CN102911729B - Method for producing diesel oil from Fischer-Tropsch synthetic oil - Google Patents
Method for producing diesel oil from Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
The invention discloses a method for producing diesel oil from Fischer-Tropsch synthetic oil. The method comprises the following steps of (1) contacting mixed oil composed of low temperature method Fischer-Tropsch synthetic light oil, low temperature method Fischer-Tropsch synthetic heavy oil and full fractions of high temperature method Fischer-Tropsch synthetic oil in presence of a hydrorefining catalyst, under hydrorefining reaction conditions; and (2) performing gas-liquid separation on the product obtained from the step (1), and cutting the product to obtain a first wax oil fraction; (3) contacting a mixture of the first wax oil fraction obtained from the step (2) and the low temperature method Fischer-Tropsch synthetic wax with hydrogen in the presence of a hydrocracking catalyst, under hydrocracking reaction conditions; and (4) performing the gas-liquid separation and a cutting operation on the product obtained from the step (3). The method has the following advantages of (1) improving the density of the obtained diesel oil, allowing the diesel oil to meet the requirement of Europe IV diesel oil standard; (2) greatly reducing a condensation point of the obtained diesel oil; and (3) effectively preventing the occurrence from a too fast coking phenomenon.
Description
Technical field
The present invention relates to a kind of method of being produced diesel oil by Fischer-Tropsch synthesis oil.
Background technology
Minimizing day by day along with petroleum resources in world wide, substitute energy technological development comes into one's own gradually, and wherein Fischer-Tropsch synthetic technology is produced the technology of fuel with high cleanness and receives much concern as the raw material that can utilize coal, Sweet natural gas, biomass etc. to contain carbon, hydrogen resource.Fischer-Tropsch synthetic technology is distinguished with service temperature, can be divided into that low temperature process Fischer-Tropsch is synthetic and pyroprocess Fischer-Tropsch synthetic, and the synthetic oil of two kinds of methods all has without sulphur, without the feature of nitrogen.Wherein low temperature process Fischer-Tropsch synthesis oil has the advantages that straight-chain paraffin is high, oil product condensation point is high, product oil density is little; The feature of pyroprocess Fischer-Tropsch synthesis oil and low temperature process synthetic oil differ larger, and pyroprocess Fischer-Tropsch synthesis oil alkene, diene content are high, contain a certain amount of naphthenic hydrocarbon, aromatic hydrocarbons, and oil product condensation point is low, product oil density is relatively high.
The preparing liquid fuel technology that Fischer-Tropsch synthetic technology is core all be take in exploitation in each major oil companies, and wherein synthetic the and low temperature process Fischer-Tropsch synthetic technology of the pyroprocess Fischer-Tropsch of Sasol company has all been successfully applied to industrial production; The low temperature process Fischer-Tropsch synthetic technology of Shell company was also successfully applied to industrial production in 1993; Domestic Shenhua Group, Lu An group, Yi Tai group all put into operation ten thousand tons/year of low temperature process Fischer-Tropsch synthesizers of 16-18.The construction of Yan ore deposit megaton low temperature process Fischer-Tropsch compound probability device is brought into schedule; Kiloton pyroprocess Fischer-Tropsch synthetic pilot scale research in Yan ore deposit completed in 2007, indicated that China has possessed the ability of building pyroprocess Fischer-Tropsch compound probability device.
As one of main purpose of Fischer-Tropsch synthetic technology, producing diesel oil is the vital task of synthetic oil factory, and low temperature process synthetic oil and pyroprocess synthetic oil are produced diesel oil process by method of hydrotreating and all had some problems.Due to the aforementioned features of low temperature process synthetic oil, make the diesel oil distillate after hydrogenation there is high, the low density feature of condensation point, cannot directly as commercial Dissel oil, sell.Pyroprocess Fischer-Tropsch synthesis oil is owing to having higher alkene and diene content, is very easy to coking in hydrogenation process, and then shortened device running period.
For the upgrading of synthetic oil hydrogenation, Ge great research institution has developed some correlation techniques, respectively low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil has been carried out to various improvement:
Shell company discloses a kind of method of producing intermediate oil in patent US6858127, what the method adopted is that at least part of synthetic oil is carried out to hydrocracking, then isolate coal diesel oil distillate wherein, tail oil carries out hydrocracking again, coal diesel oil distillate in separated product again, wherein diesel oil distillate density is 0.78g/cm
3, condensation point is-28-0 ℃.
Chevron company discloses a kind of technique of being produced gasoline, distillate, lube stock component by Fischer-Tropsch synthesis oil and fraction oil of petroleum in patent US6863802, and the method is that Fischer-Tropsch distillate and fraction oil of petroleum mixing are obtained to fuel or lube stock by the method for hydrogenation upgrading again.The method is still usingd petroleum base raw material as the stock oil of producing diesel oil.
Sasol company discloses a kind of method of being prepared low-sulfur diesel-oil and low emission aviation fuel by synthetic oil in patent US7390397, and the method is carried out fractionation by low temperature process synthetic oil, fractionates out kerosene(oil)fraction and diesel oil distillate, and its ratio is at least 1: 2.Wherein kerosene smoke point is greater than 50mm, and condensation point, lower than-47 ℃, can be used as low emission rocket engine fuel or blending component.Diesel oil distillate condensation point is at least 0.78g/cm lower than-5 ℃, density
3, can be used as low-sulfur diesel-oil or blend component.
Zhong Ke synthetic oil company discloses a kind of hydroprocessing technique of Fischer-Tropsch synthesis oil in CN200710065309, this technique is that first the full cut of Fischer-Tropsch synthesis oil is carried out to hydrotreatment, then isolate the first diesel oil distillate in product, tail oil cut carries out hydrocracking again, isocrackate carries out separation again, isolates the second diesel oil distillate wherein, and wherein the condensation point of the second diesel oil distillate is 2-5 ℃, the condensation point of the second diesel oil distillate is less than-50 ℃, and the method can production part low-coagulation diesel oil.
