CN102911722B - Hydrogenation quality-improving method for Fischer-Tropsch synthetic oil - Google Patents
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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
Along with the minimizing day by day of petroleum resources in world wide, substitute energy technological development comes into one's own gradually, and wherein Fischer-Tropsch synthetic technology is produced the technology of fuel with high cleanness and receives much concern as the raw material that can utilize coal, Sweet natural gas, biomass etc. to contain carbon, hydrogen resource.Fischer-Tropsch synthetic technology is distinguished with service temperature, can be divided into that low temperature process Fischer-Tropsch is synthetic and pyroprocess Fischer-Tropsch synthetic, and the synthetic oil of two kinds of methods all has without sulphur, without the feature of nitrogen.Wherein low temperature process Fischer-Tropsch synthesis oil has the advantages that straight-chain paraffin is high, oil product condensation point is high, product oil density is little; The feature of pyroprocess Fischer-Tropsch synthesis oil and low temperature process synthetic oil differ larger, and pyroprocess Fischer-Tropsch synthesis oil alkene, diene content are high, contain a certain amount of naphthenic hydrocarbon, aromatic hydrocarbons, and oil product condensation point is low, product oil density is relatively high.
Each major oil companies are the preparing liquid fuel technology taking Fischer-Tropsch synthetic technology as core in exploitation all, and wherein the pyroprocess Fischer-Tropsch of Sasol company is synthetic has all 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 was also successfully applied to industrial production in 1993; Domestic Shenhua Group, Lu An group, Yi Tai group all put into operation ten thousand tons/year of low temperature process Fischer-Tropsch synthesizers of 16-18.The construction of Yan ore deposit megaton low temperature process Fischer-Tropsch compound probability device is brought into schedule; Kiloton pyroprocess Fischer-Tropsch synthetic pilot scale research in Yan ore deposit completed in 2007, indicated that China has possessed the ability of building pyroprocess Fischer-Tropsch compound probability device.
As one of main purpose of Fischer-Tropsch synthetic technology, producing diesel oil is the vital task of synthetic oil factory, and low temperature process synthetic oil and pyroprocess synthetic oil are produced diesel oil process by method of hydrotreating and all had some problems.Due to the aforementioned features of low temperature process synthetic oil, make the diesel oil distillate after hydrogenation there is high, the low density feature of condensation point, cannot directly sell as commercial Dissel oil.Pyroprocess Fischer-Tropsch synthesis oil is owing to having higher alkene and diene content, is very easy to coking in hydrogenation process, and then shortened device running period.
For the upgrading of synthetic oil hydrogenation, Ge great research institution has developed some correlation techniques, respectively low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil has been carried out to various improvement:
Shell company discloses a kind of method of producing intermediate oil in patent US6858127, what the method adopted is that at least part of synthetic oil is carried out to hydrocracking, then isolate coal diesel oil distillate wherein, tail oil carries out hydrocracking again, coal diesel oil distillate in separated product again, wherein diesel oil distillate density is 0.78g/cm
3, condensation point is-28-0 DEG C.
Chevron company discloses a kind of technique of being produced gasoline, distillate, lube stock component by Fischer-Tropsch synthesis oil and fraction oil of petroleum in patent US6863802, and the method is that Fischer-Tropsch distillate and fraction oil of petroleum mixing are obtained to fuel or lube stock by the method for hydrogenation upgrading again.The method is still using petroleum base raw material as the stock oil of producing diesel oil.
Sasol company discloses a kind of method of being prepared low-sulfur diesel-oil and low emission aviation fuel by synthetic oil in patent US7390397, and low temperature process synthetic oil is carried out fractionation by the method, fractionates out kerosene(oil)fraction and diesel oil distillate, and its ratio is at least 1: 2.Wherein kerosene smoke point is greater than 50mm, and condensation point, lower than-47 DEG C, can be used as low emission rocket engine fuel or blending component.Diesel oil distillate condensation point is at least 0.78g/cm lower than-5 DEG C, density
3, can be used as low-sulfur diesel-oil or blend component.
