CN101760224B - Method for producing diesel oil by using coal - Google Patents
Method for producing diesel oil by using coal Download PDFInfo
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Abstract
The invention relates to a method for producing diesel oil by using coal, comprising the steps of: transforming coal gas into synthesis gas, and then synthesizing crude oil product by F-T; carrying out reactions such as pre-hydrogenation, hydrofining, hydrocracking and the like on the crude oil product, fractionating under the normal pressure and the reduced pressure, and obtaining F-T synthetic diesel oil fraction; meanwhile, in the processes of coal gasification and destructive distillation, obtaining by-product coal tar; and finally, after hydrofining, hydrocracking and fractionation, obtaining the diesel oil fraction of the coal tar. The two diesel oil fractions are mixed together according to the proportion of 40-99.5% of F-T synthetic diesel oil and 0.5-60% of coal tar diesel oil, so that low-sulfur and low-nitrogen clean diesel oil with the cetane number more than 51 can be produced.
Description
Technical field
The present invention relates to a kind of take the method for coal as raw material production diesel oil.
Background technology
Along with take oil as the increase of liquid fuel demand on basis and the minimizing of petroleum resources usable reserves, the method for being produced available liquid fuel by solid fuels such as coals more and more is subject to people's attention.
The coal preparing liquid fuel has two kinds of technological lines: a kind of is the direct hydrogenation liquefaction of coal synthetic oil, but liquefaction condition is harsh, strict to coal, and China only coal in minority area can use; Another kind is indirect liquefaction, and namely the F-T of indication is synthetic usually, and coal gasifies first and is synthetic gas (CO+H
2), under the condition that iron-based, cobalt-based or iron cobalt-base catalyst exist, but through F-T building-up process synthetic liquid fuel and industrial chemicals, the applicable coal of this process is extensive, and range of product is more.
Coal comes from nineteen twenty-three through F-T synthetic liquid fuel technique functions, and German Fischer and Tropsch find at synthetic gas (CO+H on the iron catalyst, under the 15MPa, 400 ℃ condition
2) can produce liquid hydrocarbon fuels, be called as afterwards the F-T synthesis method.German Rule chemical company began to build the F-T synthetic oil factory take coal as raw material in 1934, went into operation, and produced 40000 tons per year in 1936.1936～1945 years are during the Second World War, the Germany synthetic factory of 9 F-T that builds together, and ultimate production reaches 670,000 tons, and wherein gasoline accounts for 23%, and lubricating oil accounts for 3%, and paraffin and chemical account for 28%.Sa Suoer (Sosal) company has been set up in early 1950s in South Africa, begins to build first Sa Suoer factory, goes into operation in nineteen fifty-five, and Sosal-II and Sosal-III factory are built up respectively in, nineteen eighty-two in 1980.Sasol is the present in the world coal chemical industry enterprises of maximum, and more than 5,000 ten thousand tons in year consumption raw coal is produced more than 700 ten thousand tons of oil product and chemical, and wherein oil product is more than 500 ten thousand tons.
Early 1970s, Holland shell (Shell) company began the research of synthetic oil, proposition is synthesized on cobalt catalyst at utmost preparing heavy hydrocarbon by F-T, and then be converted into the concept of oil product at hydrocracking and isomerization catalyst, the mid-80, develop novel cobalt-base catalyst and heavy hydrocarbon conversion catalyst, oil product is take diesel oil, kerosene as primary and secondary product hard wax.
From output and the structure of consumer demand, China is one of country of consisting of take coal as main energy sources of minority, in China's available stock, coal accounts for 92.6%, oil accounts for 5.35%, Sweet natural gas accounts for 2.05%, coal is the abundantest Energy resources of China's reserves, take coal, Sweet natural gas as the waste synthetic gas, is important component part in China's energy development strategy by the synthetic gas synthetic liquid fuel again.
