CN103320166A - Method for producing diesel oil by utilizing Fischer-Tropsch synthesis product - Google Patents
Method for producing diesel oil by utilizing Fischer-Tropsch synthesis product Download PDFInfo
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Abstract
The invention discloses a method for producing diesel oil by utilizing a Fischer-Tropsch synthesis product. The method comprises the following steps: 1, separating the Fischer-Tropsch synthesis product to obtain LPG, naphtha, straight-run diesel oil and heavy oil; 2, carrying out hydroisomerization cracking of the heavy oil, carrying out an alkylation reaction of LPG and naphtha fractions in the synthetic oil product obtained after the hydroisomerization cracking and LPG and naphtha obtained in step 1, and hydrofining the diesel oil fraction in the synthetic oil product obtained after the hydroisomerization cracking and the straight-run diesel oil obtained in the step 1; and 3, mixing the diesel oil fraction in the obtained alkylation reaction product with hydrofinished diesel oil obtained after the hydrofinishing reaction to realize the production of diesel through utilizing the Fischer-Tropsch synthesis product. The method allows the alkylation reaction of the straight-run diesel oil fractionated from the Fischer-Tropsch synthesis product to be carried out, so the load of the hydrofinishing unit is obviously reduced. Only the diesel oil fraction is hydrofinished, so the raw material distillation range is narrow, thereby the method enables the hydrofinishing condition to be mild and the technology to be simplified.
Description
Technical field
The present invention relates to a kind of method of utilizing the Fischer-Tropsch synthetics to produce diesel oil.
Background technology
The various derivatives of oil provide powerful power for development economic and society, but but not only face increasingly exhausted crisis as non-renewable petroleum resources, and quality also worse and worse.Cause thus that the course of processing is complicated, environmental problem outstanding and the disadvantageous effect such as cost rising.
Coal or Sweet natural gas etc. are considered to the main substitute of following petroleum resources through the synthetic liquid fuel that can be converted into efficiently cleaning of Fischer-Tropsch.This production technique principle process comprises: coal or gas material are converted into hydro carbons and the synthetic oil processing such as straight-chain paraffin, alkene through gasification generation raw gas, refining synthetic gas, the synthetic gas of obtaining of raw gas purifying through the Fischer-Tropsch building-up reactions.
Relatively less for Fischer-Tropsch oil product technological method for processing at present.In published patent, various technological method for processing for oil from Fischer-Tropsch synthesis have been introduced such as US2003/0057135A1, US5378348, US6309432, US6656342, US6296757, CN1854264A, CN1854266A, CN101230291A, CN1865405A, CN101173190A philosophy, general way is exactly at first the Fischer-Tropsch synthetics to be separated, then by different material being carried out the hydroisomerizing cracking and hydrofinishing process prepares diesel oil.In this process, further promote the economy of oil from Fischer-Tropsch synthesis by process optimization and the method such as integrated.
Generally synthetic based on the Fischer-Tropsch of ferrum-based catalyst, the synthetic exactly hydrocarbon of the distinguishing feature of synthetics is mainly take positive structure hydro carbons as main, and olefin(e) centent is higher in the synthetics simultaneously, and olefin component content is up to more than the 50wt%.This shows, the Fischer-Tropsch synthetics is faced with the difficult problem that virgin naphtha utilizes in the course of processing.General virgin naphtha cut in the Fischer-Tropsch synthetics proportion up to 12wt%.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the Fischer-Tropsch synthetics to produce diesel oil.