Zhong Ke synthetic oil company discloses a kind of hydroprocessing technique of Fischer-Tropsch synthesis oil in CN200710065309, this technique is that first full Fischer-Tropsch synthesis oil cut is carried out to hydrotreatment, then isolate diesel oil distillate 1 in product, 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 DEG C, the condensation point of diesel oil distillate 2 is less than-50 DEG C, and the method can production part low-coagulation diesel oil.
Aforesaid method is by obtaining diesel oil distillate to Fischer-Tropsch synthesis oil direct hydrogenation or with the method for petroleum base raw material mixed hydrogenation.But all there are separately some defects, the diesel oil density that obtains in US6858127 is low, condensation point is high, can not meet derv fuel oil index request, the diesel oil obtaining in US7390397 only can be served as blend component, and in CN200710065309, only can obtain part low-coagulation diesel oil.
Therefore, still need development can obtain high-density, low freezing point diesel fuel and the equipment method of continuous operation for a long time.
Summary of the invention
The object of this invention is to provide one and can obtain high-density, low freezing point diesel fuel, and the equipment Fischer-Tropsch synthetic oil hydrogenation purification of continuous operation for a long time.
The invention provides a kind of Fischer-Tropsch synthetic oil hydrogenation purification, the method comprises the following steps, (1) under hydrofining reaction condition, under Hydrobon catalyst exists, full low temperature process Fischer-Tropsch synthesis oil cut is contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil; (2), under hydrocracking reaction condition, under hydrocracking catalyst exists, 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 obtaining is greater than 0.82g/cm
3, sulphur content is less than 4 μ g/g, and cetane value, higher than 51, meets the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-28 DEG C to-35 DEG C, can meet the requirement of low temp area to diesel low-temperature liquidity.And using separately low temperature process Fischer-Tropsch synthesis oil to carry out hydrogenation upgrading, the density of the diesel oil distillate obtaining is 0.7631g/cm
3, can not meet the requirement of Europe IV diesel oil standard, and condensation point of diesel oil is-2 DEG C, cannot meet the requirement of the mobility of low temp area to diesel oil at low-temperature.And use separately pyroprocess Fischer-Tropsch synthesis oil to carry out hydrogenation upgrading, and although the density of diesel oil distillate is higher, condensation point is also lower, can meet the requirement to diesel low-temperature liquidity of Europe IV diesel oil standard and low temp area, its cetane value is very low.
In addition, utilize method of the present invention to carry out the hydrogenation upgrading of Fischer-Tropsch synthesis oil, carry out continuously 240 hours, reactor does not have obvious coking phenomenon, and the hydrogenation upgrading that uses separately pyroprocess Fischer-Tropsch synthesis oil to carry out is carried out 150 hours, reactor bed pressure drop obviously increase is also increased to rapidly 0.7MPa, reaction cannot be proceeded, and device finds that the coking of beds top is serious after stopping work.
To sum up, the advantage of method of the present invention is:
(1) having overcome independent use low temperature process Fischer-Tropsch synthesis oil, to carry out the diesel oil density that hydrogenation upgrading obtains low, cause the defect that unit volume calorific value is lower, by by low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, improve the density of the diesel oil making, made it meet the requirement of Europe IV diesel oil standard;
(2) having overcome independent use low temperature process Fischer-Tropsch synthesis oil, to carry out the condensation point of diesel oil that hydrogenation upgrading obtains higher, cannot meet the defect that low temperature area requires fuel condensation point, by by low temperature process Fischer-Tropsch synthesis oil and pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, greatly reduce the condensation point of the diesel oil making;
(3) while having overcome independent use pyroprocess Fischer-Tropsch synthesis oil, because its alkene, diene content are high, carry out hydrogenation upgrading and process and be very easy to coking, cause that catalyst deactivation is fast, device is short running period.By by low temperature process Fischer-Tropsch synthesis oil and the upgrading of pyroprocess Fischer-Tropsch synthesis oil mixed hydrogenation, reduce the concentration of alkene, diolefine in raw material, effectively prevent that the too fast phenomenon of coking from occurring.