China builds coal oil mill with Japan is the most joint in the F-T synthetic technology of oil six factory's equipment Imported From German EMH Companies in Jinzhou take cobalt catalyst as core early than nineteen thirty-seven, nineteen forty-three put into production approximately 1,000,000 ton/years of crude oil, rear stopping production was suffered a defeat by Japan in 1945 years.After the founding of New, China again recovers and extends Jinzhou take coal as raw material synthetic oil device, adopt normal pressure cobalt-base catalyst fixed-bed reactor technology, use the water-gas generators preparing synthetic gas, nineteen fifty-one is produced processed oil, 4.7 ten thousand ton/years of the Gao Shida of nineteen fifty-nine output, and realizing fair margin of profit in the situation at that time.Dalian oil institute of the Chinese Academy of Sciences had once carried out 4500 ton/years iron catalyst fluidized-bed synthetic oil pilot plant in nineteen fifty-three.
Early 1980s, Shanxi Coal-Chemical Inst., Chinese Academy of Sciences proposes the synthetic fixed bed two-stage method synthesis technique (MFT technique) that combines with zeolite molecular sieve with traditional F-T, develop simultaneously the synthetic sedimentation type iron-based commercial catalysts of F-T and molecular sieve catalyst, and finish 100 ton/years of industry tests with late 1980s in Shanxi fertilizer plant of Dai County, carry out 2000 ton/years of commerical tests in Jincheng, Shanxi the second fertilizer plant between 1993～1994 years, got through flow process, and output No. 90 qualified gasoline.Early 1990s, Shanxi Coal-Chemical Inst., Chinese Academy of Sciences further developed new and effective Fe/Mn superfine catalyst, finished 3000 hours industrial single column run of continuous operation between 1996～1997 years, and yield of gasoline and quality are improved by a relatively large margin.Carrying out at present the pilot scale of 1000 ton/years of synthetic slurry oil attitude bed process, 160,000 ton/years of synthetic oil demonstration plants are estimated can go into operation in 2008 also among building.
Usually, according to contained heavy oil product in the diesel oil what, diesel oil is divided into solar oil and heavy gas oil, its leading indicator is cetane value, viscosity and zero pour etc.
The F-T synthetic product mainly is comprised of straight-chain paraffin, alkene and organic oxygen-containing compound, has without sulphur, without characteristics such as nitrogen, low aromatic hydrocarbons, can produce cetane value at the high-quality clean diesel cut more than 70 through means such as hydrogenation, hydrocracking.But the straight chain hydrocarbon of F-T combined diesel oil is more, and zero pour is higher, and the unit volume calorific value is low, the lubricity deviation.
In the coal gasification course because the technique that adopts and the type of furnace that gasifies (commonly used have Lurgi, Texaco, Shell etc.) different, but the tar of by-product different components can be divided into coalite tar and coal-tar heavy oil usually.Owing to containing the unsaturated hydrocarbons such as a large amount of alkene, polycyclic aromatic hydrocarbons and sulphur, nitrogen compound in the coal tar, be used for extracting except a small amount of that Chemicals are manyly directly uses as fuel slightly at present, cause and contain a large amount of SO in the flue gas
xAnd NO
x, cause serious environmental pollution, for abundant By Reasonable Utilizing Its Coal Resources; protection of the environment; adopt hydrogenation, hydrocracking process that coal tar is processed, can finish the purpose of desulfurization, denitrogenation, alkene, aromatic saturation, and can obtain petroleum naphtha and diesel oil distillate.
The diesel oil distillate cetane value of coal tar after hydrogenation, hydrocracked, treated is lower, does not reach present diesel oil standard requirement, can not be for the production of fine-quality diesel oil.But owing to containing " weight " component of more for example aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons in the coal tar diesel oil, therefore have advantages of than low-freezing and better lubricity.
People attempt to solve the above-mentioned shortcoming that two kinds of resulting diesel oil of approach exist of passing through for many years, and hope can reach according to different needs the best combination of performance and cost.
USP4,332,666 disclose a kind of method of producing diesel oil, aviation fuel and Number 2 fuel oil, and the raw material of the method is the cut that is suitable for doing hydrogen supply agent in the liquefied coal coil, from the hydrogenation resultant, extract naphthenic hydrocarbon as diesel oil, aviation fuel and Number 2 fuel oil, remaining as hydrogen supply agent.But the yield of diesel oil, aviation fuel product is lower.