Aforesaid method is by obtaining diesel oil distillate to Fischer-Tropsch synthesis oil direct hydrogenation or with the method for petroleum base raw material mixed hydrogenation.But all there are separately some defects, the diesel oil density that obtains in US6858127 is low, condensation point is high, can not meet derv fuel oil index request, the diesel oil obtaining in US7390397 only can be as blend component, and only can obtain part low-coagulation diesel oil in CN200710065309.
Therefore, still need development can obtain high-density, low freezing point diesel fuel and the equipment method of continuous operation for a long time.
Summary of the invention
The object of this invention is to provide and a kind ofly can obtain high-density, low freezing point diesel fuel, and the equipment method of producing diesel oil by Fischer-Tropsch synthesis oil of continuous operation for a long time.
The invention provides a kind of method of being produced diesel oil by Fischer-Tropsch synthesis oil, the method comprises the following steps, (1) under hydrofining reaction condition, under Hydrobon catalyst exists, the synthetic light oil of low temperature process Fischer-Tropsch, low temperature process Fischer-Tropsch synthesis of heavy oil are contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil; (2) the contact products therefrom of step (1) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the first naphtha fraction, the first diesel oil distillate and the first wax oil cut; (3), under hydrocracking reaction condition, under hydrocracking catalyst exists, the first wax oil cut that step (2) is obtained contacts with hydrogen with the mixture of low temperature process Fischer-Tropsch synthetic wax; (4) the contact products therefrom of step (3) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the second naphtha fraction, the second diesel oil distillate and the second wax oil cut.
The method according to this invention is carried out the hydrogenation upgrading of Fischer-Tropsch synthesis oil, and the density of the diesel oil distillate obtaining is greater than 0.82g/cm
3, sulphur content is less than 5 μ g/g, and cetane value, higher than 51, meets the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-32 ℃ to-34 ℃, can meet the requirement of low temp area to diesel low-temperature liquidity.And use separately low temperature process Fischer-Tropsch synthesis oil to carry out hydrogenation upgrading, the density of the diesel oil distillate obtaining is 0.7631g/cm
3, can not meet the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-2 ℃, cannot meet the requirement of low temp area to the mobility of diesel oil at low-temperature.And use separately pyroprocess Fischer-Tropsch synthesis oil to carry out hydrogenation upgrading, and although the density of diesel oil distillate is higher, condensation point is also lower, can meet the requirement to diesel low-temperature liquidity of Europe IV diesel oil standard and low temp area, its cetane value is very low.
In addition, utilize method of the present invention to carry out the hydrogenation upgrading of Fischer-Tropsch synthesis oil, carry out continuously 240 hours, reactor does not have obvious coking phenomenon, and the hydrogenation upgrading of using separately pyroprocess Fischer-Tropsch synthesis oil to carry out is carried out 150 hours, reactor bed pressure drop obviously increase is also increased to rapidly 0.7MPa, reaction cannot be proceeded, and device finds that the coking of beds top is serious after stopping work.
To sum up, the advantage of method of the present invention is:
(1) having overcome independent use low temperature process Fischer-Tropsch synthesis oil, to carry out the diesel oil density that hydrogenation upgrading obtains low, cause the defect that unit volume calorific value is lower, by by low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, improved the density of the diesel oil making, made it meet the requirement of Europe IV diesel oil standard;
(2) having overcome independent use low temperature process Fischer-Tropsch synthesis oil, to carry out the condensation point of diesel oil that hydrogenation upgrading obtains higher, cannot meet the defect that low temperature area requires fuel condensation point, by by low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, greatly reduce the condensation point of the diesel oil making;
(3) while having overcome independent use pyroprocess Fischer-Tropsch synthesis oil, because its alkene, diene content are high, carry out hydrogenation upgrading and process and be very easy to coking, cause that catalyst deactivation is fast, device is short running period.By by low temperature process Fischer-Tropsch synthesis oil and the upgrading of pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, reduced the concentration of alkene, diolefine in raw material, effectively prevented that the too fast phenomenon of coking from occurring.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is process flow sheet of the present invention.
Embodiment
The invention provides a kind of method of being produced diesel oil by Fischer-Tropsch synthesis oil, the method comprises the following steps,
(1) under hydrofining reaction condition, under Hydrobon catalyst exists, the synthetic light oil (LTFT-LO) of low temperature process Fischer-Tropsch, low temperature process Fischer-Tropsch synthesis of heavy oil (LTFT-HO) are contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil (HTFT);
(2) the contact products therefrom of step (1) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the first naphtha fraction, the first diesel oil distillate and the first wax oil cut;
(3), under hydrocracking reaction condition, under hydrocracking catalyst exists, the first wax oil cut that step (2) is obtained contacts with hydrogen with the mixture of low temperature process Fischer-Tropsch synthetic wax (LTFT-HW);
(4) the contact products therefrom of step (3) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the second naphtha fraction, the second diesel oil distillate and the second wax oil cut.
The present invention is carrying out the mixing oil of the full cut of low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil on the basis of hydrogenation upgrading, further optimized reaction process, first the synthetic light oil of low temperature process Fischer-Tropsch, low temperature process Fischer-Tropsch synthesis of heavy oil and the synthetic full cut of pyroprocess Fischer-Tropsch are mixed and carry out hydrofining, again by isolated heavy constituent in hydrotreated product, be that wax oil cut mixes with low temperature process Fischer-Tropsch synthetic wax, carry out hydrocracking, further isolate the diesel oil distillate in isocrackate.Compare with the method for directly mixing oil of the full cut of low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil being carried out to hydrogenation upgrading, the first step of this technique is without low temperature process Fischer-Tropsch synthetic wax is carried out to hydrofining, thereby dwindled hydrofining reactor, also reduce the consumption of Hydrobon catalyst, and then reduced the cost of technique.
