle to pretreatment unit.The petrol and diesel oil target product prepared through above-mentioned technology is the petrol and diesel oil meeting Standard.But it is hydrocracked owing to above-mentioned technology directly carries out slurry bed system to full fraction of coal tar, and full fraction of coal tar does not contain only heavy end, possibly together with midbarrel and light ends, and light ends is when carrying out slurry bed system and being hydrocracked, light ends forms diluting effect to heavy end, reduces reactant concentration, and hydrogen consumption in slurry bed system hydrocracking process so can be caused to increase, causing the wasting of resources, also can affect coal tar hydrogenating prepares the yield of liquid fuel simultaneously.
In prior art, also have and first carry out reducing pressure or after air-distillation by full fraction of coal tar, cut into light oil distillate and heavy oil fraction, then light oil distillate and heavy oil fraction are carried out catalytic hydrogenation respectively prepare the report of liquid fuel.Such as Chinese patent literature CN101864327A discloses a kind of coal tar hydrogenation modification method, and the method mainly comprises the steps: that first coal tar is cut into the heavy oil fraction of<light oil distillate of 205 DEG C and>205 DEG C through air-distillation or decompression distillation；Again to < light oil distillate of 205 DEG C carries out one section of fixed bed hydrogenation and refines, and this hydrotreated product is alkylated reaction, obtains gasoline products；Right > heavy oil fraction of 205 DEG C carries out deep hydrofinishing by weight being mixed into two ends fixed bed hydrogenation reactor with hydrogen after adding flux oil mix homogeneously for 1:1, obtains diesel oil distillate after being fractionated into processing.Although above-mentioned technology has first carried out decompression or air-distillation to full fraction of coal tar, again the light ends obtained and heavy end are carried out hydrofinishing respectively, but in above-mentioned technology, when heavy distillate is carried out catalytic hydrogenation, use again flux oil that heavy distillate is first diluted, the heavy distillate after dilution is used the hydrofinishing that fixed bed is carried out again, and the existence of flux oil also results in hydrogen consumption in unifining process and increases, causing the wasting of resources, also can affect coal tar hydrogenating prepares the quality of liquid fuel simultaneously.
That is, in prior art when the heavy distillate in coal tar being carried out slurry bed system or fixed bed hydrogenation reaction, it is all to use light ends or flux oil to carry out hydrogenation reaction again after heavy end is diluted, light ends is present in heavy end, when jointly carrying out hydrogenation reaction with heavy end, there is hydrogen consumption height, also cause coal tar hydrogenating to prepare the problems such as the yield of liquid fuel is low, the S of liquid fuel, N content high, the Cetane number content of diesel product is low simultaneously.But the present inventor has been found that the existence of light ends is the most not the most harmful, for the coal tar of complicated component, select the light ends of Sq and the mixing of heavy end, while not affecting hydrogen consumption, the total conversion improving coal tar can not only be played, more can improve the quality of hydrofinishing product during coal tar hydrogenation process, and this point is prior art those skilled in the art does not recognize.
It is known that, in hydrogenation technique, hydrogen dividing potential drop is the highest more is conducive to hydrofinishing, particularly to being difficult to the sulfur and the nitrogen that remove, if expecting the product that N, S content is low, hydrogen dividing potential drop needed for its unifining process can be higher, further increase the hydrogen consumption of whole technique, and a large amount of hydrogen carrying out containing in hydrogenation process, and the gas of each equipment exhausting that slurry bed system equipment of the prior art and fixed bed unit are independently are not reasonably utilized.
Summary of the invention
When the technical problem to be solved is, in prior art, coal tar is carried out catalytic hydrogenation, need first to use light ends or diluent to be hydrogenated with again after heavy end is diluted, so can reduce reactant concentration, hydrogen consumption in catalytic hydrogenation is caused to increase, and the yield of liquid fuel is low, the problem that product quality is low, and then by rational parameter adjustment, creatively select the cut point that light and heavy fractions is the suitableeest, thus provide slurry bed system and the fixed bed serial hydrogenation technique of a kind of coal tar；Further, for present coal tar hydrogenation process hydrogen consumption height, from each equipment, the hydrogen in isolated gas does not has the problem of Appropriate application, and then provides slurry bed system and the fixed bed serial hydrogenation technique of another coal tar.