A kind of method of utilizing the Fischer-Tropsch synthetics to produce diesel oil provided by the invention comprises the steps:
(1) the Fischer-Tropsch synthetics is separated obtain the LPG(liquefied petroleum gas (LPG)), petroleum naphtha, straight-run diesel oil and heavy oil;
(2) described heavy oil is carried out the hydroisomerizing cracking;
The described LPG and the petroleum naphtha that obtain in LPG in the synthetic oil that described hydroisomerizing cracking is obtained and naphtha fraction and the step (1) carry out alkylated reaction;
The described straight-run diesel oil that obtains in diesel oil distillate in the synthetic oil that the described hydroisomerizing cracking of step (2) is obtained and the step (1) carries out hydrofining reaction;
(3) hydrofining diesel oil that the diesel oil distillate in the product of described alkylated reaction and described hydrofining reaction is obtained mixes namely realizes utilizing the Fischer-Tropsch synthetics to produce the purpose of diesel oil.
In the above-mentioned method, in the step (2), the temperature of described hydroisomerizing cracking can be 300～450 ° of C, and such as 375 ° of C, pressure can be 2.0～15.0MPa, and such as 6.0MPa, volume space velocity can be 0.5～5.0h
-1, such as 1.6h
-1, hydrogen to oil volume ratio can be 100～1500Nm
3/ m
3, such as 300Nm
3/ m
3, described hydrogen to oil volume ratio refers to the volume ratio of hydrogen and raw material heavy oil.
In the above-mentioned method, in the step (2), the temperature of described alkylated reaction can be-30～50 ° of C, such as-5 ° of C, pressure can be 0～0.5MPa, such as 0.5MPa, alkane alkene volume ratio (referring to the ratio of all isoparaffin volume total amounts and all alkene volume total amounts in the reaction mass) is 1～15:1(v/v), such as 10:1; Described alkylated reaction carries out under the catalysis of the vitriol oil or hydrofluoric acid, acid hydrocarbon volume ratio (referring to the volume of the vitriol oil or hydrofluoric acid and the ratio of all hydrocarbons volume total amounts) is 0.5～1.5:1(v/v), such as 1.5:1, stirring velocity can be 1000～5000rpm, such as 2000.
In the above-mentioned method, in the step (2), the temperature of described hydrofining reaction can be 300～450 ° of C, and such as 300 ° of C, pressure can be 2.0～15.0MPa, and such as 6.0MPa, volume space velocity can be 0.5～5.0h
-1, such as 3.0h
-1, hydrogen to oil volume ratio is 100～1500Nm
3/ m
3, such as 300Nm
3/ m
3, described hydrogen to oil volume ratio refers to the volume ratio of hydrogen and raw material diesel oil distillate and straight-run diesel oil.
In the above-mentioned method, described Hydrobon catalyst can be metal load type catalyst;
Described metal load type catalyst is comprised of carrier and metal component, and described metal component is group vib in the periodic table of chemical element (such as W and/or Mo) and/or VIII family (such as Ni and/or Co) base metal; Described carrier is unformed aluminum oxide, such as the FDW-1 of Fushun Petrochemical Research Institute's production.
In the above-mentioned method, described hydroisomerizing cracking catalyst can be the amorphous silicon aluminium metal supported catalyst;
Metal component in the described typing sial metal supported catalyst is group vib in the periodic table of chemical element (such as W and/or Mo) and/or VIII family (such as Ni and/or Co) metal, such as the ZHC-02 of Fushun Petrochemical Research Institute's production.The present invention has following advantage:
1, through the resulting diesel cetane-number of alkylated reaction up to more than 80, be high-quality blended diesel component;
2, behind alkylated reaction, the difficult problem of the petroleum naphtha utilization in the Fischer-Tropsch synthetics is not only solved, and the simultaneously application of this technique has improved the synthetic economy of whole Fischer-Tropsch;
3, carry out alkylated reaction owing to from the Fischer-Tropsch synthetics, having fractionated out the virgin naphtha cut, obviously reduce at the hydrofining unit load.Simultaneously, because only refining to diesel oil fraction hydrogenating, the raw material boiling range narrows down, so this technique makes hydrofining mild condition, work simplification;
4, raw material or product can be adjusted flexibly according to processing requirement in alkylation operation unit, generate high-quality gasoline alkylate or diesel oil.