US4855037 has introduced a kind of Catalyst And Method of hydrogenation treatment for coal tar, and the coal tar after the hydrotreatment is used for delayed coking.The method mainly is by improving aperture, pore distribution and the metal component of catalyzer, and select suitable processing condition to improve the stability of catalyzer, make catalyzer when processing the full cut of coal tar or tar-bitumen, can keep long-term operation, and improve the quality that generates Jiao in the delayed coking.The method is mainly used in the pre-treatment of delayed coking, not production purpose product.The method is mainly processed mink cell focus, and working pressure is high, invests larger.
US6656342 discloses a kind of method of hydrogenation upgrading Fischer-Tropsch synthetic, the method with the Fischer-Tropsch synthesis product be divided into light, weigh two cuts, cut point is about 371 ℃, two cuts of weight carry out hydrogenation reaction at two reaction zones respectively.Last running enters reactor upper catalyst bed layer; enter successively the different protective material bed of particle diameter and hydrocracking catalyst bed; lighting end enters in the reactor middle and lower part; with after the reaction product of coming autoreactor top bed layer is mixed through entering later separation and fractionating system behind the hydrotreating catalyst bed, unconverted last running can loop back reactor and continue conversion reaction.
CN88105117 has introduced a kind of prescription and compound method thereof of fuel reagent replacing diesel.This invention through refining, is distilled an emulsification take coal tar as raw material, and the operations such as water mixing, purification are made fuel oil, and this product can be used as oil fuel, but is not suitable for diesel engine.
CN1147575C has introduced the method that a kind of coal tar hydrogenating is produced diesel oil.The method is separated into residual oil and distilled oil with coal tar, and this distilled oil carries out hydrogenation in hydro-refining unit, and reaction product obtains gasoline, diesel oil through high score, gas stripping column.Grating and serial connection technology scheme that the method adopts are invested greatlyr, and fundamentally do not solve the low defective of diesel cetane-number.
The inventor is through long-term research, and for the characteristics of F-T combined diesel oil cut and coal tar diesel oil distillate, the allotment by different ratios mixes, and adjustablely allots the clean diesel that indices all satisfies China's diesel oil standard.Thereby provide a kind of method that takes full advantage of coal resources: the F-T combined diesel oil without sulphur, without nitrogen, cetane value greater than 70, but condensation point is higher, lubricity is usually lower slightly, both can remedy the low defective of tar diesel cetane-number by the diesel oil allotment with coal tar production, can improve again the oilness of F-T combined diesel oil, reduce the condensation point of F-T combined diesel oil; Because the by product coal tar nature difference that gasification, destructive distillation obtain is very large, so in allocation process, need the character according to the coal tar diesel oil distillate, suitably adjust the ratio of F-T combined diesel oil cut, thereby make diesel oil indices after obtaining allocating all satisfy the clean diesel of national standard.
Summary of the invention
The purpose of this invention is to provide a kind of diesel oil that obtains take coal as the method for raw material production diesel oil and by the method.
The inventive method comprises the diesel oil of coal being produced through the Fischer-Tropsch route of synthesis with passing through, and allocates according to certain ratio by the diesel oil that coal tar processing is produced, and prepares required high-quality, the diesel oil of cleaning.
Concrete, the inventive method comprises produces diesel oil with gasification, low temperature or the pre-hydrogenation of high temperature F-T synthetic crude oil, hydrofining, hydrocracking, with coal tar deep hydrofinishing, hydrocracking are produced diesel oil, and above-mentioned two kinds of diesel oil are allocated the preparation fine-quality diesel oil according to a certain percentage.
More specifically, the present invention be may further comprise the steps by the method for coal production diesel oil:
(1) coal is converted into synthetic gas through gasification, then obtains thick oil product through the F-T synthetic reaction process, this oil product again with catalyst for pre-hydrogenation, Hydrobon catalyst and hydrocracking catalyst contact reacts, fractionate out diesel oil distillate from the gained oil product;
(2) with coal tar through pre-treatment, obtain oil product through hydrofining, hydrocracking reaction again, fractionate out diesel oil distillate from resulting oil product;
(3) step (1) being processed the diesel oil distillate that obtains through the synthetic diesel oil distillate that obtains of above-mentioned F-T and step (2) coal tar hydrogenating is to modulate at 40～99.5%: 0.5～60% according to the volume ratio of F-T combined diesel oil and Coaltar synthesized diesel, prepares described diesel oil.