The technical scheme taked for this present invention is:
The slurry bed system of a kind of coal tar and fixed bed serial hydrogenation technique, comprise the steps:
(1) carry out being dehydrated, taking off the purified treatment of mechanical admixture；
(2) carry out reducing pressure or air-distillation by the coal tar after purified treatment in described step (1), cut into light oil distillate and heavy oil fraction, the cut point 220 of light and heavy fractions～370 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing, prepare hydrofinishing product under the effect of Hydrobon catalyst after mix homogeneously；
(4) by described step (2) heavy oil fraction and hydrocracking catalyst, H2Mixing, sequentially enters one-level slurry bed system, two grades of slurry bed system carry out two-stage hydrocracking reaction after mix homogeneously, control conversion ratio between 35～85%, the hydrocracked product prepared is carried out fractional distillation process,
By isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions mix with the light oil distillate of described step (2) as the part charging of fixed bed after entrance fixed bed, remaining component returns one-level slurry bed system entrance as a part of feed cycle of one-level slurry bed system.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, in the slurry bed system of described coal tar and fixed bed serial hydrogenation technique of stable operation, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, the isolated gas of two-stage slurry bed system mixes with described hydrogen make-up after recycle compressor supercharging.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, after the first preheated process of heavy oil fraction in described step (4), then with hydrocracking catalyst, H2Mixing.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, the temperature of described the pre-heat treatment is 80～280 DEG C.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, described hydrocracking catalyst is containing the nanometer materials of one or more in hydrogenation active component Fe, Co, Ni, Mo, W.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, described one-level slurry reactor temperature 350～550 DEG C, two grades of slurry reactor temperature are 350～550 DEG C, and other reaction conditions of two-stage paste state bed reactor are: pressure is 10.0～18.0MPa, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio be 1200～5000.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, described Hydrobon catalyst is any one or a few in Co-Mo system, Ni-Mo system, Co-W system, Ni-W system.
In the slurry bed system of above-mentioned middle coalite tar and fixed bed Unionfining technique, the condition of described fixed bed hydrogenation reaction is: temperature is 220～450 DEG C, pressure is 12.0～18.0MPa, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio be 500～3000.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, described coal tar is one or both in middle coalite tar or high temperature coal-tar.
In the slurry bed system of above-mentioned coal tar and fixed bed serial hydrogenation technique, any one or a few in addition residual oil, heavy oil, high-sulfur oils, high bitumen content content of beary metal oil oily, high in the coal tar in described step (1).
The present invention compared with prior art has the advantage that
(1) in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, first coal tar being carried out purified treatment, the purpose of purified treatment is to remove solid impurity, the water etc. contained in coal tar；The coal tar after the most purified process is reduced pressure or air-distillation, cut into light oil distillate and heavy oil fraction, temperature range with 220-370 DEG C as cut point, being because in the heavy oil fraction on this cut point can be containing the light oil distillate of Sq, and the existence of this part light oil distillate has collaborative facilitation in follow-up two-stage slurry bed system is hydrocracked to heavy oil fraction, it can be greatly improved the quality of hydrogenated products of this part heavy oil fraction, after tested, the method of the invention reduces the sulfur content in Petroleum and diesel oil, nitrogen content, and substantially increase the Cetane number in diesel oil.
(2) in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, further by light oil distillate and obtain after two-stage slurry bed system is hydrocracked < fraction of 350 DEG C is mixed into fixed bed and carries out hydrofinishing, it is possible to improve further the conversion ratio of high temperature coal-tar of the present invention.The liquid fuel using the two-stage slurry bed system hydrogenation technique of high temperature coal-tar of the present invention to prepare has hydrogen and consumes low, the available raising further of product quality.
(3), in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Its reason mainly due to from paste state bed reactor and from fixed bed reactors in isolated gas containing substantial amounts of hydrogen, it can reuse through adaptive adjustment.
