CN102911729A - 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
Day by day minimizing along with petroleum resources in the world wide, the substitute energy technological development comes into one's own gradually, and wherein the Fischer-Tropsch synthetic technology is as utilizing raw material that coal, Sweet natural gas, biomass etc. contain carbon, hydrogen resource to produce the technology of fuel with high cleanness and receive much concern.The Fischer-Tropsch synthetic technology is distinguished with service temperature, and it is synthetic and the pyroprocess Fischer-Tropsch synthetic to be divided into the low temperature process Fischer-Tropsch, and the synthetic oil of two kinds of methods all has without sulphur, without the characteristics of nitrogen.Wherein the low temperature process Fischer-Tropsch synthesis oil has the advantages that straight-chain paraffin height, oil product condensation point are high, the product oil density is little; The characteristics of pyroprocess Fischer-Tropsch synthesis oil and low temperature process synthetic oil differ larger, and pyroprocess Fischer-Tropsch synthesis oil alkene, diene content height contain a certain amount of naphthenic hydrocarbon, aromatic hydrocarbons, and the oil product condensation point is low, the product oil density is relatively high.
Each major oil companies is all in the preparing liquid fuel technology of exploitation take the Fischer-Tropsch synthetic technology as core, and wherein the pyroprocess Fischer-Tropsch of Sasol company is synthetic all has been successfully applied to industrial production with low temperature process Fischer-Tropsch synthetic technology; The low temperature process Fischer-Tropsch synthetic technology of Shell company also successfully was applied to industrial production in 1993; Domestic Shenhua Group, the Lushui River peace group, Yi Tai group all put into operation ten thousand ton/years of low temperature process Fischer-Tropsch of 16-18 synthesizer.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 was finished 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 the diesel oil process by method of hydrotreating and all had some problems.Because the aforementioned features of low temperature process synthetic oil so that the diesel oil distillate behind the hydrogenation has condensation point height, low density characteristics, can't directly be sold as commercial Dissel oil.The pyroprocess Fischer-Tropsch synthesis oil is very easy to coking owing to have higher alkene and diene content in the hydrogenation process, and then has shortened device running period.
For the upgrading of synthetic oil hydrogenation, each large 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 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 hydrocracking, then isolate coal diesel oil distillate wherein, tail oil carries out hydrocracking again, the coal diesel oil distillate in the separated product again, wherein diesel oil distillate density is 0.78g/cm
3, condensation point is-28-0 ℃.
Chevron company discloses in patent US6863802 and has a kind ofly produced the technique of gasoline, distillate, lube stock component by Fischer-Tropsch synthesis oil and fraction oil of petroleum, and the method is that the method that Fischer-Tropsch distillate and fraction oil of petroleum mix by the hydrogenation upgrading is again obtained fuel or lube stock.The method is still with the stock oil of petroleum base raw material as production diesel oil.
Sasol company discloses in patent US7390397 and has a kind ofly prepared the method for low-sulfur diesel-oil and low emission aviation fuel by synthetic oil, and the method is carried out fractionation with the low temperature process synthetic oil, fractionates out kerosene(oil)fraction and diesel oil distillate, and its ratio is at least 1: 2.Wherein the kerosene smoke point is greater than 50mm, and condensation point is lower than-47 ℃, can be used as low emission rocket engine fuel or blending component.The diesel oil distillate condensation point is lower than-5 ℃, density and is at least 0.78g/cm
3, can be used as low-sulfur diesel-oil or blend component.
Synthetic oil company of middle section discloses a kind of hydroprocessing technique of Fischer-Tropsch synthesis oil in CN200710065309, this technique is that the full cut of Fischer-Tropsch synthesis oil is at first carried out hydrotreatment, then isolate the first diesel oil distillate in the product, the tail oil cut carries out hydrocracking again, isocrackate separates 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 the Fischer-Tropsch synthesis oil direct hydrogenation or with the method for petroleum base raw material mixed hydrogenation.But all there are separately some defectives, the diesel oil density that obtains among the US6858127 is low, condensation point is high, can not satisfy the derv fuel oil index request, the diesel oil that obtains among the US7390397 only can be as blend component, and only can obtain the part low-coagulation diesel oil among the CN200710065309.