In the inventive method, step (1) and (2) can adopt separately that the field is that routine techniques carries out.
Concrete, in the step (1) of the inventive method, at first coal is converted into synthetic gas through gasification, then synthetic gas is obtained thick oil product through the F-T synthetic reaction process, this oil product again with catalyst for pre-hydrogenation, Hydrobon catalyst and hydrocracking catalyst contact reacts, can fractionate out light oil fraction, diesel oil distillate and heavy oil fraction from the gained oil product, described heavy oil fraction can return cracking case and further process, and diesel oil distillate is produced in recycle.
Used catalyst for pre-hydrogenation is a kind of metal load type catalyst in the inventive method step (1), carrier is unformed aluminum oxide, metal component is the IVB metal Ti, the metal M o/W of VIB, or/and the metal Ni of VIIIB family, this catalyzer has advantages of Fischer-Tropsch synthetic crude oil hydrogenation saturated activity high, is particularly suitable for olefin(e) centent high and contain the hydrogenation saturation history of a certain amount of oxygenatedchemicals oil product.
Used Hydrobon catalyst is metal load type catalyst in the inventive method step (1), carrier is unformed aluminum oxide, metal component is the IVB metal Ti, the metal M o/Co of VIB, or/and the metal Ni of VIIIB family, this catalyzer not only has preferably olefin saturated activity, and can remove the oxygenatedchemicals in the oil product.
Used hydrocracking catalyst is Y molecular sieve/unformed alumina load IIIB metal La in the inventive method step (1), the metal M o/Co of VIB, or/and the metal Ni/Pt of VIIIB family, by molecular sieve to adjust its cracking performance and diesel oil selectivity.
In method steps of the present invention (1), wherein said F-T is synthetic can be low temperature (180 ℃～250 ℃) F-T building-up process, also can be high temperature (260 ℃～400 ℃) F-T building-up process.
The F-T synthetic crude oil is mainly by three kinds of fractions consistings: refer to light ends oil, intermediate oil and heavy distillate.Light ends oil wherein, carbon number is the low temperature cold condensate between C1～C25; A kind of is intermediate oil, and its carbon number is the high temperature condensation product between C4～C40; Another kind refers to heavy distillate, claims again F-T wax, and its carbon number is between C6～C75.Mainly be normal paraffin, alkene, organic oxygen-containing compound in the F-T synthetic product.In the inventive method step (1), wherein said F-T synthetic crude oil refers to above-mentioned light ends oil, intermediate oil and heavy distillate; The at first process processing of the thick oil product of preferred described F-T, and then carry out hydrofining, hydrocracking production diesel oil; The processing of described thick oil product refers to light ends oil is mixed with intermediate oil behind pre-hydrogenation, mixes with heavy distillate and carries out hydrofining.
Another embodiment of the inventive method step (1) is that wherein said F-T synthetic crude oil is the synthetic full cut of F-T.
In the method for the invention, the pre-hydrotreating reaction condition of the thick oil product in the wherein said step (1) is: 150 ℃～200 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; The hydrofining reaction condition of described thick oil product is: 160 ℃～350 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 400v/v～1500v/v; And the hydrocracking reaction condition of the heavy ends of described thick oil product after hydrofining, fractionation is: 260 ℃～420 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～8h
-1, hydrogen-oil ratio 400v/v～1500v/v.
In the inventive method step (2), described coal tar comprises gasification of coal tar or destructive distillation coal tar; Wherein said complete processing comprises the by product coal tar in the gasification retort process first through pre-treatment, obtain oil product through hydrofining, hydrocracking reaction again, and fractionating out three kinds of cuts of light oil fraction, diesel oil distillate and hydrogenation tail oil (＞370 ℃), hydrogenation tail oil wherein can return the hydrocracking reaction flow process and carry out recycle.
The part that the inventive method step (2) is produced diesel oil by coal tar processing can adopt following patent open in the disclosed coal tar processing method of producing diesel oil: CN1952070A, CN1952071A, CN100345946C etc.