The gas of fixed bed entrance slurry bed system relies primarily on the pressure reduction between stream oriented device to be carried out automatically, and through practical proof, in the light and heavy fractions cut coverage of the application, when heavy oil fraction carries out hydrocracked, treated in two-stage paste state bed reactor, it is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.
The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
Whole technical process has only to use a compressor, the hydrogenation process of all devices can be realized, take full advantage of the pressure reduction between fixed bed and slurry bed system device, from the point of view of reasonably make use of the isolated gas of each equipment to be separately configured, with each device in prior art, the technique that compressor carries out hydrotreating, not only reduce the quantity of compressor, reduce equipment cost, and reasonably make use of hydrogen, further mitigate the hydrogen consumption of whole technique accordingly.
(4) in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, by fixed bed reactors enter paste state bed reactor gas in addition to substantial amounts of hydrogen, possibly together with partial impurities, in this gas, C1～C4 content is high, the mean molecule quantity causing whole air inlet is high, slurry bed system is conducive to operate in turbulent area, slagging prevention predecessor deposition in the reactor.
(5) in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, further, residual oil can also be added in coal tar, high-sulfur oils, high pitch prill contains gauging, high content of beary metal oil, one or more in heavy oil form mixture, above-mentioned steps is used to carry out catalytic hydrogenation in this mixture again, owing to this mixture is arranged suitable cut point, and can be containing the light oil distillate of Sq in heavy oil fraction in the mixture on this cut point, and the existence of this part light oil distillate has collaborative facilitation in two grades of follow-up slurry bed system are hydrocracked to the heavy oil fraction in mixture, it can be greatly improved the hydrogenation conversion of the heavy oil fraction in this part mixes.Therefore, use the two-stage slurry bed system hydrogenation technique of coal tar of the present invention, it is possible not only to coal tar is carried out catalytic hydrogenation, the miscella that residual oil, high-sulfur oils, high pitch prill are formed with coal tar containing gauging, high content of beary metal oil, heavy oil can also be carried out catalytic hydrogenation, and the liquid fuel prepared has hydrogen equally and consumes low, the advantage of excellent product performance.
(6) in the slurry bed system of coal tar of the present invention and fixed bed serial hydrogenation technique, further, it is also possible to select heavy oil fraction is carried out the pre-heat treatment, then with hydrocracking catalyst, H2Mixing, so can make heavy oil fraction and catalyst, H2Mix is more uniform, in order to improve its hydrogenation catalyst efficiency further.
Accompanying drawing explanation
Fig. 1 is slurry bed system and the flow chart of fixed bed serial hydrogenation technique of coal tar of the present invention.
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) coal tar is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 230 DEG C and the heavy oil fraction more than 230 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 220 DEG C, pressure is 12.0MPa, volume space velocity is 0.5h-1, hydrogen to oil volume ratio be 500；The composition of Hydrobon catalyst is as follows: 8wt%NiO, 20wt%MoO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 35%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: reaction temperature 350 DEG C, and pressure is 10.0MPa, volume space velocity is 0.5h-1, hydrogen to oil volume ratio be 1200, hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%MoO3,5wt%NiO, surplus are oil-soluble γ-A12O3Carrier.
In the present embodiment, the total conversion of coal tar is 96.0%, diesel oil total recovery 76%.
Embodiment 2
(1) in cleaning equipment mixture to coal tar and residual oil be dehydrated, the purified treatment of de-mechanical admixture, the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 370 DEG C and the heavy oil fraction more than 370 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 260 DEG C, pressure is 18.0MPa, volume space velocity is 0.6h-1, hydrogen to oil volume ratio be 1000；The composition of Hydrobon catalyst is as follows: 9wt%CoO, 20wt%MoO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 40%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: one-level slurry bed system pressure 12MPa, two grades of slurry bed system pressure 11MPa, and other condition is: reaction temperature 4000 DEG C, and volume space velocity is 1h-1, hydrogen to oil volume ratio be 2000, hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%CoO, 8wt%WO3, surplus are oil-soluble γ-Al2O3Carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction between stream oriented device and automatically carries out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 96.0%, diesel oil total recovery 78%, hydrogen consumption 5.7%.