Embodiment
The invention provides a kind of Fischer-Tropsch synthetic oil hydrogenation purification, the method comprises the following steps,
(1), under hydrofining reaction condition, under Hydrobon catalyst exists, full low temperature process Fischer-Tropsch synthesis oil cut (LTFT) is contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil (HTFT);
(2), under hydrocracking reaction condition, under hydrocracking catalyst exists, step (1) contact products therefrom is contacted with hydrogen.
The present invention is not particularly limited for the weight ratio of the full cut of low temperature process Fischer-Tropsch synthesis oil in mixing oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil, as long as described mixing oil can meet certain oxygen level and normal paraffin content, too high oxygen level can affect the performance of catalyzer, and suitable normal paraffin content can ensure the performance of the diesel fuel oil finally obtaining.The present inventor finds, taking the total amount of described mixing oil as benchmark, when oxygen level in described mixing oil is 0.2-6.0 % by weight, when normal paraffin content is 10-95 % by weight, the diesel fuel oil quality obtaining is good, and equipment coking is not obvious, further preferably, taking the total amount of described mixing oil as benchmark, in described mixing oil, oxygen level is 0.2-5.0 % by weight, and normal paraffin content is 20-80 % by weight; More preferably, taking the total amount of described mixing oil as benchmark, in described mixing oil, oxygen level is 0.2-3.0 % by weight, and normal paraffin content is 30-70 % by weight; Most preferably, taking the total amount of described mixing oil as benchmark, in described mixing oil, oxygen level is 1-3 % by weight, and normal paraffin content is 40-60 % by weight.
For the full cut of described low temperature process Fischer-Tropsch synthesis oil and the full cut of pyroprocess Fischer-Tropsch synthesis oil, there is no particular limitation in the present invention, can be the low temperature process of this area routine and the synthetic full distillate oil product that obtain of pyroprocess Fischer-Tropsch.Preferably, the initial boiling point of the full cut of described low temperature process Fischer-Tropsch synthesis oil is 20-100 DEG C, and final boiling point is 550-750 DEG C; Taking the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, in the full cut of described low temperature process Fischer-Tropsch synthesis oil, oxygen level is 0.2-5 % by weight; Normal paraffin content is 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 DEG C, most preferably is 30-50 DEG C, and final boiling point is 650-750 DEG C; Taking the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, in the full cut of described low temperature process Fischer-Tropsch synthesis oil, oxygen level is 0.3-2 % by weight; Normal paraffin content is 75-95 % by weight, most preferably is 85-95 % by weight.
And preferably, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H
2with CO be under 170-260 DEG C, the reaction pressure condition that is 1.5-4.5MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.Further preferably, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H
2with CO be under 190-240 DEG C, the reaction pressure condition that is 2-4MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
Equally, preferably, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 DEG C, and final boiling point is 300-450 DEG C; Taking the total amount of the full cut of described pyroprocess Fischer-Tropsch synthesis oil as benchmark, in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 1-10 % by weight, and normal paraffin content is 4-30 % by weight, and olefin(e) centent is 40-95 % by weight.Further preferably, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-50 DEG C, most preferably is 35-50 DEG C, and final boiling point is 300-400 DEG C; Taking the total amount of the full cut of described pyroprocess Fischer-Tropsch synthesis oil as benchmark, in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 1-7 % by weight, most preferably is 2-4 % by weight, and normal paraffin content is 10-20 % by weight, olefin(e) centent is 50-80 % by weight, most preferably is 60-80 % by weight.
And preferably, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
2with CO be under 280-380 DEG C, the reaction pressure condition that is 1.5-4.5MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.Further preferably, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
2with CO be under 300-360 DEG C, the reaction pressure condition that is 2-4MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
To described hydrogen, there is no particular limitation in the present invention, can, for the synthetic field of Fischer-Tropsch various hydrogen conventional used, be preferably new hydrogen.
According to the present invention, described fischer-tropsch synthetic catalyst can be conventional various fischer-tropsch synthetic catalysts, 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 can be all conventional catalyst and the reaction conditions of this area.