Employed hydrofining and hydrocracking catalyst are catalyzer commonly used in the similar technique in the inventive method step (2).For example, the used Hydrobon catalyst of step (2) is metal load type catalyst, and carrier is unformed aluminum oxide, and metal component is that the metal M o/W of VIB is or/and the metal Ni of VIIIB family.This catalyzer not only has better desulfurization, nitrogen removal performance, and has the saturated performance of most of hydrogenation of unsaturated hydrocarbons that makes in the coal tar.And for example, used hydrocracking catalyst is Y molecular sieve/unformed alumina load IIIB metal La in the step (2), and the metal M o/W of VIB is or/and the metal Ni of VIIIB family, by molecular sieve to adjust its cracking performance and diesel oil selectivity.
Preferably, the hydrofining reaction condition of coal tar is described in the inventive method step (2): 300 ℃～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.5h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; And the hydrocracking reaction condition of coal tar is: 320 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0MPa～20MPa, liquid hourly space velocity 0.5h
-1～4h
-1, hydrogen-oil ratio 600v/v～2000v/v.
In the step (3) of the inventive method, the diesel oil distillate that coal is obtained through hydrotreatment through the synthetic diesel oil distillate that obtains of F-T and coal tar is 40～99.5%: 0.5～60% according to the volume ratio of F-T combined diesel oil and coal tar diesel oil, preferably according to volume ratio 30～70%: 70～30%, be to be modulated into low-sulfur, low nitrogen, cetane value at 1: 1 greater than 51 clean diesel according to volume ratio more preferably.The ratio of preparation can be determined according to the performance of required diesel oil.
Preferred, the method that the present invention produces diesel oil may further comprise the steps:
1, produces diesel oil distillate by the F-T route of synthesis
F-T synthesis unit part light ends oil is reacted in the presence of hydrogenation catalyst, and reaction conditions is: 150 ℃～200 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; Product behind the hydrogenation and F-T intermediate oil, heavy distillate are mixed into hydrofining reactor, and in the Hydrobon catalyst contact, reaction conditions is: 160 ℃～350 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 400v/v～1500v/v; Then the heavy ends after hydrofining, fractionation is carried out hydrocracking reaction in hydrocracking reactor, condition is: 260 ℃～420 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～8h
-1, hydrogen-oil ratio 400v/v～1500v/v; Crackate is separated through high pressure, low pressure, isolate hydrogen and gaseous hydrocarbon, the product liquid fractionation is obtained diesel oil distillate; Heavy ends can be back to hydrocracking process circulation cracking.
2, diesel oil distillate is produced in coal tar hydrorefining, hydrocracking
With coal tar after filtration, separate and to carry out hydrofining after the pre-treatment remove mechanical impurity and moisture etc. and process, the hydrofining reaction condition is: 300 ℃～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.5h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; Fractionation is carried out in the products therefrom lighting end; Hydrogenated oil carries out hydrocracking reaction, and the hydrocracking reaction condition is: 320 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0MPa～20MPa, liquid hourly space velocity 0.5h
-1～4h
-1, hydrogen-oil ratio 600v/v～2000v/v; Products therefrom obtains light ends, diesel oil distillate and tail oil (＞370 ℃ of cuts), capable of circulation time hydrocracking process circulation of described tail oil cracking after fractionation;
3, the two kinds of diesel oil that are mixed
Performance according to required diesel oil, the diesel oil distillate that the diesel oil distillate that step (1) obtains and step (2) obtain is 40～99.5%: 0.5～60% according to the volume ratio of F-T combined diesel oil and coal tar diesel oil, preferred 30～70%: 70～30%, more preferably 1: 1 ratio is modulated into low-sulfur, low nitrogen, cetane value greater than 51 clean diesel.
Another object of the present invention has provided a kind of diesel oil that obtains with aforesaid method, the diesel oil that is mixed that is obtained by the inventive method is a kind of novel product, described diesel-fuel cetane number is greater than 51, and the diesel oil distillate that is obtained through hydrotreatment through the synthetic diesel oil distillate that obtains of F-T and coal tar by coal is 40～99.5%: 0.5～60% according to the volume ratio of F-T combined diesel oil and coal tar diesel oil; The volume ratio of preferred two kinds of diesel oil distillates is 30～70%: 70～30%; More preferably the volume ratio of two kinds of diesel oil distillates is 1: 1.
In diesel oil of the present invention, wherein said F-T combined diesel oil and coal tar diesel oil all refer to the cut between 150 ℃～370 ℃.