Embodiment 3
(1) mixture that coal tar, high-sulfur oils and high bitumen content are oily is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 240 DEG C and the heavy oil fraction more than 240 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 300 DEG C, pressure is 14.0MPa, volume space velocity is 0.8h-1, hydrogen to oil volume ratio be 1500；The composition of Hydrobon catalyst is as follows: 8wt%CoO, 25wt%WO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction carry out at 80 DEG C after the pre-heat treatment with hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 65%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: reaction temperature 550 DEG C, and pressure is 18.0MPa, volume space velocity is 1.5h-1, hydrogen to oil volume ratio be 2500, hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%Fe2O3,5wt%NiO, surplus are oil-soluble γ-Al2O3Carrier.
In the present embodiment, the total conversion of coal tar is 96.2%, diesel oil total recovery 77.4%.
Embodiment 4
(1) mixture that coal tar, heavy oil and high heavy metal are oily is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 320 DEG C and the heavy oil fraction more than 320 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 350 DEG C, pressure is 18.0MPa, volume space velocity is 1.0h-1, hydrogen to oil volume ratio be 2000；The composition of Hydrobon catalyst is as follows: 10wt%NiO, 20wt%WO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction carry out at 100 DEG C after the pre-heat treatment with hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 50%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: one-level slurry bed system pressure 16MPa, two grades of slurry bed system pressure 15MPa, and other condition is: reaction temperature 510 DEG C, and volume space velocity is 2h-1, hydrogen to oil volume ratio be 3000, hydrocracking catalyst is oil solubility nanometer level material, consisting of 10wt%Fe2O3,15wt%WO3, surplus are natural zeolite molecular sieve carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction between stream oriented device and automatically carries out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 97.0%, diesel oil total recovery 75.3%, hydrogen consumption 5.8%..
Embodiment 5
(1) coal tar is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 300 DEG C and the heavy oil fraction more than 300 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 400 DEG C, pressure is 18.0MPa, volume space velocity is 1.5h-1, hydrogen to oil volume ratio be 2500；The composition of Hydrobon catalyst is as follows: 4wt%NiO, 10wt%MoO3, 5wt%CoO, 10wt%WO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction carry out at 150 DEG C after the pre-heat treatment with hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 55%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: one-level slurry bed system pressure 18MPa, two grades of slurry bed system pressure 17MPa, and other condition is: reaction temperature 450 DEG C, and volume space velocity is 1.8h-1, hydrogen to oil volume ratio be 3500, hydrocracking catalyst is oil solubility nanometer level material, consisting of 18wt%MoO3,5wt%CoO surplus is natural zeolite molecular sieve carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction between stream oriented device and automatically carries out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 97.2%, diesel oil total recovery 78.2%, hydrogen consumption 6%.
Embodiment 6
(1) coal tar is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out air-distillation, cut into the light oil distillate less than 280 DEG C and the heavy oil fraction more than 280 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 450 DEG C, pressure is 16.0MPa, volume space velocity is 2.0h-1, hydrogen to oil volume ratio be 3000；The composition of Hydrobon catalyst is as follows: 8wt%NiO, 10wt%WO3, 10wt%CoO surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction carry out at 250 DEG C after the pre-heat treatment with hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 70%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: one-level slurry bed system pressure 15MPa, two grades of slurry bed system pressure 14MPa, and other condition is: reaction temperature 380 DEG C, and volume space velocity is 1.3h-1, hydrogen to oil volume ratio be 4000, hydrocracking catalyst is oil solubility nanometer level material, consisting of 30wt%FeS surplus is natural zeolite molecular sieve carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction between stream oriented device and automatically carries out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 94.0%, diesel oil total recovery 78.4%, hydrogen consumption 5.9%.