According to the present invention, preferably, described Hydrobon catalyst contains shaping carrier A1 and loads on the hydrogenation active metals component A2 on this shaping carrier A1, taking the total amount of this Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 10-50 % by weight; Metal in described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and taking the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight; Further preferably, taking the total amount of this Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 52-75 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 25-48 % by weight, the middle metal of described hydrogenation active metals component A2 is nickel, molybdenum and tungsten, in oxide compound and taking the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst A, the content of nickel is 2-7 % by weight, the content of molybdenum is 1-6 % by weight, and the content of tungsten is 22-35 % by weight; Most preferably, in described Hydrobon catalyst, the content of shaping carrier A1 is 58-75 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is that the metal in hydrogenation active metals component A2 is nickel and tungsten described in 25-42 % by weight, in oxide compound and taking the weight of Hydrobon catalyst as benchmark, in affiliated Hydrobon catalyst A, the content of nickel is 2-7 % by weight, and the content of tungsten is 23-35 % by weight.
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 obtain the effect of good olefin saturated, hydrogenation deoxidation and hydrogenating desulfurization.The Hydrobon catalyst with above-mentioned preferred composition and content can be for example the Hydrobon catalyst that the trade names of China Petrochemical Industry's catalyzer Chang Ling branch office production are RTF-1.
According to the present invention, preferably, described hydrocracking catalyst contains shaping carrier B1 and loads on the hydrogenation active metals B component 2 on this shaping carrier B1, and taking the total amount of this hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of shaping carrier B1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals B component 2 is 10-50 % by weight; Metal in described hydrogenation active metals B component 2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and taking the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight.Further preferably, taking the total amount of this hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of shaping carrier B1 is 57-77 % by weight, and in oxide compound, the content of described hydrogenation active metals B component 2 is 23-43 % by weight; Metal in described hydrogenation active metals B component 2 is nickel and tungsten, and in oxide compound and taking the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 3-8 % by weight, and the content of tungsten is 20-35 % by weight.
The present inventor finds, adopts above-mentioned preferred shaping carrier B1 and hydrogenation active metals B component 2 to carry out hydrocracking reaction as hydrocracking catalyst, can obtain good cracking effect, contributes 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 taking the weight of shaping carrier B1 as benchmark, in described shaping carrier B1, the content of silicon oxide is 1-40 % by weight, and the content of aluminum oxide is 60-99 % by weight, further preferably, in described shaping carrier B1, the content of silicon oxide is 3-30 % by weight, and the content of aluminum oxide is 70-97 % by weight.The hydrocracking catalyst with above-mentioned preferred composition and content can be for example the hydrocracking catalyst that the trade names of China Petrochemical Industry's catalyzer Chang Ling branch office production are RCF-1.
According to the present invention, preferably, described hydrofining reaction condition comprises: temperature be 200-400 DEG C, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 200-1000; Further preferably, described hydrofining reaction condition comprises: temperature be 250-350 DEG C, hydrogen dividing potential drop while being 4-8MPa, liquid volume space velocity be 1-8h
-1, hydrogen to oil volume ratio is 300-800.
According to the present invention, preferably, described hydrocracking reaction condition comprises: temperature be 300-450 DEG C, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 500-1500, further preferably, described hydrocracking reaction condition comprises: temperature be 350-400 DEG C, hydrogen dividing potential drop while being 4-8MPa, liquid volume space velocity be 1-8h
-1, hydrogen to oil volume ratio is 800-1200.
According to the present invention, preferably, the method also comprises that step (2) is contacted to products therefrom to be separated, and obtains diesel oil distillate.The method of described separation can be the method for this area routine, and as separated by separation column, described diesel oil distillate is the cut of 150-350 DEG C.
Method provided by the invention, can adopt periodical operation, also can operate continuously etc., feed way can be also any suitable way well known by persons skilled in the art, the present invention, does not repeat at this all without particular requirement one by one to this.
Below, by embodiment, the present invention will be described in more detail.
In foregoing description of the present invention and following embodiment, the density of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records by SH0604 method.The oxygen level of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records by ASTM D5622 method.The bromine valency of the diesel oil distillate that described LTFT, HTFT, mixing oil, separation obtain records according to the method for recording in RIPP 66-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.).The sulphur content of the diesel oil distillate that separation obtains records by GB17040 method.The condensation point of the diesel oil distillate that separation obtains records by GB510 method.The cetane value of the diesel oil distillate that separation obtains records by GB386 method.In HTFT, olefin(e) centent records by the method for recording in RIPP 153-90 (Petrochemical Engineering Analysis method, Yang Cuiding etc.).The normal paraffin content of LTFT, HTFT and mixing oil records by SH/T0729 method.Boiling range records by ASTMD86/D1160 method.
In embodiment, Hydrobon catalyst used is RTF-1, and hydrocracking catalyst is RCF-1, is China Petrochemical Industry's catalyzer Chang Ling branch office and produces.
Embodiment 1
The mixing oil LH-1 that LTFT-1 and HTFT-1 are mixed using the weight ratio of 1: 2 is as hydrogenation upgrading raw material, and the character of LTFT-1, HTFT-1 and mixing oil LH-1 is in table 1.Mixing oil LH-1 and hydrogen enter hydrofining reactor after mixing and carry out hydrofining, and the hydrotreated product obtaining enters hydrocracking reactor and carries out hydrocracking, and the isocrackate obtaining cuts out diesel oil distillate P1 by true boiling point distillation instrument.
Wherein, hydrorefined condition is: volume space velocity 3h when 300 DEG C 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 DEG C of temperature of reaction, reaction pressure 6.4MPa, liquid
-1, hydrogen to oil volume ratio 800.
Under aforementioned operation condition, carry out respectively the running of 24h and 240h and investigated.Isolate diesel oil distillate P1-1 and P1-2, character is in table 4.
Comparative example 1
Carry out hydrogenation of Fischer-Tropsch synthesis oil upgrading according to the method for embodiment 1, different, the raw material using LTFT-1 as hydrogenation upgrading, isocrackate cuts out diesel oil distillate DP1 by true boiling point distillation instrument.The character of diesel oil distillate DP1 is in table 5.
Comparative example 2
Carry out hydrogenation of Fischer-Tropsch synthesis oil upgrading according to the method for embodiment 1, different, the raw material using HTFT-1 as hydrogenation upgrading, isocrackate cuts out diesel oil distillate DP2 by true boiling point distillation instrument.The character of diesel oil distillate DP2 is in table 5.
Embodiment 2
The mixing oil LH-2 that LTFT-2 and HTFT-2 are mixed using the weight ratio of 1: 1.5 is as hydrogenation upgrading raw material, and the character of LTFT-2, HTFT-2 and mixing oil LH-2 is in table 2.Mixing oil LH-2 and hydrogen enter hydrofining reactor after mixing and carry out hydrofining, and the hydrotreated product obtaining enters hydrocracking reactor and carries out hydrocracking, and the isocrackate obtaining cuts out diesel oil distillate P2 by true boiling point distillation instrument.The character of diesel oil distillate P2 is in table 4.
Wherein, hydrofining operational condition is: volume space velocity 1h when 250 DEG C of temperature of reaction, reaction pressure 8MPa, liquid
-1, hydrogen to oil volume ratio 500.
Hydrocracking operational condition is: volume space velocity 4h when 350 DEG C of temperature of reaction, reaction pressure 8MPa, liquid
-1, hydrogen to oil volume ratio 1000.
Under aforementioned operation condition, carry out the running of 240h and investigated.
Embodiment 3
The mixing oil LH-3 that LTFT-3 and HTFT-3 are mixed using the weight ratio of 1: 1 is as hydrogenation upgrading raw material, and the character of LTFT-3, HTFT-3 and mixing oil LH-3 is in table 3.Mixing oil LH-3 and hydrogen enter hydrofining reactor after mixing and carry out hydrofining, and the hydrotreated product obtaining enters hydrocracking reactor and carries out hydrocracking, and the isocrackate obtaining cuts out diesel oil distillate P3 by true boiling point distillation instrument.The character of diesel oil distillate P3 is in table 4.
Wherein, hydrofining operational condition is: volume space velocity 8h when 350 DEG C of temperature of reaction, reaction pressure 4MPa, liquid
-1, hydrogen to oil volume ratio 800.
Hydrocracking operational condition is: volume space velocity 8h when 400 DEG C of temperature of reaction, reaction pressure 4MPa, liquid
-1, hydrogen to oil volume ratio 1200.
Under aforementioned operation condition, carry 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 |
| 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, DEG C | D-1160 | D-86 | D-1160 |
| Initial boiling point, DEG C | 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 |
| Bromine valency, gBr/100g | 38.1 | ||
| Initial boiling point, DEG C | 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 |
| Bromine valency, gBr/100g | 53.2 | ||
| Initial boiling point, DEG C | 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, DEG C | -33 | -35 | -32 | -28 |
| Cetane value | 56 | 59 | 62 | |
| Bromine valency, gBr/100g | ＜0.1 | ＜0.1 | ＜0.1 | ＜0.1 |
| Boiling range, DEG C | D-1160 | D-1160 | D-1160 | |
| Initial boiling point, DEG C | 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, be greater than 0.82g/cm by synthetic oil hydrogenation gained diesel oil distillate density
3, sulphur content is less than 4 μ g/g, cetane value higher than 51, meets the requirement of Europe IV diesel oil index.Carry out by method of the present invention the condensation point of diesel oil that hydrogenation upgrading aftercut obtains and be-28 DEG C to-35 DEG C, can meet the requirement of low temp area to diesel low-temperature liquidity.
After 240h steady running, device works well, and reactor has no obvious pressure drop, and product oil nature is stable.
Table 5
| DP1 | DP2 | |
| Density, g/cm 3 | 0.7631 | 0.8339 |
| Oxygen level, % by weight | 0 | 0 |
| Sulphur, μ g/g | 3.1 | 2.0 |
| Condensation point, DEG C | -2 | -50 |
| Cetane value | 77 | 44 |
| Bromine valency, gBr/100g | 0.1 | 0.2 |
| Boiling range, DEG C | D-1160 | D-1160 |
| Initial boiling point, DEG C | 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, taking LTFT as raw material, the method gained diesel oil distillate density by hydrogenation upgrading is 0.7631g/cm
3, can not meet derv fuel oil index request.The condensation point of diesel oil that separation obtains is-2 DEG C, cannot meet the requirement of low temp area to diesel low-temperature liquidity.
Can meet the requirement of Europe IV diesel oil index by the method gained diesel oil distillate density of hydrogenation upgrading taking HTFT as raw material, condensation point of diesel oil is-50 DEG C, can meet the requirement of low temp area to diesel low-temperature liquidity, but cetane value is lower.And when this test proceeds to 150h, reactor bed pressure drop obviously increases and is increased to rapidly 0.7MPa, and test cannot be proceeded, and device finds that the coking of beds top is serious after stopping work.In this explanation stock oil, alkene, especially diolefine generation polymerization generate coke, have had a strong impact on the long period steady running of device.
Data by embodiment 1 and comparative example 1-2 can be found out, by method of the present invention, as carrying out hydrogenation upgrading, raw material can directly obtain the diesel oil distillate that meets Europe IV diesel oil standard taking LTFT and HTFT, the serious problem of the easy coking in beds top while simultaneously having avoided taking HTFT as raw material, has guaranteed the long-term operation installing.
Claims (10)
1. a Fischer-Tropsch synthetic oil hydrogenation purification, is characterized in that, the method comprises the following steps,
(1), under hydrofining reaction condition, under Hydrobon catalyst exists, full low temperature process Fischer-Tropsch synthesis oil cut is contacted with hydrogen with the mixing oil of the full cut of pyroprocess Fischer-Tropsch synthesis oil;
(2), under hydrocracking reaction condition, under hydrocracking catalyst exists, step (1) contact products therefrom is contacted with hydrogen;
Wherein, taking the total amount of described mixing oil as benchmark, in described mixing oil, oxygen level is 0.2-5.0 % by weight, and normal paraffin content is 20-80 % by weight.
2. 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 DEG C, final boiling point is 550-750 DEG C; Taking the total amount of the full cut of described low temperature process Fischer-Tropsch synthesis oil as benchmark, in the full cut of described low temperature process Fischer-Tropsch synthesis oil, oxygen level is 0.2-5 % by weight; Normal paraffin content is 50-95 % by weight.
3. method according to claim 2, wherein, the full cut of described low temperature process Fischer-Tropsch synthesis oil is H
2with CO be under 170-260 DEG C, the reaction pressure condition that is 1.5-4.5MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
4. method according to claim 1, wherein, the initial boiling point of the full cut of described pyroprocess Fischer-Tropsch synthesis oil is 20-100 DEG C, final boiling point is 300-450 DEG C; Taking the total amount of the full cut of described pyroprocess Fischer-Tropsch synthesis oil as benchmark, in the full cut of described pyroprocess Fischer-Tropsch synthesis oil, oxygen level is 1-10 % by weight, and normal paraffin content is 4-30 % by weight, and olefin(e) centent is 40-95 % by weight.
5. method according to claim 4, wherein, the full cut of described pyroprocess Fischer-Tropsch synthesis oil is H
2with CO be under 280-380 DEG C, the reaction pressure condition that is 1.5-4.5MPa in temperature of reaction, synthetic obtaining under fischer-tropsch synthetic catalyst exists.
6. according to the method described in any one in claim 1-5, wherein, described Hydrobon catalyst contains shaping carrier A1 and loads on the hydrogenation active metals component A2 on this shaping carrier A1, taking the total amount of this Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of shaping carrier A1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals component A2 is 10-50 % by weight; Metal in described hydrogenation active metals component A2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and taking the weight of Hydrobon catalyst as benchmark, in described Hydrobon catalyst, the content of nickel is 0-8 % by weight, and the content of molybdenum is 0-7 % by weight, and the content of tungsten is 0-35 % by weight; Described shaping carrier A1 is aluminum oxide and/or silicon oxide.
7. according to the method described in any one in claim 1-5, wherein, described hydrocracking catalyst contains shaping carrier B1 and loads on the hydrogenation active metals B component 2 on this shaping carrier, and taking the total amount of this hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of shaping carrier B1 is 50-90 % by weight, in oxide compound, the content of described hydrogenation active metals B component 2 is 10-50 % by weight; Metal in described hydrogenation active metals B component 2 is at least two kinds in nickel, molybdenum and tungsten, in oxide compound and taking the weight of hydrocracking catalyst as benchmark, in described hydrocracking catalyst, the content of nickel is 0-8 % by weight, the content of molybdenum is 0-7 % by weight, the content of tungsten is 0-35 % by weight, described shaping carrier B1 is silicon oxide and aluminum oxide, and taking the weight of shaping carrier B1 as benchmark, in described shaping carrier B1, the content of silicon oxide is 1-40 % by weight, and the content of aluminum oxide is 60-99 % by weight.
8. according to the method described in any one in claim 1-5, wherein, described hydrofining reaction condition comprises: temperature be 200-400 DEG C, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 200-1000.
9. according to the method described in any one in claim 1-5, wherein, described hydrocracking reaction condition comprises: temperature be 300-450 DEG C, hydrogen dividing potential drop while being 2.4-10MPa, liquid volume space velocity be 0.5-10h
-1, hydrogen to oil volume ratio is 500-1500.
10. according to the method described in any one in claim 1-5, wherein, the method also comprises that step (2) is contacted to products therefrom to be separated, and obtains diesel oil distillate.
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| US20020144929A1 (en) * | 2001-04-04 | 2002-10-10 | Moore Richard O. | Method for upgrading Fischer-Tropsch wax using split-feed hydrocracking/hydrotreating |
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