The diesel product known with respect to prior art, product of the present invention and method have the following advantages:
1, both can remedy the low defective of coal tar diesel cetane-number by the diesel oil that makes F-T combined diesel oil and the coal tar production novel diesel of producing that is mixed, can improve again the oilness of F-T combined diesel oil, reduce the condensation point of F-T combined diesel oil, make it have both advantages concurrently.
2, the coal tar of by-product is allocated through diesel oil and the F-T combined diesel oil of processing in the synthetic Gas-making of F-T, F-T synthetic oil enterprise product is optimized, thereby obtained maximum profit.
3, the by product coal tar nature difference that obtains because of gasification, destructive distillation is very large, can suitably adjust the ratio of F-T combined diesel oil cut and coal tar diesel oil distillate according to the character of coal tar diesel oil distillate, obtains the clean diesel that indices meets national standard.
4, can select suitable operational path according to the quality of coal, can fully, reasonably utilize existing coal resources, solve the problem that low grade coal is difficult to produce qualified diesel product.
Embodiment
Method of the present invention comprises coal gasification, low temperature or the pre-hydrogenation of high temperature F-T synthetic crude oil, hydrofining, hydrocracking production diesel oil, and diesel oil is produced in coal tar deep hydrofinishing, hydrocracking, and the allotment of two kinds of diesel oil.The below is described further method of the present invention, and emphasis describes F-T synthetic crude oil processing diesel oil and coal tar hydrogenating, hydrocracked, treated are produced the diesel oil technological process.
Step (1): F-T synthetic crude oil processing diesel oil
Part light ends oil and intermediate oil product that the F-T synthesis unit is obtained enter pre-hydrogenator, react with hydrogenation catalyst, and reaction conditions is: 150 ℃～200 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v.Product behind the hydrogenation with contact with Hydrobon catalyst by being mixed into hydrofining reactor from F-T synthetic heavy distillate, reaction conditions is: 160 ℃～350 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 400v/v～1500v/v; Reaction product is after fractionation, and heavy ends wherein enters hydrocracking reactor and carries out hydrocracking, and the reaction conditions of hydrocracking is: 260 ℃～420 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～8h
-1, hydrogen-oil ratio 400v/v～1500v/v.Resulting crackate is transported to separating unit, separate through high pressure, low pressure, isolate the product liquid that obtains behind hydrogen, the hydrocarbon gas and enter separation column, fractionate out respectively light oil fraction and diesel oil distillate, the heavy ends that fractionates out is back to hydrocracking reactor circulation cracking.
Step (2): diesel oil distillate is produced in coal tar hydrorefining, hydrocracking
Coal tar pretreatment unit after filtration, separate and to remove mechanical impurity, moisture and be delivered to later on hydrofining reactor and process through hydrofining, the hydrofining reaction condition is: 300 ℃～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.5h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v, the products therefrom lighting end is transported to separation column, the hydrogenated oil that fractionation obtains is transported to hydrocracking reactor and carries out hydrocracking, the reaction conditions of hydrocracking is: 320 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0MPa～20MPa, liquid hourly space velocity 0.5h
-1～4h
-1, hydrogen-oil ratio 600v/v～2000v/v; The fractionation in separation column of hydrocracking products therefrom obtains light ends oil, diesel oil distillate and tail oil (370 ℃), capable of circulation time hydrocracking reactor of described tail oil, residue obtained discharge.
Step (3): F-T combined diesel oil and coal tar diesel oil are deployed into the diesel oil of desired properties by volume required ratio, this step can be finished in the conventional equipments such as storage tank, mixing tank.
Below by embodiment technical scheme of the present invention is further described, but the scope that these embodiment do not limit the present invention in any way.Temperature of reaction wherein refers to average reaction temperature.