Embodiment 7
(1) coal tar is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 260 DEG C and the heavy oil fraction more than 260 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 400 DEG C, pressure is 18.0MPa, volume space velocity is 2h-1, hydrogen to oil volume ratio be 2500；The composition of Hydrobon catalyst is as follows: 8wt%NiO, 20wt%MoO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction carry out at 280 DEG C after the pre-heat treatment with hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 85%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: one-level slurry bed system pressure 15MPa, two grades of slurry bed system pressure 14MPa, and other condition is: reaction temperature 530 DEG C, and volume space velocity is 0.8h-1, hydrogen to oil volume ratio be 5000, hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%MoO3,5wt%NiO, surplus are oil-soluble γ-A12O3Carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction between stream oriented device and automatically carries out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 95.0%, diesel oil total recovery 77.6%, hydrogen consumption 5.7%.
Embodiment 8
(1) coal tar is dehydrated in cleaning equipment, takes off the purified treatment of mechanical admixture, and the coal tar water content after dehydration is less than 0.5wt%；
(2) coal tar after purified treatment in described step (1) is carried out decompression distillation, cuts into the light oil distillate less than 350 DEG C and the heavy oil fraction more than 350 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, carries out hydrofinishing under the effect of Hydrobon catalyst after mix homogeneously, and hydrofinishing product is carried out fractional distillation obtains Petroleum and diesel oil.In this step, the condition of described fixed bed hydrogenation reaction is: temperature is 360 DEG C, pressure is 14.0MPa, volume space velocity is 1.0h-1, hydrogen to oil volume ratio be 1200；The composition of Hydrobon catalyst is as follows: 8wt%NiO, 20wt%MoO3, surplus be ZSM-5 molecular sieve.
(4) by described step (2) heavy oil fraction and hydrocracking catalyst, H2Mixing, sequentially enter one-level slurry bed system after mix homogeneously, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio 35%, the hydrocracked product prepared is carried out fractional distillation process, by isolated>arrange outside 540 DEG C of fractions, isolated<350 DEG C of fractions, as fixed bed a part charging mix with the light oil distillate of described step (2) after entrance fixed bed, remaining component returns one-level slurry bed system as a part of feed cycle of one-level slurry bed system；In this step, the reaction condition of two-stage slurry bed system is: reaction temperature 455 DEG C, and pressure is 13.2MPa, volume space velocity is 0.6h-1, hydrogen to oil volume ratio be 2500, hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%MoO3,5wt%NiO, surplus are oil-soluble γ-Al2O3Carrier.
In the most whole hydrogenation technique, as it is shown in figure 1, the hydrogen entering described fixed bed includes being replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；And the described isolated gas of fixed bed is back to described one-level slurry bed system and described two grades of slurry bed system respectively as the feed gas of two-stage slurry bed system.Fixed bed enters the gas of slurry bed system and relies primarily on the pressure reduction that stream oriented device asks and automatically carry out, and is directly met hydrocracking process necessary requirement by the isolated gas of fixed bed as the feed gas of two-stage slurry bed system.The gas being entered fixed bed by two-stage slurry bed system forms the gases at high pressure feed gas as fixed bed with extraneous hydrogen make-up under the pressurization of a compressor, meets the fixed bed hydrogenation process for refining demand to hydrogen partial pressure by the adjustment of extraneous hydrogen.
In the present embodiment, the total conversion of coal tar is 96.2%, diesel oil total recovery 78%, total hydrogen consumption 5.7%.
In addition, present invention also offers coal tar, residual oil, heavy oil, high-sulfur oils, the oily and high content of beary metal oil properties of high bitumen content used in above-mentioned all embodiments, as shown in table 1, and further provide the Petroleum prepared and bavin oil properties, as shown in table 2.