Therefore, still need develop and to obtain for a long time method of continuous operation of high-density, low freezing point diesel fuel and equipment.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can obtain high-density, low freezing point diesel fuel, and the long-term method of producing diesel oil by Fischer-Tropsch synthesis oil of continuous operation of equipment.
The invention provides a kind of method of being produced diesel oil by Fischer-Tropsch synthesis oil, the method may further comprise the steps, (1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, 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 with step (1) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains the first naphtha fraction, the first diesel oil distillate and the first wax oil cut; (3) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, 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 with step (3) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains 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 that obtains is greater than 0.82g/cm
3, sulphur content is less than 5 μ g/g, and cetane value is higher than 51, satisfies the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-32 ℃ to-34 ℃, can satisfy low temp area to the requirement of diesel low-temperature liquidity.And use separately the low temperature process Fischer-Tropsch synthesis oil to carry out the hydrogenation upgrading, the density of the diesel oil distillate that obtains is 0.7631g/cm
3, can not satisfy the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-2 ℃, can't satisfy low temp area to the requirement of the flowability of diesel oil at low-temperature.And use separately the pyroprocess Fischer-Tropsch synthesis oil to carry out the hydrogenation upgrading, and although the density of diesel oil distillate is higher, condensation point is also lower, can satisfy Europe IV diesel oil standard and low temp area to the requirement of diesel low-temperature liquidity, 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, carried out continuously 240 hours, reactor does not have obvious coking phenomenon, and the hydrogenation upgrading of using separately the pyroprocess Fischer-Tropsch synthesis oil to carry out was carried out 150 hours, and reactor bed pressure drop obviously increase also is increased to rapidly 0.7MPa, so that reaction can't be proceeded, after stopping work, device finds that beds top coking is serious.
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 the hydrogenation upgrading obtains low, cause the lower defective of unit volume calorific value, by with low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, improved the density of the diesel oil that makes, made it satisfy 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 the hydrogenation upgrading obtains higher, can't satisfy the defective that low temperature area requires the fuel condensation point, by with low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, greatly reduce the condensation point of the diesel oil that makes;
When (3) having overcome independent use pyroprocess Fischer-Tropsch synthesis oil, because its alkene, diene content are high, carry out the hydrogenation upgrading and process and be very easy to coking, cause that catalyst deactivation is fast, device is short running period.By with 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 the raw material, prevented that effectively the too fast phenomenon of coking from occuring.
Description of drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and consists of the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is process flow sheet of the present invention.
Embodiment
The invention provides a kind of method of producing diesel oil by Fischer-Tropsch synthesis oil, the method may further comprise the steps,
(1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, 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 with step (1) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains the first naphtha fraction, the first diesel oil distillate and the first wax oil cut;
(3) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, 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 with step (3) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains the second naphtha fraction, the second diesel oil distillate and the second wax oil cut.
The present invention carries out on the basis of hydrogenation upgrading at the mixing oil with the full cut of low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil, 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 isolated restructuring in the hydrotreated product is divided, be that the wax oil cut mixes with low temperature process Fischer-Tropsch synthetic wax, carry out hydrocracking, further isolate the diesel oil distillate in the isocrackate.Compare with the method that direct mixing oil with the full cut of low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil carries out the hydrogenation upgrading, the first step of this technique need not low temperature process Fischer-Tropsch synthetic wax is carried out 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 the 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 of final acquisition and the content of normal paraffin are depended in the selection of the two part by weight, among 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 the 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 the 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; The 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.
Among 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 in 15-200 ℃ of scope.The boiling range of described the first diesel oil distillate and the second diesel oil distillate can be independently of one another in 150-370 ℃ of scope.The boiling range of described the first wax oil cut and the second wax oil cut can be independently of one another in 320-750 ℃ of scope.Described contact products therefrom with step (1) carries out gas-liquid separation, and the oil phase cutting that gas-liquid separation obtains can be the method for this area routine, as by high-pressure separator, light pressure separator liquid phase being separated, and the water in the liquid phase removed, obtain oil phase, by separation column oil phase cutting is obtained above-mentioned naphtha fraction, diesel oil distillate and wax oil cut again.