Description of drawings
Fig. 1 is the schema of the inventive method.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Utilize method provided by the invention to produce high-quality diesel oil, idiographic flow as shown in Figure 1, detailed process is described below:
Synthetic gas after the purification enters Fischer-Tropsch synthesis device A reaction through pipeline 1, reaction product enters knockout tower B through pipeline 2, isolates respectively the heavy oil that dry gas that pipeline 3 obtains, LPG that pipeline 4 obtains, petroleum naphtha that pipeline 5 obtains, diesel oil that pipeline 6 obtains and pipeline 7 obtain.Resulting heavy oil is entered hydroisomerizing cracking case C reaction through pipeline 8, the product that generates enters knockout tower D through pipeline 9 again, and that isolates respectively that dry gas that pipeline 10 obtains, LPG that pipeline 12 obtains, petroleum naphtha that pipeline 13 obtains, diesel oil that pipeline 15 obtains and pipeline 16 obtain is the heavy oil completely of cracking not.Wherein, dry gas and Fischer-Tropsch synthetics gained dry gas are got rid of plant areas through pipeline 11 in the lump, not cracking completely heavy oil incorporate the pipeline 8 hydroisomerizing cracking that circulates into.Resulting diesel oil distillate mixes with diesel oil in the Fischer-Tropsch synthetics, enters hydrofining reactor F reaction through pipeline 17, and refined products is discharged through pipeline 23.Resulting LPG and petroleum naphtha are mixed into pipeline 14, be mixed into alkylation reactor E reaction with LPG and the petroleum naphtha by the resulting separation of Fischer-Tropsch synthetics that enter pipeline 15 ', products therefrom enters knockout tower G through pipeline 18, the LPG that separation is discharged by pipeline 19 directly sends plant area, incorporate pipeline 14 through the isolated petroleum naphthas part of pipeline 20 into through pipeline 21 and proceed alkylated reaction, mix through the diesel oil of pipeline 22 isolated diesel oil distillates with hydrofining and send outside the factory.
Take whole Fischer-Tropsch synthetics as raw material, its character sees Table 1.
Hydroisomerizing cracking catalyst and Hydrobon catalyst are respectively the ZHC-02 hydroisomerizing cracking catalyst of Fushun Petrochemical Research Institute and the FDW-1 diesel hydro-pour-reducing catalyst of Fushun Petrochemical Research Institute.Experiment is carried out according to technical process provided by the present invention on medium-sized fixed bed hydrogenation device.Alkylation catalyst adopts the vitriol oil, and alkylation experiment carries out in special sealed reactor.
Produce diesel oil according to flow process shown in Figure 1 by the Fischer-Tropsch synthetics, the Fischer-Tropsch synthetics is separated, obtain respectively dry gas, LPG, petroleum naphtha, diesel oil and heavy oil five parts, wherein heavy oil partly enters the hydroisomerizing cracking case reaction of filling ZHC-02 catalyzer, reaction conditions is: the hydrogen dividing potential drop is 6.0MPa, temperature of reaction is 375 ° of C, and volume space velocity is 1.6h
-1Hydrogen to oil volume ratio is 300v/v, completely heavy oil continuation of unreacted circulation cracking in the cracked reaction product, diesel oil distillate with mix from the isolated diesel oil distillate of Fischer-Tropsch synthetics after enter in the lump the hydrofining reactor reaction that the FDW-1 catalyzer is housed, reaction conditions is: the hydrogen dividing potential drop is 6.0MPa, temperature of reaction is 300 ° of C, is 3.0h on the volume space velocity
-1, hydrogen to oil volume ratio is 300v/v.Jointly enter the alkylation reactor reaction with the LPG of hydroisomerizing cracking and naphtha fraction and from the isolated LPG of Fischer-Tropsch synthetics and virgin naphtha cut at last, catalyzer is used the vitriol oil, reaction conditions is: reaction pressure is 0.5MPa, temperature of reaction is-5 ° of C, and alkane alkene volume ratio is 10:1; Acid hydrocarbon volume ratio is 1.5:1, and stirring velocity is 2000rpm.