Table 1 raw material oil properties
Petroleum that table 2 prepares and bavin oil properties
Comparative example 1
The present invention uses the process route provided in documents CN103059973A as comparative example of the present invention, and it is with the coal tar that uses in above-described embodiment as raw material, uses following technique to prepare liquid fuel:
Pretreatment removes the water in raw material and mechanical admixture, mixs homogeneously with hydrocracking catalyst and enters paste state bed reactor, and hydrocracking catalyst is oil solubility nanometer level material, consisting of 20wt%MoO3,5wt%NiO, surplus are oil-soluble γ-Al2O3Carrier, hydrocracking condition is as follows: preheating temperature 150 DEG C, reaction temperature 455 DEG C, pressure is 13.2MPa, volume space velocity is 0.6h-1, hydrogen to oil volume ratio be 2500, head product after hydrogenated cracking enters fractionating column, light fraction enters back segment fixed bed reactors and carries out hydrofinishing, this part fraction accounts for 15wt%, midbarrel about 65wt% loops back paste state bed reactor to be continued to be hydrocracked, the heavy end of about 20wt% enters raw material storage tank after the coke produced is removed by filtration in partial catalyst and course of reaction, the cyclic utilization rate of catalyst is about 80%, and wherein light ends fixed bed hydrogenation refining reaction condition is as follows: temperature is 360 DEG C, pressure is 14.0MPa, volume space velocity is 1.0h-1, hydrogen to oil volume ratio be 1200, Hydrobon catalyst consist of 8wt%NiO, 20wt%MoO3, surplus be ZSM-5 molecular sieve.
The performance using the gasoline that above-mentioned technology prepares is as follows: density 0.82g/cm-3, < < 50ppm, octane number 94, the performance of the diesel oil distillate prepared is as follows: density 0.81g/cm for 50ppm, nitrogen content for sulfur content-3, sulfur content < 50ppm, nitrogen content < 50ppm, Cetane number 34.
Comparative example 2
The present invention uses the process route provided in documents CN103059973A as comparative example of the present invention, and it uses following technique to prepare liquid fuel with the full fraction of tar for raw material:
Pretreatment removes the water in raw material and mechanical admixture, mixs homogeneously with hydrocracking catalyst and enters paste state bed reactor, and hydrocracking catalyst is 35%WO3, 10%NiO, 3%P2O5, surplus be USY molecular sieve, hydrocracking condition is as follows: preheating temperature 150 DEG C, reaction pressure break 12MPa, reaction temperature are 390 DEG C, volume space velocity 0.5h-1, hydrogen to oil volume ratio be 1600, head product after hydrogenated cracking enters fractionating column, light fraction enters back segment fixed bed reactors and carries out hydrofinishing, this part fraction accounts for 15wt%, midbarrel about 65wt% loops back paste state bed reactor to be continued to be hydrocracked, the heavy end of about 20wt% enters raw material storage tank after the coke produced is removed by filtration in partial catalyst and course of reaction, the cyclic utilization rate of catalyst is about 80%, wherein light ends fixed bed hydrogenation refining reaction condition is as follows: reaction pressure 8MPa, reaction temperature 375 DEG C, volume space velocity 0.5h-1, hydrogen to oil volume ratio 1600；Product after fixed bed is refined is fractionated into obtaining gasoline and diesel oil；
The performance using the gasoline that above-mentioned technology prepares is as follows: density 0.80g/cm-3, < < 55ppm, octane number 90, the performance of the diesel oil distillate prepared is as follows: density 0.70g/cm for 55ppm, nitrogen content for sulfur content-3, sulfur content < 55ppm, nitrogen content < 55ppm, Cetane number 35.
From above-mentioned two comparative example, using Petroleum that the method for the invention prepares, the sulfur content of diesel oil, nitrogen content to be substantially reduced, diesel-fuel cetane number is also greatly improved.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also cannot all of embodiment be given exhaustive, and the obvious change thus extended out or variation still in the invention scope of the claims among.
Claims (11)
1. the slurry bed system of coal tar and a fixed bed serial hydrogenation technique, comprise the steps:
(1) carry out being dehydrated, taking off the purified treatment of mechanical admixture；
(2) carry out reducing pressure or air-distillation by the coal tar after purified treatment in described step (1), cut into light oil
Fraction and heavy oil fraction, the cut point 220 of light and heavy fractions～370 DEG C；
(3) will be through the light oil distillate in described step (2) and H2Mixing, enters fixed bed, at hydrogenation after mix homogeneously
Carry out hydrofinishing under the effect of catalyst for refining, prepare hydrofinishing product；
(4) by described step (2) heavy oil fraction and hydrocracking catalyst, H2Mixing, depends on after mix homogeneously
Secondary entrance one-level slurry bed system, two grades of slurry bed system carry out two-stage hydrocracking reaction, control conversion ratio between 35～85%,
The hydrocracked product prepared is carried out fractional distillation process,
To arrange outside 540 DEG C of fractions of isolated ＞, 350 DEG C of fractions of isolated ＜ feed and institute as a part for fixed bed
Entering fixed bed after stating the light oil distillate mixing of step (2), remaining component is entered as a part for one-level slurry bed system
Material loops back one-level slurry bed system entrance.