According to the present invention, in step (1), the synthetic light oil of described low temperature process Fischer-Tropsch and the gross weight of low temperature process Fischer-Tropsch synthesis of heavy oil and the weight ratio of the full cut of pyroprocess Fischer-Tropsch synthesis oil can in very large range change, the oxygen level of mixing oil and the content of normal paraffin of final acquisition is depended in the selection of the two part by weight, in the present invention, preferably, the synthetic light oil of described low temperature process Fischer-Tropsch and the gross weight of low temperature process Fischer-Tropsch synthesis of heavy oil and the weight ratio of the full cut of pyroprocess Fischer-Tropsch synthesis oil are 5: 95-95: 5, more preferably 1: 0.5-2.In above-mentioned preferable range, can obtain better hydrofining effect, but one skilled in the art may determine that method of the present invention is not limited only to above-mentioned preferred scope.
According to the present invention, in step (3), the first wax oil cut that described step (2) obtains and the weight ratio of low temperature process Fischer-Tropsch synthetic wax can in very large range change, ratio between the two depends on oxygen level and normal paraffin content equal size in mixture, preferably, the first wax oil cut that described step (2) obtains and the weight ratio of low temperature process Fischer-Tropsch synthetic wax are 5: 95-95: 5, more preferably 1: 1-5, in the present invention, most preferably be 1: 3-5.In above-mentioned preferable range, can obtain better hydrogenation; Cracking effect, but one skilled in the art may determine that method of the present invention is not limited only to above-mentioned preferred scope.
In the present invention, naphtha fraction, diesel oil distillate and wax oil cut are concept well known in the art, and the boiling range of described the first naphtha fraction and the second naphtha fraction can be independently of one another within the scope of 15-200 ℃.The boiling range of described the first diesel oil distillate and the second diesel oil distillate can be independently of one another within the scope of 150-370 ℃.The boiling range of described the first wax oil cut and the second wax oil cut can be independently of one another within the scope of 320-750 ℃.The described contact products therefrom by step (1) carries out gas-liquid separation, and the oil phase cutting that gas-liquid separation is obtained can be the method for this area routine, as passed through high-pressure separator, light pressure separator by liquid phase separation, and the water in liquid phase is removed, obtain oil phase, then by separation column, oil phase cutting is obtained to above-mentioned naphtha fraction, diesel oil distillate and wax oil cut.
According to the present invention, the method that the separated method that obtains the synthetic light oil of low temperature process Fischer-Tropsch, low temperature process Fischer-Tropsch synthesis of heavy oil and the synthetic wax oil of low temperature process Fischer-Tropsch is known to the skilled person from the full cut of low temperature process Fischer-Tropsch synthesis oil, as carried out separation by distillation tower.Wherein, preferably, the initial boiling point of the synthetic light oil of described low temperature process Fischer-Tropsch is 20-100 ℃, and final boiling point is 250-350 ℃, and further preferably, the initial boiling point of the synthetic light oil of described low temperature process Fischer-Tropsch is 20-50 ℃, most preferably is 30-50 ℃; Final boiling point is 300-350 ℃.Preferably, the weight of the synthetic light oil of the low temperature process Fischer-Tropsch of take is benchmark, in the synthetic light oil of described low temperature process Fischer-Tropsch, oxygen level is 0.5-8 % by weight, further preferably, the weight of the synthetic light oil of the low temperature process Fischer-Tropsch of take is benchmark, in the synthetic light oil of described low temperature process Fischer-Tropsch, oxygen level is 0.2-3 % by weight, most preferably is 1-3 % by weight.
Preferably, the initial boiling point of described low temperature process Fischer-Tropsch synthesis of heavy oil is 100-400 ℃, and final boiling point is 300-500 ℃, and further preferably, the initial boiling point of described low temperature process Fischer-Tropsch synthesis of heavy oil is 200-300 ℃, and final boiling point is 400-500 ℃.Preferably, the weight of low temperature process Fischer-Tropsch synthesis of heavy oil of take is benchmark, in described low temperature process Fischer-Tropsch synthesis of heavy oil, oxygen level is 0.2-5 % by weight, further preferably, the weight of low temperature process Fischer-Tropsch synthesis of heavy oil of take is benchmark, in described low temperature process Fischer-Tropsch synthesis of heavy oil, oxygen level is 0.1-2 % by weight, most preferably is 0.5-1.5 % by weight.
Preferably, the initial boiling point of described low temperature process Fischer-Tropsch synthetic wax is 300-500 ℃, and final boiling point is 600-750 ℃, and further preferably, the initial boiling point of described low temperature process Fischer-Tropsch synthetic wax is 300-400 ℃, and final boiling point is 650-750 ℃.Preferably, the weight of low temperature process Fischer-Tropsch synthetic wax of take is benchmark, in described low temperature process Fischer-Tropsch synthetic wax, oxygen level is 0-2 % by weight, further preferably, the weight of low temperature process Fischer-Tropsch synthetic wax of take is benchmark, in described low temperature process Fischer-Tropsch synthetic wax, oxygen level is 0-1 % by weight, most preferably is 0.2-0.5 % by weight.
According to the present invention, described low temperature process Fischer-Tropsch synthesizes light oil, described low temperature process Fischer-Tropsch synthesis of heavy oil and described low temperature process Fischer-Tropsch synthetic wax can be the product under same Fischer-Tropsch synthesis condition, also can not be the product under same Fischer-Tropsch synthesis condition, preferably, described low temperature process Fischer-Tropsch synthesizes light oil, described low temperature process Fischer-Tropsch synthesis of heavy oil and described low temperature process Fischer-Tropsch synthetic wax are the product under same Fischer-Tropsch synthesis condition, wherein, described same Fischer-Tropsch synthesis condition comprises: temperature of reaction is preferably 170-260 ℃, reaction pressure is preferably 1.5-4.5MPa, further preferably, temperature of reaction is 180-240 ℃, reaction pressure is 2-4MPa.
