CN102911722A - Hydrogenation quality-improving method for Fischer-Tropsch synthetic oil - Google Patents
Hydrogenation quality-improving method for Fischer-Tropsch synthetic oil Download PDFInfo
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Abstract
The invention provides a hydrogenation quality-improving method for Fischer-Tropsch synthetic oil. The method comprises the steps of contacting mixed oil of full fractions of low temperature method Fischer-Tropsch synthetic oil and full fractions of high temperature method Fischer-Tropsch synthetic oil in presence of hydrorefining catalyst, under hydrorefining reaction conditions; and (2) contacting the product obtained from the step (1) in the presence of a hydrocracking catalyst, under hydrocracking reaction conditions. The method comprises 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, meeting the requirement of fuel condensation points for low temperature regions; and (3) effectively preventing the occurrence from a too fast coking phenomenon.
Description
Technical field
The present invention relates to a kind of Fischer-Tropsch synthetic oil hydrogenation purification.
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, can be divided into that the low temperature process Fischer-Tropsch is synthetic and the pyroprocess Fischer-Tropsch synthetic, 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 is high, the oil product condensation point is 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 are high, 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 high, the low density characteristics of condensation point, can't directly be sold as commercial Dissel oil.The pyroprocess Fischer-Tropsch synthesis oil is very easy to coking owing to having 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 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, the method is that Fischer-Tropsch distillate and fraction oil of petroleum mixing are obtained fuel or lube stock by the method for hydrogenation upgrading again.The method is still with the stock oil of petroleum base raw material as production diesel oil.
Sasol company discloses a kind of method that is prepared low-sulfur diesel-oil and low emission aviation fuel by synthetic oil in patent US7390397, 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 diesel oil distillate 1 in the product, the tail oil cut carries out hydrocracking again, isocrackate separates again, isolates diesel oil distillate 2 wherein, and wherein the condensation point of diesel oil distillate 1 is 2-5 ℃, the condensation point of diesel oil distillate 2 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 Fischer-Tropsch synthetic oil hydrogenation purification of continuous operation of equipment.
The invention provides a kind of Fischer-Tropsch synthetic oil hydrogenation purification, the method may further comprise the steps, (1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, the mixing oil of the full cut of low temperature process Fischer-Tropsch synthesis oil with the full cut of pyroprocess Fischer-Tropsch synthesis oil contacted with hydrogen; (2) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, step (1) contact products therefrom is contacted with hydrogen.
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 4 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-28 ℃ to-35 ℃, 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.
Embodiment
The invention provides a kind of Fischer-Tropsch synthetic oil hydrogenation purification, the method may further comprise the steps,
(1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, the mixing oil of the full cut of low temperature process Fischer-Tropsch synthesis oil (LTFT) with the full cut of pyroprocess Fischer-Tropsch synthesis oil (HTFT) contacted with hydrogen;
(2) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, step (1) contact products therefrom is contacted with hydrogen.
The present invention does not limit especially for the weight ratio of the full cut of low temperature process Fischer-Tropsch synthesis oil in the mixing oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil, as long as described mixing oil can satisfy certain oxygen level and normal paraffin content, too high oxygen level can affect the performance of catalyzer, and suitable normal paraffin content can guarantee the performance of the diesel fuel oil that finally obtains.The present inventor finds, take the total amount of described mixing oil as benchmark, oxygen level is the 0.2-6.0 % by weight in described mixing oil, when normal paraffin content was the 10-95 % by weight, the diesel fuel oil quality that obtains was good, and the equipment coking is not obvious, further preferably, take the total amount of described mixing oil as benchmark, oxygen level is the 0.2-5.0 % by weight in the described mixing oil, and normal paraffin content is the 20-80 % by weight; More preferably, take the total amount of described mixing oil as benchmark, oxygen level is the 0.2-3.0 % by weight in the described mixing oil, and normal paraffin content is the 30-70 % by weight; Most preferably, take the total amount of described mixing oil as benchmark, oxygen level is the 1-3 % by weight in the described mixing oil, and normal paraffin content is the 40-60 % by weight.
There is no particular limitation for the full cut of described low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil in the present invention, can be low temperature process and the synthetic full distillate oil product that obtain of pyroprocess Fischer-Tropsch of this area routine.Preferably, the initial boiling point of the full cut of described low temperature process Fischer-Tropsch synthesis oil is 20-100 ℃, and final boiling point is 550-750 ℃; Take the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 0.2-5 % by weight in the full cut of described low temperature process Fischer-Tropsch synthesis oil; Normal paraffin content is the 50-95 % by weight.Further preferably, the initial boiling point of the full cut of described low temperature process Fischer-Tropsch synthesis oil is 20-50 ℃, most preferably is 30-50 ℃, and final boiling point is 650-750 ℃; Take the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 0.3-2 % by weight in the full cut of described low temperature process Fischer-Tropsch synthesis oil; Normal paraffin content is the 75-95 % by weight, most preferably is the 85-95 % by weight.
And preferably, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H
2With CO be that 170-260 ℃, 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.Further preferably, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H
2With CO be that 190-240 ℃, reaction pressure are under the condition of 2-4MPa in temperature of reaction, synthetic obtaining in the presence of fischer-tropsch synthetic catalyst.
Equally, preferably, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 ℃, and final boiling point is 300-450 ℃; Take the total amount of the full cut of described 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, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-50 ℃, most preferably is 35-50 ℃, and final boiling point is 300-400 ℃; Take the total amount of the full cut of described pyroprocess Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 1-7 % by weight in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, most preferably is the 2-4 % by weight, and normal paraffin content is the 10-20 % by weight, olefin(e) centent is the 50-80 % by weight, most preferably is the 60-80 % by weight.
And preferably, 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.Further preferably, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
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 for the conventional used various hydrogen in the synthetic field of Fischer-Tropsch, be preferably new 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.
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, and the catalyzer of described hydrofining and hydrocracking and reaction conditions all can be conventional catalyst and the reaction conditions of this area.
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 among the described Hydrobon catalyst A, 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.
According to the present invention, described shaping carrier A1 is preferably aluminum oxide and/or silicon oxide, more preferably aluminum oxide.
The present inventor finds, adopts above-mentioned preferred shaping carrier A1 and hydrogenation active metals component A2 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 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, 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 B1 is the 57-77 % by weight in the described hydrocracking catalyst, and in oxide compound, the content of described hydrogenation active metals B component 2 is the 23-43 % by weight; Metal in the described hydrogenation active metals B component 2 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 preferred shaping carrier B1 and hydrogenation active metals B component 2 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 B1 is silicon oxide and aluminum oxide, and take the weight of shaping carrier B1 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, further preferably, the content of silicon oxide is the 3-30 % by weight among the described shaping carrier B1, 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.
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, preferably, the method also comprises separates step (2) contact products therefrom, obtains diesel oil distillate.The method of described separation can be the method for this area routine, and as separating by separation column, described diesel oil distillate is 150-350 ℃ cut.
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, the present invention will be described in more detail by embodiment.
Among foregoing description of the present invention and the following embodiment, 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 the ASTMD86/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
The mixing oil LH-1 that LTFT-1 and HTFT-1 are mixed with 1: 2 weight ratio is as hydrogenation upgrading raw material, and the character of LTFT-1, HTFT-1 and mixing oil LH-1 sees Table 1.Enter hydrofining reactor after mixing oil LH-1 and hydrogen mix and carry out hydrofining, the hydrotreated product that obtains enters hydrocracking reactor and carries out hydrocracking, and the isocrackate that obtains cuts out diesel oil distillate P1 by the true boiling point distillation instrument.
Wherein, hydrorefined condition is: volume space velocity 3h when 300 ℃ of temperature of reaction, reaction pressure 6.4MPa, liquid
-1, hydrogen to oil volume ratio 300.
The condition of hydrocracking is: volume space velocity 2h when 368 ℃ of temperature of reaction, reaction pressure 6.4MPa, liquid
-1, hydrogen to oil volume ratio 800.
Under the aforementioned operation condition, carried out respectively the running of 24h and 240h and investigated.Isolate diesel oil distillate P1-1 and P1-2, character 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 that with the raw material of LTFT-1 as the hydrogenation upgrading, 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
Method according to embodiment 1 is carried out the hydrogenation of Fischer-Tropsch synthesis oil upgrading, and different is that with the raw material of HTFT-1 as the hydrogenation upgrading, isocrackate 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
The mixing oil LH-2 that LTFT-2 and HTFT-2 are mixed with 1: 1.5 weight ratio is as hydrogenation upgrading raw material, and the character of LTFT-2, HTFT-2 and mixing oil LH-2 sees Table 2.Enter hydrofining reactor after mixing oil LH-2 and hydrogen mix and carry out hydrofining, the hydrotreated product that obtains enters hydrocracking reactor and carries out hydrocracking, and the isocrackate that obtains cuts out diesel oil distillate P2 by the true boiling point distillation instrument.The character of diesel oil distillate P2 sees Table 4.
Wherein, hydrofining operational condition is: volume space velocity 1h when 250 ℃ of temperature of reaction, reaction pressure 8MPa, liquid
-1, hydrogen to oil volume ratio 500.
The hydrocracking operational condition is: volume space velocity 4h when 350 ℃ of temperature of reaction, reaction pressure 8MPa, liquid
-1, hydrogen to oil volume ratio 1000.
Under the aforementioned operation condition, carried out the running of 240h and investigated.
Embodiment 3
The mixing oil LH-3 that LTFT-3 and HTFT-3 are mixed with 1: 1 weight ratio is as hydrogenation upgrading raw material, and the character of LTFT-3, HTFT-3 and mixing oil LH-3 sees Table 3.Enter hydrofining reactor after mixing oil LH-3 and hydrogen mix and carry out hydrofining, the hydrotreated product that obtains enters hydrocracking reactor and carries out hydrocracking, and the isocrackate that obtains cuts out diesel oil distillate P3 by the true boiling point distillation instrument.The character of diesel oil distillate P3 sees Table 4.
Wherein, hydrofining operational condition is: volume space velocity 8h when 350 ℃ of temperature of reaction, reaction pressure 4MPa, liquid
-1, hydrogen to oil volume ratio 800.
The hydrocracking operational condition is: volume space velocity 8h when 400 ℃ of temperature of reaction, reaction pressure 4MPa, liquid
-1, hydrogen to oil volume ratio 1200.
Under the aforementioned operation condition, carried out the running of 240h and investigated.
Table 1
| LTFT-1 | HTFT-1 | LH-1 | |
| Density, g/cm 3 | 0.8038 | 0.7636 | 0.7770 |
| Oxygen level, % by weight | 0.49 | 3.96 | 2.80 |
| The bromine valency, gBr/100g | 49.12 | ||
| Normal paraffin content, % by weight | 90.5 | 15.4 | 40.4 |
| Olefin(e) centent, % by weight | 71.2 | 23.7 | |
| Boiling range, ℃ | D-1160 | D-86 | D-1160 |
| Initial boiling point, ℃ | 38 | 44 | 40 |
| 10％，℃ | 126 | 70 | 109 |
| 30％，℃ | 251 | 94 | 145 |
| 50％，℃ | 362 | 115 | 172 |
| 70％，℃ | 454 | 168 | 289 |
| 90％，℃ | 548 | 251 | 387 |
| 95％，℃ | 570 | 555 | |
| FBP，℃ | 352 |
Table 2
| LTFT-2 | HTFT-2 | LH-2 | |
| Density, g/cm 3 | 0.8194 | 0.7528 | 0.7794 |
| Oxygen level, % by weight | 1.02 | 2.18 | 1.72 |
| Normal paraffin content, % by weight | 89.8 | 11.3 | 42.7 |
| Olefin(e) centent, % by weight | 9.2 | 62.4 | 41.1 |
| The bromine valency, gBr/100g | 38.1 | ||
| Initial boiling point, ℃ | 49 | 48 | 48 |
| 10％，℃ | 168 | 75 | 115 |
| 30％，℃ | 289 | 96 | 146 |
| 50％，℃ | 399 | 116 | 175 |
| 70％，℃ | 478 | 158 | 291 |
| 90％，℃ | 569 | 243 | 392 |
| 95％，℃ | 595 | 562 | |
| FBP，℃ | 338 |
Table 3
| LTFT-3 | HTFT-3 | LH-3 | |
| Density, g/cm 3 | 0.8254 | 0.7415 | 0.7834 |
| Oxygen level, % by weight | 0.88 | 3.62 | 2.25 |
| Normal paraffin content, % by weight | 85.4 | 19.6 | 52.5 |
| Olefin(e) centent, % by weight | 13.2 | 78.1 | 45.6 |
| The bromine valency, gBr/100g | 53.2 | ||
| Initial boiling point, ℃ | 46 | 39 | 42 |
| 10％，℃ | 163 | 76 | 118 |
| 30％，℃ | 291 | 95 | 149 |
| 50％，℃ | 401 | 113 | 178 |
| 70％，℃ | 479 | 155 | 295 |
| 90％，℃ | 571 | 239 | 397 |
| 95％，℃ | 599 | 569 | |
| FBP，℃ | 330 |
Table 4
| P1-1 | P1-2 | P2 | P3 | |
| Runtime, h | 24 | 240 | 240 | 240 |
| Density, g/cm 3 | 0.8208 | 0.8210 | 0.8283 | 0.8312 |
| Oxygen level, % by weight | 0 | 0 | 0 | 0 |
| Sulphur, μ g/g | 3.1 | 2.3 | 2.2 | 2.1 |
| Condensation point, ℃ | -33 | -35 | -32 | -28 |
| Cetane value | 56 | 59 | 62 | |
| The bromine valency, gBr/100g | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Boiling range, ℃ | D-1160 | D-1160 | D-1160 | |
| Initial boiling point, ℃ | 159 | 156 | 155 | |
| 10％，℃ | 188 | 186 | 183 | |
| 30％，℃ | 210 | 209 | 211 | |
| 50％，℃ | 266 | 265 | 267 | |
| 70％，℃ | 263 | 262 | 264 | |
| 90％，℃ | 317 | 315 | 319 | |
| FBP，℃ | 357 | 355 | 359 |
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 4 μ g/g, cetane value, satisfies the requirement of Europe IV diesel oil index.Carry out the condensation point of diesel oil that hydrogenation upgrading aftercut obtains by method of the present invention and be-28 ℃ to-35 ℃, 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 | 0.7631 | 0.8339 |
| Oxygen level, % by weight | 0 | 0 |
| Sulphur, μ g/g | 3.1 | 2.0 |
| Condensation point, ℃ | -2 | -50 |
| Cetane value | 77 | 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 0.7631g/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-2 ℃, 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 (11)
1. a Fischer-Tropsch synthetic oil hydrogenation purification is characterized in that, the method may further comprise the steps,
(1) under the hydrofining reaction condition, in the presence of Hydrobon catalyst, the mixing oil of the full cut of low temperature process Fischer-Tropsch synthesis oil with the full cut of pyroprocess Fischer-Tropsch synthesis oil contacted with hydrogen;
(2) under the hydrocracking reaction condition, in the presence of hydrocracking catalyst, step (1) contact products therefrom is contacted with hydrogen.
2. method according to claim 1, wherein, take the total amount of described mixing oil as benchmark, oxygen level is the 0.2-6.0 % by weight in the described mixing oil, normal paraffin content is the 10-95 % by weight.
3. method according to claim 1, wherein, the initial boiling point of the full cut of described low temperature process Fischer-Tropsch synthesis oil is 20-100 ℃, final boiling point is 550-750 ℃; Take the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, oxygen level is the 0.2-5 % by weight in the full cut of described low temperature process Fischer-Tropsch synthesis oil; Normal paraffin content is the 50-95 % by weight.
4. method according to claim 3, wherein, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H2 and CO in temperature of reaction is that 170-260 ℃, reaction pressure are under the condition of 1.5-4.5MPa, synthetic obtaining in the presence of fischer-tropsch synthetic catalyst.
5. method according to claim 1, wherein, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 ℃, final boiling point is 300-450 ℃; Take the total amount of the full cut of described 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.
6. method according to claim 5, wherein, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H2 and CO in temperature of reaction is that 280-380 ℃, reaction pressure are under the condition of 1.5-4.5MPa, synthetic obtaining in the presence of fischer-tropsch synthetic catalyst.
7. 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 A1 is aluminum oxide and/or silicon oxide.
8. 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, 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 B1 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.
9. 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.
10. 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.
11. the described method of any one according to claim 1-6, wherein, the method also comprises separates step (2) contact products therefrom, obtains diesel oil distillate.
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| WO2017181813A1 (en) * | 2016-04-18 | 2017-10-26 | 武汉凯迪工程技术研究总院有限公司 | Method and equipment thereof for producing high-quality diesel using low-temperature fischer-tropsch synthetic oil and low-grade oil feedstock |
| CN107418622A (en) * | 2017-06-07 | 2017-12-01 | 神华集团有限责任公司 | Improve the device and method of F- T synthesis diesel oil density |
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