The slurry bed system of coal tar the most according to claim 1 and fixed bed serial hydrogenation technique, it is characterised in that
In the slurry bed system of described coal tar and fixed bed serial hydrogenation technique of stable operation, enter the hydrogen of described fixed bed
Gas bag includes and is replenished the hydrogen make-up of fixed bed and from the isolated gas of two-stage slurry bed system by the external world；
And the described isolated gas of fixed bed is back to described one-level slurry bed system respectively as the feed gas of two-stage slurry bed system
With described two grades of slurry bed system.
The slurry bed system of coal tar the most according to claim 2 and fixed bed serial hydrogenation technique, it is characterised in that
The isolated gas of two-stage slurry bed system mixes with described hydrogen make-up after recycle compressor supercharging.
4. according to slurry bed system and the fixed bed serial hydrogenation technique of the arbitrary described coal tar of claims 1 to 3, it is characterised in that
After the first preheated process of heavy oil fraction in described step (4), then with hydrocracking catalyst, H2Mixing.
The slurry bed system of coal tar and fixed bed serial hydrogenation technique the most according to claim 4, it is characterised in that described
The temperature of the pre-heat treatment is 80～280 DEG C.
6. according to slurry bed system and fixed bed serial hydrogenation technique, its feature of coal tar described in claim 1,2,3 or 5
It is,
Described hydrocracking catalyst is containing one or more in hydrogenation active component Fe, Co, Ni, Mo, W
Nanometer materials.
The slurry bed system of coal tar and fixed bed serial hydrogenation technique the most according to claim 6, it is characterised in that
Described one-level slurry reactor temperature 350～550 DEG C, two grades of slurry reactor temperature are 350～550 DEG C, and two-stage is starched
Other reaction conditions of state bed reactor are: pressure is 10.0～18.0MPa, volume space velocity is 0.5～2.0h‐1, hydrogen oil
Volume ratio is 1200～5000.
8. according to slurry bed system and the fixed bed serial hydrogenation technique of coal tar described in claim 1,2,3,5 or 7, its
It is characterised by,
Described Hydrobon catalyst be in Co Mo system, Ni Mo system, Co W system, Ni W system any one or several
Kind.
The slurry bed system of coal tar and fixed bed serial hydrogenation technique the most according to claim 8, it is characterised in that
The condition of described fixed bed hydrogenation reaction is: temperature is 220～450 DEG C, pressure is 12.0～18.0MPa, volume is empty
Speed is 0.5～2.0h‐1, hydrogen to oil volume ratio be 500～3000.
10. according to slurry bed system and the fixed bed serial hydrogenation work of the coal tar described in claim 1,2,3,5,7 or 9
Skill, it is characterised in that
Described coal tar is one or both in middle coalite tar or high temperature coal-tar.
11. slurry bed system of coal tar and fixed bed serial hydrogenation techniques according to claim 10, it is characterised in that
Coal tar in described step (1) adds residual oil, heavy oil, high-sulfur oils, high bitumen content oil, a high huge sum of money
Belong to containing any one or a few in gauging.
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| CN108219840B (en) * | 2017-12-27 | 2020-12-11 | 北京三聚环保新材料股份有限公司 | Method for converting heavy oil into light oil by using suspension bed hydrogenation process |
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| CN101240191A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for producing lightweight fuel oil by coal tar heavy fractioning hydrogenation |
| CN101864327A (en) * | 2010-04-29 | 2010-10-20 | 长岭炼化岳阳工程设计有限公司 | Coal tar hydrogenation modification method |
| 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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| CN101240191A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for producing lightweight fuel oil by coal tar heavy fractioning hydrogenation |
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