According to the present invention, separation obtains the method for 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 for well known to a person skilled in the art method, as separating by distillation tower from the full cut of low temperature process Fischer-Tropsch synthesis oil.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, synthesize the weight of light oil as benchmark take the low temperature process Fischer-Tropsch, oxygen level is the 0.5-8 % by weight in the synthetic light oil of described low temperature process Fischer-Tropsch, further preferably, synthesize the weight of light oil as benchmark take the low temperature process Fischer-Tropsch, oxygen level is the 0.2-3 % by weight in the synthetic light oil of described low temperature process Fischer-Tropsch, most preferably is the 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, take the weight of low temperature process Fischer-Tropsch synthesis of heavy oil as benchmark, oxygen level is the 0.2-5 % by weight in the described low temperature process Fischer-Tropsch synthesis of heavy oil, further preferably, take the weight of low temperature process Fischer-Tropsch synthesis of heavy oil as benchmark, oxygen level is the 0.1-2 % by weight in the described low temperature process Fischer-Tropsch synthesis of heavy oil, most preferably is the 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, take the weight of low temperature process Fischer-Tropsch synthetic wax as benchmark, oxygen level is the 0-2 % by weight in the described low temperature process Fischer-Tropsch synthetic wax, further preferably, take the weight of low temperature process Fischer-Tropsch synthetic wax as benchmark, oxygen level is the 0-1 % by weight in the described low temperature process Fischer-Tropsch synthetic wax, most preferably is the 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 the same Fischer-Tropsch synthesis condition, it also can not be the product under the 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 the 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 ℃, and reaction pressure is 2-4MPa.
Among the present invention, there is no particular limitation to the full cut of described pyroprocess Fischer-Tropsch synthesis oil, 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 ℃; Take the total amount of the full cut of pyroprocess Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 1-10 % by weight in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, and normal paraffin content is the 4-30 % by weight, and olefin(e) centent is the 40-95 % by weight; Further preferably, oxygen level is the 2-8 % by weight in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, most preferably is the 3-5 % by weight; Normal paraffin content is the 10-20 % by weight, and olefin(e) centent is the 60-80 % by weight, most preferably is the 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 be that 280-380 ℃, reaction pressure are under the condition of 1.5-4.5MPa in temperature of reaction, synthetic obtaining further preferably, is H in the presence of fischer-tropsch synthetic catalyst
2With CO be that 300-360 ℃, reaction pressure are under the condition of 2-4MPa in temperature of reaction, synthetic obtaining in the presence of fischer-tropsch synthetic catalyst.
There is no particular limitation to described hydrogen in the present invention, can be for the conventional used various hydrogen in the synthetic field of Fischer-Tropsch, and such 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 the hydrogenation active metals component A2 that loads on this shaping carrier A1, take the total amount of this Hydrobon catalyst as benchmark, the content of shaping carrier A1 is the 50-90 % by weight in the described Hydrobon catalyst, in oxide compound, the content of described hydrogenation active metals component A2 is the 10-50 % by weight; Metal among the described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and the tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, the content of nickel is the 0-8 % by weight in the described Hydrobon catalyst, and the content of molybdenum is the 0-7 % by weight, and the content of tungsten is the 0-35 % by weight; Further preferably, take the total amount of this Hydrobon catalyst as benchmark, the content of shaping carrier A1 is the 52-75 % by weight in the described Hydrobon catalyst, in oxide compound, the content of described hydrogenation active metals component A2 is the 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, the content of nickel is the 2-7 % by weight in the described Hydrobon catalyst, the content of molybdenum is the 1-6 % by weight, and the content of tungsten is the 22-35 % by weight; Most preferably, the content of shaping carrier A1 is the 58-75 % by weight in the described Hydrobon catalyst, in oxide compound, the content of described hydrogenation active metals component A2 is that the metal among the described hydrogenation active metals component of the 25-42 % by weight A2 is nickel and tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, the content of nickel is the 2-7 % by weight among the affiliated Hydrobon catalyst A, and the content of tungsten is the 23-35 % by weight.
Among 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.Hydrobon catalyst with above-mentioned preferred composition and content can be the Hydrobon catalyst of RTF-1 for the trade names of catalyzer Chang Ling branch office of China Petrochemical Industry production for example.
According to the present invention, preferably, described hydrocracking catalyst contains shaping carrier B1 and the hydrogenation active metals B component 2 that loads on this shaping carrier B1, and take the total amount of this hydrocracking catalyst as benchmark, the content of shaping carrier is the 50-90 % by weight in the described hydrocracking catalyst, in oxide compound, the content of described hydrogenation active metals component is the 10-50 % by weight; Metal in the described hydrogenation active metals component is at least two kinds in nickel, molybdenum and the tungsten, in oxide compound and take the weight of hydrocracking catalyst as benchmark, the content of nickel is the 0-8 % by weight in the described hydrocracking catalyst, and the content of molybdenum is the 0-7 % by weight, and the content of tungsten is the 0-35 % by weight.Further preferably, take the total amount of this hydrocracking catalyst as benchmark, the content of shaping carrier is the 57-77 % by weight in the described hydrocracking catalyst, and in oxide compound, the content of described hydrogenation active metals component is the 23-43 % by weight; Metal in the described hydrogenation active metals component is nickel and tungsten, and in oxide compound and take the weight of hydrocracking catalyst as benchmark, the content of nickel is the 3-8 % by weight in the described hydrocracking catalyst, and the content of tungsten is the 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, helps 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 take the weight of shaping carrier as benchmark, the content of silicon oxide is the 1-40 % by weight in the described shaping carrier, and the content of aluminum oxide is the 60-99 % by weight, further preferably, the content of silicon oxide is the 3-30 % by weight in the described shaping carrier, and the content of aluminum oxide is the 70-97 % by weight.Hydrocracking catalyst with above-mentioned preferred composition and content can be the hydrocracking catalyst of RCF-1 for the trade names of catalyzer Chang Ling branch office of China Petrochemical Industry production for example.
Because core of the present invention is the mixing with 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 all can be ordinary method and the condition of this area.
According to the present invention, preferably, described hydrofining reaction condition comprises: temperature is 200-400 ℃, volume space velocity was 0.5-10h when the hydrogen dividing potential drop was 2.4-10MPa, liquid
-1, hydrogen to oil volume ratio is 200-1000; Further preferably, described hydrofining reaction condition comprises: temperature is 250-350 ℃, volume space velocity was 1-8h when the hydrogen dividing potential drop was 4-8MPa, liquid
-1, hydrogen to oil volume ratio is 300-800.
According to the present invention, preferably, described hydrocracking reaction condition comprises: temperature is 300-450 ℃, volume space velocity was 0.5-10h when the hydrogen dividing potential drop was 2.4-10MPa, liquid
-1, hydrogen to oil volume ratio is 500-1500, further preferably, described hydrocracking reaction condition comprises: temperature is 350-400 ℃, volume space velocity was 1-8h when the hydrogen dividing potential drop was 4-8MPa, liquid
-1, hydrogen to oil volume ratio is 800-1200.
According to the present invention, described contact products therefrom is carried out the described products therefrom that contacts is carried out gas-liquid separation and can finish in gas-liquid separation and the step (2) in the step (4) in identical or different separation system, preferably, in identical separation system, finish.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 also can be any suitable way well known by persons skilled in the art, the present invention, does not give unnecessary details 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.The mixing oil that the 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 through pipeline 1 with mix from the hydrogen of pipeline 2 and from the recycle hydrogen of pipeline 3 after, through the reactor 4 of Hydrobon catalyst is housed, under the 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 the 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 the cold high pressure separator 8, the gas part enters compressor 12 through pipeline 11, loop back hydrofining reactor 4 and hydrocracking reactor 14 through pipeline 3, pipeline 13 respectively, remaining gas effluxes through pipeline 15.Cold high pressure separator 8 isolated water efflux through pipeline 16, and liquid hydrocarbon enters cold low separator 18 through pipeline 17, carry out flash distillation in cold low separator 18, and the gas that flashes off part effluxes through pipeline 19, and liquid portion enters separation column 21 through pipeline 20.Enter cold low separator 18 by the isolated gases part of thermal low-pressure separators 10 through pipeline 22, liquid portion through pipeline 23 with enter separation column 21 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, the wax oil cut is through pipeline 26 and low temperature process Fischer-Tropsch synthetic wax from pipeline 27, new hydrogen from pipeline 28, enter the reactor 14 that hydrocracking catalyst is housed after the recycle hydrogen mixing from pipeline 13, in reactor 14, carry out hydrocracking, isocrackate enters high pressure hot separator after pipeline 29 and mixing of materials from pipeline 5 separates, and carries out follow-up separating step.