In the present invention, to the full cut of described pyroprocess Fischer-Tropsch synthesis oil, there is no particular limitation, and preferably, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 ℃, and final boiling point is at 300-450 ℃; Further preferably, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-50 ℃, most preferably is 30-50 ℃; Final boiling point is at 300-400 ℃; The total amount of the full cut of pyroprocess Fischer-Tropsch synthesis oil of take is benchmark, and in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 1-10 % by weight, and normal paraffin content is 4-30 % by weight, and olefin(e) centent is 40-95 % by weight; Further preferably, in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 2-8 % by weight, most preferably is 3-5 % by weight; Normal paraffin content is 10-20 % by weight, and olefin(e) centent is 60-80 % by weight, most preferably is 60-70 % by weight.
According to the present invention, preferably, the full cut of above-mentioned pyroprocess Fischer-Tropsch synthesis oil is H
2with CO in temperature of reaction, be under 280-380 ℃, the reaction pressure condition that is 1.5-4.5MPa, under fischer-tropsch synthetic catalyst exists, synthetic obtaining, further preferably, is H
2with CO in temperature of reaction, be under 300-360 ℃, the reaction pressure condition that is 2-4MPa, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
To described hydrogen, there is no particular limitation in the present invention, can synthesize field various hydrogen conventional used for Fischer-Tropsch, as high-purity new hydrogen, and hydrogen-rich gas isolated from reaction product, that use as recycle hydrogen.
According to the present invention, described fischer-tropsch synthetic catalyst can be the various fischer-tropsch synthetic catalysts of routine, for example, and iron-base fischer-tropsch synthesis catalyst and Co based Fischer-Tropsch synthesis catalyst.
According to the present invention, preferably, described Hydrobon catalyst contains shaping carrier A1 and loads on the hydrogenation active metals component A2 on this shaping carrier A1, the total amount of this Hydrobon catalyst of take is benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 10-50 % by weight; Metal in described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight; Further preferably, the total amount of this Hydrobon catalyst of take is benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 52-75 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 25-48 % by weight, the middle metal of described hydrogenation active metals component A2 is nickel, molybdenum and tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of nickel is 2-7 % by weight, the content of molybdenum is 1-6 % by weight, and the content of tungsten is 22-35 % by weight; Most preferably, in described Hydrobon catalyst, the content of shaping carrier A1 is 58-75 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is that the metal in hydrogenation active metals component A2 is nickel and tungsten described in 25-42 % by weight, in oxide compound and take the weight of Hydrobon catalyst as benchmark, in affiliated Hydrobon catalyst A, the content of nickel is 2-7 % by weight, and the content of tungsten is 23-35 % by weight.
In the present invention, preferably, described shaping carrier is aluminum oxide and/or silicon oxide.Preferably, described shaping carrier is aluminum oxide.
The present inventor finds, adopts above-mentioned preferred shaping carrier and hydrogenation active metals component to carry out hydrofining reaction as Hydrobon catalyst, can access the effect of good olefin saturated, hydrogenation deoxidation and hydrogenating desulfurization.The Hydrobon catalyst that the Hydrobon catalyst with above-mentioned preferred composition and content can be for example RTF-1 for the trade names of China Petrochemical Industry's catalyzer Chang Ling branch office production.
According to the present invention, preferably, described hydrocracking catalyst contains shaping carrier B1 and loads on the hydrogenation active metals B component 2 on this shaping carrier B1, and the total amount of this hydrocracking catalyst of take is benchmark, in described hydrocracking catalyst, the content of shaping carrier is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals component is 10-50 % by weight; Metal in described hydrogenation active metals component is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and take the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight.Further preferably, the total amount of this hydrocracking catalyst of take is benchmark, and in described hydrocracking catalyst, the content of shaping carrier is 57-77 % by weight, and in oxide compound, the content of described hydrogenation active metals component is 23-43 % by weight; Metal in described hydrogenation active metals component is nickel and tungsten, and in oxide compound and take the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 3-8 % by weight, and the content of tungsten is 20-35 % by weight.The present inventor finds, adopts above-mentioned preferably shaping carrier and hydrogenation active metals component to carry out hydrocracking reaction as hydrocracking catalyst, can access good cracking effect, contributes to promote the quality of gained diesel oil distillate.
According to the present invention, preferably, described shaping carrier is silicon oxide and aluminum oxide, and the weight of shaping carrier of take is benchmark, in described shaping carrier, the content of silicon oxide is 1-40 % by weight, and the content of aluminum oxide is 60-99 % by weight, further preferably, in described shaping carrier, the content of silicon oxide is 3-30 % by weight, and the content of aluminum oxide is 70-97 % by weight.The hydrocracking catalyst that the hydrocracking catalyst with above-mentioned preferred composition and content can be for example RCF-1 for the trade names of China Petrochemical Industry's catalyzer Chang Ling branch office production.
Because core of the present invention is the mixing of the full cut of low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil, therefore, the catalyzer of described hydrofining and hydrocracking and reaction conditions can be all ordinary method and the condition of this area.
According to the present invention, preferably, described hydrofining reaction condition comprises: temperature be 200-400 ℃, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 200-1000; Further preferably, described hydrofining reaction condition comprises: temperature be 250-350 ℃, hydrogen dividing potential drop while being 4-8MPa, liquid volume space velocity be 1-8h
-1, hydrogen to oil volume ratio is 300-800.
According to the present invention, preferably, described hydrocracking reaction condition comprises: temperature be 300-450 ℃, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 500-1500, further preferably, described hydrocracking reaction condition comprises: temperature be 350-400 ℃, hydrogen dividing potential drop while being 4-8MPa, liquid volume space velocity be 1-8h
-1, hydrogen to oil volume ratio is 800-1200.
According to the present invention, in step (4), described contact products therefrom is carried out to gas-liquid separation and the described products therefrom that contacts is carried out to gas-liquid separation and can complete in step (2) in identical or different separation system, preferably, in identical separation system, complete.When adopting identical separation system, separating obtained whole wax oil cuts enter step (3) and carry out hydrocracking reaction.
Method provided by the invention, can adopt periodical operation, also can operate continuously etc., feed way can be also any suitable way well known by persons skilled in the art, the present invention, does not repeat at this all without particular requirement one by one to this.
Below, in conjunction with Fig. 1, method of the present invention is described in detail.After the mixing oil that low temperature process Fischer-Tropsch synthesizes light oil, low temperature process Fischer-Tropsch synthesis of heavy oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil mixes through pipeline 1 and hydrogen from pipeline 2 and from the recycle hydrogen of pipeline 3, through the reactor 4 of Hydrobon catalyst is housed, under hydrofining reaction condition, carry out hydrofining.The hydrotreated product of hydrofining reactor 4 enters high pressure hot separator 6 through pipeline 5 and carries out gas-liquid separation, and gas part enters cold high pressure separator 8 through pipeline 7, and liquid portion enters thermal low-pressure separators 10 through pipeline 9.Enter the logistics further gas-liquid separation in separator in cold high pressure separator 8, gas part enters compressor 12 through pipeline 11, through pipeline 3, pipeline 13, loop back hydrofining reactor 4 and hydrocracking reactor 14 respectively, remaining gas is through the outer row of pipeline 15.The isolated water of cold high pressure separator 8 is through the outer row of pipeline 16, and liquid hydrocarbon enters cold low separator 18 through pipeline 17, carries out flash distillation in cold low separator 18, and the gas flashing off part is through the outer row of pipeline 19, and liquid portion enters separation column 21 through pipeline 20.By the isolated gas of thermal low-pressure separators 10 part, through pipeline 22, enter cold low separator 18, liquid portion enters separation column 21 through pipeline 23 after logistics from pipeline 20 mixes.In separation column 21, charging is separated into naphtha fraction, diesel oil distillate and wax oil cut, wherein naphtha fraction is through pipeline 24 dischargers, diesel oil distillate is through pipeline 25 dischargers, wax oil cut is through pipeline 26 and low temperature process Fischer-Tropsch synthetic wax from pipeline 27, new hydrogen from pipeline 28, after recycle hydrogen mixing from pipeline 13, enter the reactor 14 that hydrocracking catalyst is housed, in reactor 14, carry out hydrocracking, isocrackate through pipeline 29 with after mixing of materials from pipeline 5, enter high pressure hot separator and carry out separated, and carry out follow-up separating step.
Below, by embodiment, the present invention will be described in more detail.
In the embodiment of the present invention, technological process is shown in Fig. 1.The density of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records by SH0604 method.The oxygen level of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records by ASTM D5622 method.The bromine valency of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records according to the method for recording in RIPP 66-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.).The sulphur content of the diesel oil distillate that separation obtains records by GB17040 method.The condensation point of the diesel oil distillate that separation obtains records by GB510 method.The cetane value of the diesel oil distillate that separation obtains records by GB386 method.In HTFT, olefin(e) centent records by the method for recording in RIPP 153-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.).The normal paraffin content of LTFT, HTFT and mixing oil records by SH/T0729 method.Boiling range records by ASTM D86/D1160 method.
In embodiment, Hydrobon catalyst used is RTF-1, and hydrocracking catalyst is RCF-1, is China Petrochemical Industry's catalyzer Chang Ling branch office and produces.
Embodiment 1
Raw material using the mixing oil LLH-1 of LTFT-LO-1, LTFT-HO-1 and HTFT-1 as hydrofining reaction, wherein, described LTFT-LO-1, LTFT-HO-1 and HTFT-1 are that the product separation making under same Fischer-Tropsch synthesis condition obtains, character is in Table 1.Wherein, the weight ratio of LTFT-LO-1: LTFT-HO-1: LTFT-HW-1 is 10: 3: 12.
As shown in Figure 1, hydrotreated product is separated into hydrogen-rich gas, water and liquid hydrocarbon through separation system, and hydrogen-rich gas loops back reactive system, water discharge device.Liquid hydrocarbon enters the wax oil cut of 350 ℃ of the diesel oil distillate of naphtha fraction that separation column fractionates out 150 ℃ of <, 150-350 ℃ and >, and wherein naphtha fraction and diesel oil distillate are as product.After the wax oil cut that the > that fractionates out through separation column is 350 ℃ mixes with LTFT-HW-1 (character is in Table 1), enter hydrocracking reactor and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
In hydrofining reactor, RTF-1 catalyzer loading amount is 30ml, the amount of charging LTFT-LO-1, LTFT-HO-1, HTFT-1 is respectively 20g/h, 6g/h, 24g/h, the inlet amount of new hydrogen is 440ml/min (hydrogen to oil volume ratio is 420, and during liquid, volume space velocity is 2.1).290 ℃ of reactor service temperatures, reaction pressure 6.4MPa.
In hydrocracking reactor, RCF-1 catalyzer loading amount is 20ml, charging is 350 ℃ of cuts of > (inlet amount is 5g/h) and the LTFT-HW-1 that hydrotreated product fractionates out, wherein LTFT-HW-1 inlet amount is 24g/h, the inlet amount of new hydrogen is 500ml/min (hydrogen to oil volume ratio is 880, and during liquid, volume space velocity is 1.7); 365 ℃ of reactor service temperatures, reaction pressure 6.4MPa.
Under aforementioned operation condition, carried out 240h running and investigated.The character of the diesel oil distillate P1 fractionating out through separation column is in Table 4.
Comparative example 1
According to the method for embodiment 1, carry out hydrogenation of Fischer-Tropsch synthesis oil upgrading, different, in the raw material of hydrofining reaction, do not contain HTFT-1, isocrackate cuts out diesel oil distillate DP1 by true boiling point distillation instrument.The character of diesel oil distillate DP1 is in Table 5.
Comparative example 2
The HTFT-1 of take carries out hydrofining as raw material, and in hydrofining reactor, the loading amount of RTF-1 catalyzer is 15ml, and the inlet amount of HTFT-1 is 30ml/h, and the inlet amount of new hydrogen is 200ml/min.290 ℃ of reactor service temperatures, reaction pressure 6.4MPa.Hydrotreated product cuts out diesel oil distillate DP2 by true boiling point distillation instrument.The character of diesel oil distillate DP2 is in Table 5.
Embodiment 2
Raw material using the mixing oil LLH-2 of LTFT-LO-2, LTFT-HO-2 and HTFT-2 as hydrofining reaction, wherein, described LTFT-LO-2, LTFT-HO-2 and HTFT-2 are that the product separation making under same Fischer-Tropsch synthesis condition obtains, character is in Table 2.Wherein, the weight ratio of LTFT-LO-2: LTFT-HO-2: LTFT-HW-2 is 5.1: 2.6: 8.9.
As shown in Figure 1, hydrotreated product is separated into hydrogen-rich gas, water and liquid hydrocarbon through separation system, hydrogen-rich gas and water discharge device.Liquid hydrocarbon enters the wax oil cut of 350 ℃ of the diesel oil distillate of naphtha fraction that separation column fractionates out 150 ℃ of <, 150-350 ℃ and >, and wherein naphtha fraction and diesel oil distillate are as product.After the wax oil cut that the > that fractionates out through separation column is 350 ℃ mixes with LTFT-HW-2 (character is in Table 1), enter hydrocracking reactor and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
In hydrofining reactor, RTF-1 catalyzer loading amount is 30ml, and the amount of charging LTFT-LO-2, LTFT-HO-2, HTFT-2 is respectively 11.8g/h, 6g/h, 20.5g/h, and the inlet amount of new hydrogen is 600ml/min.250 ℃ of reactor service temperatures, reaction pressure 8MPa.
In hydrocracking reactor, RCF-1 catalyzer loading amount is 20ml, charging is 350 ℃ of cuts of > (inlet amount is 6g/h) and the LTFT-HW-2 that hydrotreated product fractionates out, wherein LTFT-HW-2 inlet amount is 24g/h, and the inlet amount of new hydrogen is 800ml/min; 350 ℃ of reactor service temperatures, reaction pressure 8MPa.
Under aforementioned operation condition, carried out 240h running and investigated.The character of the diesel oil distillate P2 fractionating out through separation column is in Table 4.
Embodiment 3
Raw material using the mixing oil LLH-3 of LTFT-LO-3, LTFT-HO-3 and HTFT-3 as hydrofining reaction, wherein, described LTFT-LO-3, LTFT-HO-3 and HTFT-3 are that the product separation making under same Fischer-Tropsch synthesis condition obtains, character is in Table 3.Wherein, the weight ratio of LTFT-LO-3: LTFT-HO-3: LTFT-HW-3 is 6.2: 2.3: 10.2.
As shown in Figure 1, hydrotreated product is separated into hydrogen-rich gas, water and liquid hydrocarbon through separation system, hydrogen-rich gas and water discharge device.Liquid hydrocarbon enters the wax oil cut of 350 ℃ of the diesel oil distillate of naphtha fraction that separation column fractionates out 150 ℃ of <, 150-350 ℃ and >, and wherein naphtha fraction and diesel oil distillate are as product.After the wax oil cut that the > that fractionates out through separation column is 350 ℃ mixes with LTFT-HW-3 (character is in Table 1), enter hydrocracking reactor and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
In hydrofining reactor, RTF-1 catalyzer loading amount is 30ml, and the amount of charging LTFT-LO-3, LTFT-HO-3, HTFT-3 is respectively 16.2g/h, 6g/h, 26.6g/h, and the inlet amount of new hydrogen is 920ml/min.400 ℃ of reactor service temperatures, reaction pressure 4.0MPa.
In hydrocracking reactor, RCF-1 catalyzer loading amount is 20ml, charging is 350 ℃ of cuts of > (inlet amount is 5g/h) and the LTFT-HW-3 that hydrotreated product fractionates out, wherein LTFT-HW-3 inlet amount is 18g/h, and the inlet amount of new hydrogen is 1000ml/min; 350 ℃ of reactor service temperatures, reaction pressure 4.0MPa.
Under aforementioned operation condition, carried out 240h running and investigated.The character of the diesel oil distillate P3 fractionating out through separation column is in Table 4.
Table 1
| LTFT-LO-1 | LTFT-HO-1 | LTFT-HW-1 | HTFT-1 | |
| Density, g/cm 3 | 0.7700 | 0.8093 | 0.7936 | |
| Oxygen level, % by weight | 2.93 | 1.03 | 0.32 | 3.96 |
| Bromine valency, gBr/100g | 13.0 | 49.12 | ||
| Normal paraffin content, weight | 74.3 | 79.2 | 84.8 | 12.7 |
| Olefin(e) centent, % by weight | 63.2 | |||
| Boiling range, ℃ | ||||
| Initial boiling point, ℃ | 39 | 249 | 320 | 45 |
| 10％，℃ | 106 | 332 | 392 | 80 |
| 30％，℃ | 160 | 358 | 462 | 101 |
| 50％，℃ | 210 | 380 | 517 | 120 |
| 70％，℃ | 243 | 399 | 580 | 168 |
| 90％，℃ | 303 | 426 | 651 | 251 |
| 95％，℃ | 336 | 440 | 665 | |
| FBP，℃ | 349 | 352 |
Table 2
| LTFT-LO-2 | LTFT-HO-2 | LTFT-HW-2 | HTFT-2 | |
| Density, g/cm 3 | 0.7639 | 0.8023 | 0.8112 | |
| Oxygen level, % by weight | 2.83 | 1.11 | 0.22 | 3.02 |
| Normal paraffin content, weight | 73.1 | 77.9 | 80.1 | 16.1 |
| Olefin(e) centent, % by weight | 60.6 | |||
| Bromine valency, gBr/100g | 15.2 | 33.5 | ||
| Initial boiling point, ℃ | 46 | 244 | 383 | 45 |
| 10％，℃ | 103 | 330 | 399 | 82 |
| 30％，℃ | 158 | 356 | 468 | 104 |
| 50％，℃ | 207 | 377 | 522 | 122 |
| 70％，℃ | 240 | 395 | 588 | 170 |
| 90％，℃ | 299 | 422 | 659 | 253 |
| 95％，℃ | 333 | 435 | 672 | |
| FBP，℃ | 343 | 355 |
Table 3
| LTFT-LO-3 | LTFT-HO-3 | LTFT-HW-3 | HTFT-3 | |
| Density, g/cm 3 | 0.7569 | 0.7913 | 0.7629 | |
| Oxygen level, % by weight | 2.32 | 0.83 | 0.41 | 3.93 |
| Normal paraffin content, weight | 64.9 | 70.3 | 82.5 | 13.7 |
| Olefin(e) centent, % by weight | 62.5 | |||
| Bromine valency, gBr/100g | 15.2 | 37.3 | ||
| Initial boiling point, ℃ | 41 | 255 | 399 | 39 |
| 10％，℃ | 99 | 328 | 417 | 102 |
| 30％，℃ | 155 | 353 | 456 | 157 |
| 50％，℃ | 202 | 373 | 520 | 206 |
| 70％，℃ | 235 | 391 | 578 | 238 |
| 90％，℃ | 289 | 418 | 641 | 297 |
| 95％，℃ | 328 | 431 | 652 | 331 |
| FBP，℃ | 332 | 341 |
Table 4
| P1-1 | P1-2 | P2 | P3 | |
| Runtime, h | 24 | 240 | 240 | 240 |
| Density, g/cm 3 | 0.8303 | 0.8310 | 0.8211 | 0.8206 |
| Oxygen level, % by weight | 0 | 0 | 0 | 0 |
| Sulphur, μ g/g | 2.9 | 2.1 | 2.2 | 2.1 |
| Condensation point, ℃ | -32 | -33 | -32 | -34 |
| Cetane value | 59 | 61 | 60 | |
| Bromine valency, gBr/100g | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Boiling range, ℃ | D-1160 | D-1160 | D-1160 | |
| Initial boiling point, ℃ | 158 | 155 | 159 | |
| 10％，℃ | 187 | 186 | 188 | |
| 30％，℃ | 210 | 211 | 211 | |
| 50％，℃ | 265 | 266 | 267 | |
| 70％，℃ | 262 | 264 | 264 | |
| 90％，℃ | 316 | 318 | 319 | |
| FBP，℃ | 355 | 359 | 358 |
As can be seen from Table 4, by method of the present invention, by synthetic oil hydrogenation gained diesel oil distillate density, be greater than 0.82g/cm
3, sulphur content is less than 5 μ g/g, cetane value higher than 51, meets the requirement of Europe IV diesel oil index.The condensation point that the method according to this invention is carried out the diesel oil that hydrogenation upgrading separation obtains is-32 ℃ to-34 ℃, can meet the requirement of low temp area to diesel low-temperature liquidity.
After 240h steady running, device works well, and reactor has no obvious pressure drop, and product oil nature is stable.
Table 5
| DP1 | DP2 | |
| Density, g/cm 3 | 0.7643 | 0.8339 |
| Oxygen level, % by weight | 0 | 0 |
| Sulphur, μ g/g | 2.6 | 2.0 |
| Condensation point, ℃ | -5 | -50 |
| Cetane value | 79 | 44 |
| Bromine valency, gBr/100g | 0.1 | 0.2 |
| Boiling range, ℃ | D-1160 | D-1160 |
| Initial boiling point, ℃ | 158 | 157 |
| 10％，℃ | 186 | 186 |
| 30％，℃ | 211 | 210 |
| 50％，℃ | 268 | 266 |
| 70％，℃ | 265 | 263 |
| 90％，℃ | 318 | 316 |
| FBP，℃ | 359 | 357 |
As can be seen from Table 5, take LTFT as the method gained diesel oil distillate density of raw material by hydrogenation upgrading be 0.7643g/cm
3, can not meet derv fuel oil index request.The condensation point of diesel oil that separation obtains is-5 ℃, cannot meet the requirement of low temp area to diesel low-temperature liquidity.
The HTFT of take can meet the requirement of Europe IV diesel oil index by the method gained diesel oil distillate density of hydrogenation upgrading as raw material, and condensation point of diesel oil is-50 ℃, can meet the requirement of low temp area to diesel low-temperature liquidity, but cetane value is lower.And when this test proceeds to 150h, reactor bed pressure drop obviously increases and is increased to rapidly 0.7MPa, and test cannot be proceeded, and device finds that the coking of beds top is serious after stopping work.In this explanation stock oil, alkene, especially diolefine generation polymerization generate coke, have had a strong impact on the long period steady running of device.
Data by embodiment 1 and comparative example 1-2 can be found out, by method of the present invention, take LTFT and HTFT can directly obtain as raw material carries out hydrogenation upgrading the diesel oil distillate that meets Europe IV diesel oil standard, the serious problem of the easy coking in beds top while simultaneously having avoided take HTFT as raw material, has guaranteed the long-term operation installing.
Claims (14)
1. by Fischer-Tropsch synthesis oil, produced a method for diesel oil, it is characterized in that, the method comprises the following steps,
(1), under hydrofining reaction condition, under Hydrobon catalyst exists, the synthetic light oil of low temperature process Fischer-Tropsch, low temperature process Fischer-Tropsch synthesis of heavy oil are contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil;
(2) the contact products therefrom of step (1) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the first naphtha fraction, the first diesel oil distillate and the first wax oil cut;
(3), under hydrocracking reaction condition, under hydrocracking catalyst exists, the first wax oil cut that step (2) is obtained contacts with hydrogen with the mixture of low temperature process Fischer-Tropsch synthetic wax;
(4) the contact products therefrom of step (3) is carried out to gas-liquid separation, and the oil phase that gas-liquid separation is obtained cuts, obtain the second naphtha fraction, the second diesel oil distillate and the second wax oil cut;
Wherein, the initial boiling point of the synthetic light oil of described low temperature process Fischer-Tropsch is 20-100 ℃, and final boiling point is 250-350 ℃, and the weight of the synthetic light oil of the low temperature process Fischer-Tropsch of take is benchmark, and in the synthetic light oil of described low temperature process Fischer-Tropsch, oxygen level is 0.5-8 % by weight; The initial boiling point of described low temperature process Fischer-Tropsch synthesis of heavy oil is 100-400 ℃, and final boiling point is 300-500 ℃, and the weight of low temperature process Fischer-Tropsch synthesis of heavy oil of take is benchmark, and in described low temperature process Fischer-Tropsch synthesis of heavy oil, oxygen level is 0.2-5 % by weight; The initial boiling point of described low temperature process Fischer-Tropsch synthetic wax is 300-500 ℃, and final boiling point is 600-750 ℃, and the weight of low temperature process Fischer-Tropsch synthetic wax of take is benchmark, and in described low temperature process Fischer-Tropsch synthetic wax, oxygen level is 0-2 % by weight.
2. method according to claim 1, wherein, in step (1), the synthetic light oil of described low temperature process Fischer-Tropsch and the gross weight of low temperature process Fischer-Tropsch synthesis of heavy oil and the weight ratio of the full cut of pyroprocess Fischer-Tropsch synthesis oil are 5:95-95:5.
3. method according to claim 2, wherein, in step (1), the synthetic light oil of described low temperature process Fischer-Tropsch and the gross weight of low temperature process Fischer-Tropsch synthesis of heavy oil and the weight ratio of the full cut of pyroprocess Fischer-Tropsch synthesis oil are 1:0.5-2.
4. method according to claim 1, wherein, in step (3), the first wax oil cut that described step (2) obtains and the weight ratio of low temperature process Fischer-Tropsch synthetic wax are 5:95-95:5.
5. method according to claim 4, wherein, in step (3), the first wax oil cut that described step (2) obtains and the weight ratio of low temperature process Fischer-Tropsch synthetic wax are 1:1-5.
6. method according to claim 1, wherein, the boiling range of described the first naphtha fraction and the second naphtha fraction is independently of one another within the scope of 15-200 ℃, the boiling range of described the first diesel oil distillate and the second diesel oil distillate is independently of one another within the scope of 150-370 ℃, and the boiling range of described the first wax oil cut and the second wax oil cut is independently of one another within the scope of 320-700 ℃.
7. according to claim, be the method described in any one in 1-6, wherein, it is the product under same Fischer-Tropsch synthesis condition that described low temperature process Fischer-Tropsch synthesizes light oil, described low temperature process Fischer-Tropsch synthesis of heavy oil and described low temperature process Fischer-Tropsch synthetic wax, and described same Fischer-Tropsch synthesis condition comprises: temperature of reaction is that 170-260 ℃, reaction pressure are 1.5-4.5MPa.
8. according to the method described in any one in claim 1-6, wherein, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 ℃, and final boiling point is at 300-450 ℃; The total amount of the full cut of pyroprocess Fischer-Tropsch synthesis oil of take is benchmark, and in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 1-10 % by weight, and normal paraffin content is 4-30 % by weight, and olefin(e) centent is 40-95 % by weight.
9. according to the method described in any one in claim 1-6, wherein, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
2with CO in temperature of reaction, be under 280-380 ℃, the reaction pressure condition that is 1.5-4.5MPa, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
10. according to the method described in any one in claim 1-6, wherein, described Hydrobon catalyst contains shaping carrier A1 and loads on the hydrogenation active metals component A2 on this shaping carrier A1, the total amount of this Hydrobon catalyst of take is benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 10-50 % by weight; Metal in described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight; Described shaping carrier A1 is aluminum oxide and/or silicon oxide.
11. according to the method described in any one in claim 1-6, wherein, described hydrocracking catalyst contains shaping carrier B1 and loads on the hydrogenation active metals B component 2 on this shaping carrier B1, and the total amount of this hydrocracking catalyst of take is benchmark, in described hydrocracking catalyst, the content of shaping carrier B1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals B component 2 is 10-50 % by weight; Metal in described hydrogenation active metals B component 2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and take the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 0-8 % by weight, the content of molybdenum is 0-7 % by weight, the content of tungsten is 0-35 % by weight, described shaping carrier B1 is silicon oxide and aluminum oxide, and the weight of shaping carrier of take is benchmark, in described shaping carrier B1, the content of silicon oxide is 1-40 % by weight, and the content of aluminum oxide is 60-99 % by weight.
12. according to the method described in any one in claim 1-6, and wherein, described hydrofining reaction condition comprises: temperature be 200-400 ℃, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 200-1000.
13. according to the method described in any one in claim 1-6, and wherein, described hydrocracking reaction condition comprises: temperature be 300-450 ℃, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 500-1500.
14. according to the method described in any one in claim 1-6, and wherein, the gas-liquid separation in the gas-liquid separation in described step (2) and step (4) is carried out in same separation system.
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| CN104449821A (en) * | 2014-12-11 | 2015-03-25 | 山西潞安煤基合成油有限公司 | Low-load n-alkane solvent oil production process |
| CN105505331A (en) * | 2016-01-27 | 2016-04-20 | 山西潞安煤基合成油有限公司 | Phase-change paraffin preparation method |
| CN105778995B (en) * | 2016-04-18 | 2018-03-20 | 武汉凯迪工程技术研究总院有限公司 | The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil |
| CN107794080B (en) * | 2016-08-31 | 2019-11-15 | 中国石油化工股份有限公司 | The method for modifying of F- T synthesis naphtha |
| CN108179027A (en) * | 2018-02-11 | 2018-06-19 | 中薪油武汉化工工程技术有限公司 | Gasification of biomass by-product tar is kneaded the technique and system of made fuel oil with Fischer-Tropsch synthesis oil |
| CN113105913B (en) * | 2021-03-29 | 2022-11-01 | 国家能源集团宁夏煤业有限责任公司 | Fischer-Tropsch synthesis kerosene preparation method and method for preparing semi-synthetic aviation kerosene from Fischer-Tropsch synthesis kerosene |
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