Embodiment 1 and 2
(1) the synthetic light ends oil of F-T product is at 160 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 4.0Mpa, liquid hourly space velocity 1.0h
-1, hydrogen-oil ratio 800v/v condition under contact with catalyzer and to carry out pre-hydrotreating, reaction product enters hydrofining reactor with Fischer-Tropsch synthetic mesophase cut oil, heavy distillate after mixing, at 260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0Mpa, liquid hourly space velocity 2.0h
-1, hydrogen-oil ratio 1500v/v condition under contact with catalyzer and to carry out hydrofining, reacted product enters hydrocracking reactor and contacts with cracking catalyst, reaction conditions sees Table 2, crackate fractionates out light oil fraction, diesel oil distillate (150 ℃～370 ℃) and heavy oil fraction (＞370 ℃) through separation, fractionation apparatus, and its heavy oil fraction loops back hydrocracking reactor.In aforesaid method, employed catalyst for pre-hydrogenation is the open middle embodiment 2 disclosed catalyzer of CN1276057C patent; Hydrobon catalyst is the open middle embodiment 2 disclosed catalyzer of CN1272102C patent; Embodiment 4 disclosed catalyzer during hydrocracking catalyst CN1136298C patent is open.
In the above-mentioned steps, the synthetic full cut character of F-T sees Table 1; The operating procedure condition of the synthetic full cut processing diesel oil of F-T sees Table 2; The synthetic diesel oil distillate character that obtains of producing of F-T sees Table 3;
Table 1 F-T synthesizes full cut character
Wherein IBP and FBP are respectively initial boiling point and final boiling point, and percentage ratio wherein is the weight percentage that the cut that distillates accounts for total amount.
The synthetic full cut processing diesel oil processing condition of table 2:F-T
The synthetic diesel oil distillate character of producing of table 3:F-T
(2) processing treatment of coal tar is carried out with reference to the method for the open disclosed producing cleaning oil from coal-tar oil of CN1952071A of Chinese patent in the present embodiment.With coal tar after moisture, mechanical impurity are removed in pre-treatment, enter successively hydrofining reactor, hydrocracking reactor, products therefrom fractionates out light ends oil, diesel oil distillate (150 ℃～370 ℃), hydrogenation tail oil and residue through separation column, and wherein hydrogenation tail oil loops back hydrocracking reactor.The coal tar hydrorefining reaction conditions is: 350 ℃ of temperature of reaction, hydrogen dividing potential drop 8.0MPa, liquid hourly space velocity 1.0h
-1, hydrogen-oil ratio 1200v/v.
In the above-mentioned steps, the full cut character of coal tar sees Table 4; The full cut processing of coal tar diesel oil processing condition see Table 5; Coal tar hydrorefining, the resulting diesel oil distillate character of hydrocracking see Table 6.
The full cut character of table 4 coal tar
Table 5: the full cut processing of coal tar diesel oil processing condition
Table 6: producing diesel by utilizing coal tar cut character
(3) diesel oil distillate that F-T is synthetic and be mixed with diesel product in 7: 3 by volume and 1: 1 respectively by the synthetic diesel oil distillate of coal tar, the character of embodiment 1 and embodiment 2 resulting diesel oil sees Table 7.
The character that table 7 embodiment 1 and 2 different ratioss are allocated resulting diesel oil
Its zero pour of diesel oil that obtains with method of the present invention obviously descends, and wear scar diameter reduces, and illustrates that lubricity has clear improvement, can satisfying the market to the multiple demand of diesel oil.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these changes and improvements are all within protection scope of the present invention.
Claims (15)
1. method of being produced diesel oil by coal, the method may further comprise the steps:
(1) coal is converted into synthetic gas through gasification, then obtains thick oil product through the F-T synthetic reaction process, this oil product again with catalyst for pre-hydrogenation, Hydrobon catalyst and hydrocracking catalyst contact reacts, fractionate out diesel oil distillate from the gained oil product;
(2) with coal tar through pre-treatment, obtain oil product through hydrofining, hydrocracking reaction again, fractionate out diesel oil distillate from resulting oil product;
(3) step (1) being processed the diesel oil distillate that obtains through the synthetic diesel oil distillate that obtains of above-mentioned F-T and step (2) coal tar hydrogenating is to modulate at 30～99.5%: 70～0.5% according to the volume ratio of F-T combined diesel oil and Coaltar synthesized diesel, prepares described diesel oil.
2. according to the production method of the described diesel oil of claim 1, wherein the volume ratio of the diesel oil distillate that obtains of the synthetic diesel oil distillate that obtains of F-T and coal tar hydrogenating processing is 30～70%: 70～30%.