The operational condition of said process and product distribute as shown in table 2, and the naphtha fraction product property is listed in the table 3, and the diesel oil distillate product property is listed in the table 4.
Data can be found out from table, and the total recovery of diesel product is up to more than the 90wt%, and its cetane value surpasses 80, are diesel oil blending components preferably; Naphtha fraction mainly is that normal paraffin consists of, and is preferably preparing ethylene by steam cracking, propylene feedstocks.
The main character of table 1 Fischer-Tropsch synthetics
| Project | Data |
| Dry gas, wt% | 3.7 |
| LPG，wt% | 3.0 |
| Petroleum naphtha, wt% | 12.0 |
| Boiling range (ASTM2892), ° C | ? |
| IBP/10% | 31/67 |
| 30%/50% | 96/113 |
| 90%/FBP | 134/150 |
| Diesel oil, wt% | 33.0 |
| Boiling range (ASTM2892), ° C | ? |
| IBP/10% | 150/172 |
| 30%/50% | 214/245 |
| 90%/FBP | 316/370 |
| Heavy oil, wt% | 48.3 |
| Boiling range (ASTM5326), ° C | ? |
| IBP/10% | 370/419 |
| 30%/50% | 490/555 |
| 90%/FBP | 720/>750 |
Table 2 operational condition and product distribute
| The hydroisomerizing cracking: | ? |
| Catalyzer | ZHC-02 |
| Operational condition | ? |
| The hydrogen dividing potential drop, MPa | 6.0 |
| Temperature of reaction, ° C | 375 |
| Volume space velocity, h -1 | 1.6 |
| Hydrogen to oil volume ratio, v/v | 300 |
| Product distributes | ? |
| The dry gas yield, wt% | <1 |
| The LPG yield, wt% | <1 |
| Naphtha yield, wt% | 10 |
| Diesel yield, wt% | 80 |
| The tail oil yield, wt% | 8 |
| ? | ? |
| Hydrofining: | ? |
| Catalyzer | FDW-1 |
| Operational condition | ? |
| The hydrogen dividing potential drop, MPa | 6.0 |
| Temperature of reaction, ° C | 300 |
| Volume space velocity, h -1 | 3.0 |
| Hydrogen to oil volume ratio, v/v | 300 |
| Product distributes | ? |
| The dry gas yield, wt% | <1 |
| The LPG yield, wt% | <1 |
| Naphtha yield, wt% | <4 |
| Diesel yield, wt% | 94 |
| ? | ? |
| Alkylation: | ? |
| Catalyzer | The vitriol oil |
| Operational condition | ? |
| Reaction pressure, MPa | 0.5 |
| Temperature of reaction, ° C | -5 |
| Alkane alkene ratio, v/ |
10 |
| Acid hydrocarbon ratio, v/v | 1.5 |
| Stirring velocity, rpm | 2000 |
| Product distributes | ? |
| The LPG yield, wt% | <1 |
| Naphtha yield, wt% | 30 |
| Diesel yield, wt% | 69 |
Table 3 naphtha fraction product property
| Project | Data |
| Boiling range | <150°C |
| |
4 |
| Density (20 ° of C), g/cm 3 | 0.6999 |
| Form wt% | ? |
| Normal paraffin | 88 |
| Isoparaffin | 12 |
Table 4 diesel oil distillate product property
| Project | Data |
| Boiling range | 150～370 |
| Total recovery | 92 |
| Density (20 ° of C), g/cm 3 | 0.7725 |
| Condensation point, ° C | -10 |
| Cetane value | 81 |
| Sulphur content, μ g/g | <5 |
| Nitrogen content, μ g/g | <5 |
| Aromaticity content, wt% | <1.0 |
Claims (6)
1. a method of utilizing the Fischer-Tropsch synthetics to produce diesel oil comprises the steps:
(1) the Fischer-Tropsch synthetics is separated obtains LPG, petroleum naphtha, straight-run diesel oil and heavy oil;
(2) described heavy oil is carried out the hydroisomerizing cracking;
The described LPG and the petroleum naphtha that obtain in LPG in the synthetic oil that described hydroisomerizing cracking is obtained and naphtha fraction and the step (1) carry out alkylated reaction;
The described straight-run diesel oil that diesel oil distillate in the synthetic oil that described hydroisomerizing cracking is obtained and step (1) obtain is through hydrofining reaction;
(3) hydrofining diesel oil that the diesel oil distillate in the product of described alkylated reaction and described hydrofining reaction is obtained mixes namely realizes utilizing the Fischer-Tropsch synthetics to produce the purpose of diesel oil.
2. method according to claim 1, it is characterized in that: in the step (2), the temperature of described hydroisomerizing cracking is 300～450 ° of C, and pressure is 2.0～15.0MPa, and volume space velocity is 0.5～5.0h
-1, hydrogen to oil volume ratio is 100～1500Nm
3/ m
3
3. method according to claim 1 and 2, it is characterized in that: in the step (2), the temperature of described alkylated reaction is-30～50 ° of C, and pressure is 0～0.5MPa, and alkane alkene volume ratio is 1～15:1;
Described alkylated reaction carries out under the catalysis of the vitriol oil or hydrofluoric acid, and its sour hydrocarbon volume ratio is 0.5～1.5:1, and stirring velocity is 1000～5000rpm.
4. each described method according to claim 1-3 is characterized in that: in the step (2), the temperature of described hydrofining reaction is 300～450 ° of C, and pressure is 2.0～15.0MPa, and volume space velocity is 0.5～5.0h
-1, hydrogen to oil volume ratio is 100～1500Nm
3/ m
3
5. each described method according to claim 1-4 is characterized in that: described Hydrobon catalyst is metal load type catalyst;
Described metal load type catalyst is comprised of carrier and metal component, and described metal component is group vib and/or VIII family base metal in the periodic table of chemical element, and described carrier is unformed aluminum oxide.
6. each described method according to claim 1-5 is characterized in that: described hydroisomerizing cracking catalyst is the amorphous silicon aluminium metal supported catalyst;
Metal component in the described typing sial metal supported catalyst is group vib and/or VIII family metal in the periodic table of chemical element.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046126A (en) * | 2021-02-24 | 2021-06-29 | 中科合成油工程有限公司 | Method for improving diesel oil yield of process for producing diesel oil by Fischer-Tropsch synthesis oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854266A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation purifying combined process for Fischer-Tropsch synthetic substance |
| CN101230291A (en) * | 2007-01-23 | 2008-07-30 | 中国石油化工股份有限公司 | Low consumption energy method for processing fischer-tropsch synthesis |
| US20120160739A1 (en) * | 2010-12-22 | 2012-06-28 | Chevron U.S.A. Inc. | Processes for upgrading fischer-tropsch condensate olefins by alkylation of hydrocrackate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854266A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation purifying combined process for Fischer-Tropsch synthetic substance |
| CN101230291A (en) * | 2007-01-23 | 2008-07-30 | 中国石油化工股份有限公司 | Low consumption energy method for processing fischer-tropsch synthesis |
| US20120160739A1 (en) * | 2010-12-22 | 2012-06-28 | Chevron U.S.A. Inc. | Processes for upgrading fischer-tropsch condensate olefins by alkylation of hydrocrackate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113046126A (en) * | 2021-02-24 | 2021-06-29 | 中科合成油工程有限公司 | Method for improving diesel oil yield of process for producing diesel oil by Fischer-Tropsch synthesis oil |
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