Below, the present invention will be described in more detail by embodiment.
In the embodiment of the invention, technological process is shown in Figure 1.The density of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records by the 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 record among the RIPP 66-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.).The sulphur content of separating the diesel oil distillate that obtains records by the GB17040 method.The condensation point of separating the diesel oil distillate that obtains records by the GB510 method.The cetane value of separating the diesel oil distillate that obtains records by the GB386 method.Olefin(e) centent records by the method for record among the RIPP 153-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.) among the HTFT.The normal paraffin content of LTFT, HTFT and mixing oil records by the SH/T0729 method.Boiling range records by ASTM D86/D1160 method.
Used Hydrobon catalyst is RTF-1 among the embodiment, and hydrocracking catalyst is RCF-1, is catalyzer Chang Ling branch office of China Petrochemical Industry and produces.
Embodiment 1
With the mixing oil LLH-1 of LTFT-LO-1, LTFT-HO-1 and the HTFT-1 raw material as hydrofining reaction, wherein, described LTFT-LO-1, LTFT-HO-1 and HTFT-1 are that the product separation that makes under the same Fischer-Tropsch synthesis condition obtains, and character sees 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 separation column and fractionates out＜diesel oil distillate of 150 ℃ naphtha fraction, 150-350 ℃ and＞350 ℃ wax oil cut, wherein naphtha fraction and diesel oil distillate are as product.Through separation column fractionate out＞350 ℃ wax oil cut with enter hydrocracking reactor after LTFT-HW-1 (character sees Table 1) mixes and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
RTF-1 catalyzer loading amount is 30ml in the hydrofining reactor, 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 volume space velocity is 2.1 during liquid).290 ℃ of reactor service temperatures, reaction pressure 6.4MPa.
RCF-1 catalyzer loading amount is 20ml in the hydrocracking reactor, charging is that hydrotreated product fractionates out＞350 ℃ of cuts (inlet amount is 5g/h) and LTFT-HW-1, wherein the 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 volume space velocity is 1.7 during liquid); 365 ℃ of reactor service temperatures, reaction pressure 6.4MPa.
Under the aforementioned operation condition, carried out the 240h running and investigated.The character of the diesel oil distillate P1 that fractionates out through separation column sees Table 4.
Comparative Examples 1
Method according to embodiment 1 is carried out the hydrogenation of Fischer-Tropsch synthesis oil upgrading, and different is, does not contain HTFT-1 in the raw material of hydrofining reaction, and isocrackate cuts out diesel oil distillate DP1 by the true boiling point distillation instrument.The character of diesel oil distillate DP1 sees Table 5.
Comparative Examples 2
Carry out hydrofining take HTFT-1 as raw material, the loading amount of RTF-1 catalyzer is 15ml in the hydrofining reactor, 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 the true boiling point distillation instrument.The character of diesel oil distillate DP2 sees Table 5.
Embodiment 2
With the mixing oil LLH-2 of LTFT-LO-2, LTFT-HO-2 and the HTFT-2 raw material as hydrofining reaction, wherein, described LTFT-LO-2, LTFT-HO-2 and HTFT-2 are that the product separation that makes under the same Fischer-Tropsch synthesis condition obtains, and character sees 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 separation column and fractionates out＜diesel oil distillate of 150 ℃ naphtha fraction, 150-350 ℃ and＞350 ℃ wax oil cut, wherein naphtha fraction and diesel oil distillate are as product.Through separation column fractionate out＞350 ℃ wax oil cut with enter hydrocracking reactor after LTFT-HW-2 (character sees Table 1) mixes and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
RTF-1 catalyzer loading amount is 30ml in the hydrofining reactor, 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.
RCF-1 catalyzer loading amount is 20ml in the hydrocracking reactor, charging is that hydrotreated product fractionates out＞350 ℃ of cuts (inlet amount is 6g/h) and LTFT-HW-2, wherein the 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 the aforementioned operation condition, carried out the 240h running and investigated.The character of the diesel oil distillate P2 that fractionates out through separation column sees Table 4.
Embodiment 3
With the mixing oil LLH-3 of LTFT-LO-3, LTFT-HO-3 and the HTFT-3 raw material as hydrofining reaction, wherein, described LTFT-LO-3, LTFT-HO-3 and HTFT-3 are that the product separation that makes under the same Fischer-Tropsch synthesis condition obtains, and character sees 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 separation column and fractionates out＜diesel oil distillate of 150 ℃ naphtha fraction, 150-350 ℃ and＞350 ℃ wax oil cut, wherein naphtha fraction and diesel oil distillate are as product.Through separation column fractionate out＞350 ℃ wax oil cut with enter hydrocracking reactor after LTFT-HW-3 (character sees Table 1) mixes and carry out hydrocracking reaction, isocrackate also enters aforementioned separation system.
RTF-1 catalyzer loading amount is 30ml in the hydrofining reactor, 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.
RCF-1 catalyzer loading amount is 20ml in the hydrocracking reactor, charging is that hydrotreated product fractionates out＞350 ℃ of cuts (inlet amount is 5g/h) and LTFT-HW-3, wherein the 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 the aforementioned operation condition, carried out the 240h running and investigated.The character of the diesel oil distillate P3 that fractionates out through separation column sees 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 |
| The 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 | |||
| The 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 | |||
| The 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 | |
| The 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 greater than 0.82g/cm
3, sulphur content is higher than 51 less than 5 μ g/g, cetane value, satisfies the requirement of Europe IV diesel oil index.The method according to this invention is carried out the condensation point that the hydrogenation upgrading separates the diesel oil obtain and is-32 ℃ to-34 ℃, can satisfy low temp area to the requirement of diesel low-temperature liquidity.
After the 240h steady running, device works well, and reactor has no obvious pressure drop, and the 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 |
| The 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, the method gained diesel oil distillate density by the hydrogenation upgrading is 0.7643g/cm take LTFT as raw material
3, can not satisfy the derv fuel oil index request.Separate the condensation point of diesel oil that obtains and be-5 ℃, can't satisfy low temp area to the requirement of diesel low-temperature liquidity.
Can satisfy the requirement of Europe IV diesel oil index by the method gained diesel oil distillate density of hydrogenation upgrading take HTFT as raw material, condensation point of diesel oil is-50 ℃, can satisfy low temp area to the requirement of diesel low-temperature liquidity, but cetane value is lower.And when this test proceeded to 150h, the reactor bed pressure drop obviously increased and is increased to rapidly 0.7MPa, and test can't be proceeded, and found that beds top coking is serious after device is stopped work.Alkene, especially diolefine generation polymerization generate coke in this explanation stock oil, have had a strong impact on the long period steady running of device.
Data by embodiment 1 and Comparative Examples 1-2 can be found out, by method of the present invention, carry out the diesel oil distillate that the hydrogenation upgrading can directly obtain to satisfy Europe IV diesel oil standard take LTFT and HTFT as raw material, the serious problem of the easy coking in beds top when having avoided simultaneously take HTFT as raw material has been guaranteed the long-term operation that installs.
Claims (15)
1. a method of producing diesel oil by Fischer-Tropsch synthesis oil is characterized in that the method may further comprise the steps,
(1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, 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 with step (1) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains the first naphtha fraction, the first diesel oil distillate and the first wax oil cut;
(3) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, 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 with step (3) carries out gas-liquid separation, and the oil phase that gas-liquid separation obtains is cut, and obtains the second naphtha fraction, the second diesel oil distillate and the second wax oil cut.
2. method according to claim 1, wherein, in the 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 the 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 the 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 the 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 in 15-200 ℃ of scope, in 150-370 ℃ of scope, the boiling range of described the first wax oil cut and the second wax oil cut is independently of one another in 320-700 ℃ of scope independently of one another for the boiling range of described the first diesel oil distillate and the second diesel oil distillate.
7. the described method of any one according to claim 1-6, wherein, the initial boiling point of the synthetic light oil of described low temperature process Fischer-Tropsch is 20-100 ℃, final boiling point is 250-350 ℃, take the weight of the synthetic light oil of low temperature process Fischer-Tropsch as benchmark, oxygen level is the 0.5-8 % by weight in the synthetic light oil of described low temperature process Fischer-Tropsch; 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 take the weight of low temperature process Fischer-Tropsch synthesis of heavy oil as benchmark, oxygen level is the 0.2-5 % by weight in the described low temperature process Fischer-Tropsch synthesis of heavy oil; The initial boiling point of described low temperature process Fischer-Tropsch synthetic wax is 300-500 ℃, and final boiling point is 600-750 ℃, and take the weight of low temperature process Fischer-Tropsch synthetic wax as benchmark, oxygen level is the 0-2 % by weight in the described low temperature process Fischer-Tropsch synthetic wax.
8. be the described method of any one among the 1-6 according to claim, wherein, it is product under the 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.
9. the described method of any one according to claim 1-6, wherein, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 ℃, final boiling point is at 300-450 ℃; Take the total amount of the full cut of pyroprocess Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 1-10 % by weight in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, and normal paraffin content is the 4-30 % by weight, and olefin(e) centent is the 40-95 % by weight.
10. the described method of any one according to claim 1-6, wherein, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
2With CO be that 280-380 ℃, reaction pressure are under the condition of 1.5-4.5MPa in temperature of reaction, synthetic obtaining in the presence of fischer-tropsch synthetic catalyst.
11. the described method of any one according to claim 1-6, wherein, described Hydrobon catalyst contains shaping carrier A1 and the hydrogenation active metals component A2 that loads on this shaping carrier A1, take the total amount of this Hydrobon catalyst as benchmark, the content of shaping carrier A1 is the 50-90 % by weight in the described Hydrobon catalyst, in oxide compound, the content of described hydrogenation active metals component A2 is the 10-50 % by weight; Metal among the described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and the tungsten, in oxide compound and take the weight of Hydrobon catalyst as benchmark, the content of nickel is the 0-8 % by weight in the described Hydrobon catalyst, and the content of molybdenum is the 0-7 % by weight, and the content of tungsten is the 0-35 % by weight; Described shaping carrier is aluminum oxide and/or silicon oxide.
12. the described method of any one according to claim 1-6, wherein, described hydrocracking catalyst contains shaping carrier B1 and the hydrogenation active metals B component 2 that loads on this shaping carrier B1, and take the total amount of this hydrocracking catalyst as benchmark, the content of shaping carrier B1 is the 50-90 % by weight in the described hydrocracking catalyst, in oxide compound, the content of described hydrogenation active metals B component 2 is the 10-50 % by weight; Metal in the described hydrogenation active metals B component 2 is at least two kinds in nickel, molybdenum and the tungsten, in oxide compound and take the weight of hydrocracking catalyst as benchmark, the content of nickel is the 0-8 % by weight in the described hydrocracking catalyst, the content of molybdenum is the 0-7 % by weight, the content of tungsten is the 0-35 % by weight, described shaping carrier B1 is silicon oxide and aluminum oxide, and take the weight of shaping carrier as benchmark, the content of silicon oxide is the 1-40 % by weight among the described shaping carrier B1, and the content of aluminum oxide is the 60-99 % by weight.
13. the described method of any one according to claim 1-6, wherein, described hydrofining reaction condition comprises: temperature is 200-400 ℃, volume space velocity was 0.5-10h when the hydrogen dividing potential drop was 2.4-10MPa, liquid
-1, hydrogen to oil volume ratio is 200-1000.
14. the described method of any one according to claim 1-6, wherein, described hydrocracking reaction condition comprises: temperature is 300-450 ℃, volume space velocity was 0.5-10h when the hydrogen dividing potential drop was 2.4-10MPa, liquid
-1, hydrogen to oil volume ratio is 500-1500.
15. the described method of any one according to claim 1-6, wherein, the gas-liquid separation in the gas-liquid separation in the described step (2) and the step (4) is carried out in same separation system.
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| CN107794080A (en) * | 2016-08-31 | 2018-03-13 | 中国石油化工股份有限公司 | The method for modifying of F- T synthesis naphtha |
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| CN105778995A (en) * | 2016-04-18 | 2016-07-20 | 武汉凯迪工程技术研究总院有限公司 | Method and device for producing good-quality diesel oil through combined hydrogenation of low-temperature Fischer-Tropsch synthesis oil and inferior crude oil |
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| 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 |
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