3. according to the production method of the described diesel oil of claim 2, wherein the volume ratio of the diesel oil distillate that obtains through hydrotreatment of the synthetic diesel oil distillate that obtains of F-T and coal tar is 1: 1.
4. according to the production method of the described diesel oil of claim 1-3 any one, wherein said F-T combined diesel oil and coal tar diesel oil are the cut between 150 ℃～370 ℃.
5. according to the production method of the described diesel oil of claim 4, wherein said F-T synthesizes and comprises 180 ℃～250 ℃ of low temperature and 260 ℃～400 ℃ F-T building-up processes of high temperature.
6. according to the production method of the described diesel oil of claim 1, the pre-hydrotreating reaction condition of the thick oil product in the wherein said step (1) is: 150 ℃～200 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; The hydrofining reaction condition of described thick oil product is: 160 ℃～350 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～10h
-1, hydrogen-oil ratio 400v/v～1500v/v; And the hydrocracking reaction condition of the heavy ends of described thick oil product after hydrofining, fractionation is: 260 ℃～420 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.1h
-1～8h
-1, hydrogen-oil ratio 400v/v～1500v/v.
7. according to the production method of the described diesel oil of claim 6, wherein the described F-T synthetic crude oil of step (1) refers to the full cut that F-T is synthetic.
8. according to the production method of the described diesel oil of claim 1, wherein the described F-T synthetic crude oil of step (1) refers to light ends oil, intermediate oil and heavy distillate; Wherein said light ends oil carbon number is C1-C25, and described intermediate oil carbon number is C4-C40, and described heavy distillate carbon number is C6-C75.
9. according to the production method of the described diesel oil of claim 8, wherein said thick oil product at first process is processed, and then carries out hydrocracking and produce diesel oil; Described thick oil product processing refers to light ends oil is mixed with intermediate oil behind pre-hydrogenation, mixes with heavy distillate and carries out hydrofining.
10. according to the production method of the described diesel oil of claim 1, the coal tar in the wherein said step (2) comprises gasification of coal tar or destructive distillation coal tar.
11. according to the production method of the described diesel oil of claim 10, the hydrofining reaction condition of wherein said coal tar is: 300 ℃～400 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～15MPa, liquid hourly space velocity 0.5h
-1～5h
-1, hydrogen-oil ratio 400v/v～1500v/v; And the hydrocracking reaction condition of coal tar is: 320 ℃～450 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0MPa～20MPa, liquid hourly space velocity 0.5h
-1～4h
-1, hydrogen-oil ratio 600v/v～2000v/v.
12. the diesel oil that the described method of claim 1-11 any one is produced, wherein said product diesel-fuel cetane number is greater than 51, and the diesel oil distillate that is obtained through hydrotreatment through the synthetic diesel oil distillate that obtains of F-T and coal tar by coal is that 30～99.5%:70～0.5% is modulated and formed according to the volume ratio of F-T combined diesel oil and coal tar diesel oil.
13. according to the described diesel oil of claim 12, wherein the volume ratio of the diesel oil distillate that obtains through hydrotreatment of the synthetic diesel oil distillate that obtains of F-T and coal tar is 30～70%: 70～30%.
14. according to the described diesel oil of claim 13, wherein the volume ratio of the diesel oil distillate that obtains through hydrotreatment of the synthetic diesel oil distillate that obtains of F-T and coal tar is 1: 1.
15. according to the described diesel oil of claim 12-14 any one, wherein said F-T combined diesel oil and coal tar diesel oil all refer to the cut between 150 ℃～370 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB502802A (en) * | 1936-09-24 | 1939-03-24 | Steinkohlen Bergwerk Rheinpreu | Process for the treatment of coal and like tar oils |
| CN101240193A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Coal tar multistage hydrogenation treatment technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB502802A (en) * | 1936-09-24 | 1939-03-24 | Steinkohlen Bergwerk Rheinpreu | Process for the treatment of coal and like tar oils |
| CN101240193A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Coal tar multistage hydrogenation treatment technique |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 030006, Shanxi, Taiyuan hi tech Development Zone, South Central Street, Cyberport 2, port 4, A, B District Patentee before: Zhongke Synthetic Oil Technology Co., Ltd. |
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Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |