CN103320166B - A kind of method utilizing F-T synthesis thing to produce diesel oil - Google Patents
A kind of method utilizing F-T synthesis thing to produce diesel oil Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing F-T synthesis thing to produce diesel oil, comprise the steps: that F-T synthesis thing is carried out separation and obtains LPG, petroleum naphtha, straight-run diesel oil and heavy oil by (1); (2) heavy oil is carried out hydroisomerizing cracking; The LPG obtained in LPG in the synthetic oil obtain hydroisomerizing cracking and naphtha fraction and step (1) and petroleum naphtha carry out alkylated reaction; The straight-run diesel oil that diesel oil distillate in the synthetic oil obtain hydroisomerizing cracking and step (1) obtain is through hydrofining reaction; (3) hydrofining diesel oil that the diesel oil distillate in the product of alkylated reaction and hydrofining reaction obtain is carried out mixing namely realize utilizing F-T synthesis thing to produce the object of diesel oil.Method of the present invention, carries out alkylated reaction owing to having fractionated out virgin naphtha cut from F-T synthesis thing, obviously reduces at hydrofining unit load.Meanwhile, owing to only refining diesel oil fraction hydrogenating, raw material boiling range narrows, and therefore this technique makes Hydrofinishing conditions gentleness, work simplification.
Description
Technical field
The present invention relates to a kind of method utilizing F-T synthesis thing to produce diesel oil.
Background technology
The various derivatives of oil are that development that is economic and society provides powerful power, but but not only face increasingly exhausted crisis as non-renewable petroleum resources, and quality also worse and worse.Cause that the course of processing is complicated, environmental problem outstanding thus and the disadvantageous effect such as cost increase.
Coal or Sweet natural gas etc. can be converted into clean liquid fuel efficiently through F-T synthesis, are considered to the main substitute of following petroleum resources.This production technique principle process comprises: coal or gas material generate through gasification that raw gas, raw gas purifying refiningly obtain synthetic gas, synthetic gas is converted into the hydro carbons such as straight-chain paraffin, alkene and synthetic oil processing through Fischer-Tropsch synthesis.
Relatively less for Fischer-Tropsch oil product technological method for processing at present.In published patent, as US2003/0057135A1, US5378348, US6309432, US6656342, US6296757, CN1854264A, CN1854266A, CN101230291A, CN1865405A, CN101173190A etc. describe the various technological method for processing for oil from Fischer-Tropsch synthesis respectively, general way is exactly first be separated F-T synthesis thing, then by carrying out hydroisomerizing cracking to different material and hydrofinishing process prepares diesel oil.In the process, the economy of oil from Fischer-Tropsch synthesis is promoted further by process optimization and the method such as integrated.
Generally based on the F-T synthesis of ferrum-based catalyst, the distinguishing feature of synthetics synthesizes hydrocarbon exactly mainly based on positive structure hydro carbons, and in synthetics, olefin(e) centent is higher simultaneously, and olefin component content is up to more than 50wt%.As can be seen here, F-T synthesis thing is faced with the difficult problem that virgin naphtha utilizes in the course of processing.General virgin naphtha cut in F-T synthesis thing proportion up to 12wt%.
Summary of the invention
The object of this invention is to provide a kind of method utilizing F-T synthesis thing to produce diesel oil.
A kind of method utilizing F-T synthesis thing to produce diesel oil provided by the invention, comprises the steps:
(1) F-T synthesis thing is carried out separation and obtains LPG(liquefied petroleum gas (LPG)), petroleum naphtha, straight-run diesel oil and heavy oil;
(2) described heavy oil is carried out hydroisomerizing cracking;
The described LPG obtained in LPG in the synthetic oil obtain described hydroisomerizing cracking and naphtha fraction and step (1) and petroleum naphtha carry out alkylated reaction;
The described straight-run diesel oil obtained in diesel oil distillate in the synthetic oil obtain the cracking of step (2) described hydroisomerizing and 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 obtain is carried out mixing namely realize utilizing F-T synthesis thing to produce the object of diesel oil.
In above-mentioned method, in step (2), the temperature of described hydroisomerizing cracking can be 300 ~ 450 ° of C, and as 375 ° of C, pressure can be 2.0 ~ 15.0MPa, and as 6.0MPa, volume space velocity can be 0.5 ~ 5.0h
-1, as 1.6h
-1, hydrogen to oil volume ratio can be 100 ~ 1500Nm
3/ m
3, as 300Nm
3/ m
3, described hydrogen to oil volume ratio refers to the volume ratio of hydrogen and raw material heavy oil.
In above-mentioned method, in step (2), the temperature of described alkylated reaction can be-30 ~ 50 ° of C, as-5 ° of C, pressure can be 0 ~ 0.5MPa, as 0.5MPa, alkane alkene volume ratio (referring to the ratio of all isoparaffin volume total amounts and all alkene volume total amounts in reaction mass) is 1 ~ 15:1(v/v), 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), as 1.5:1, stirring velocity can be 1000 ~ 5000rpm, as 2000.
In above-mentioned method, in step (2), the temperature of described hydrofining reaction can be 300 ~ 450 ° of C, and as 300 ° of C, pressure can be 2.0 ~ 15.0MPa, and as 6.0MPa, volume space velocity can be 0.5 ~ 5.0h
-1, as 3.0h
-1, hydrogen to oil volume ratio is 100 ~ 1500Nm
3/ m
3, 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 above-mentioned method, described Hydrobon catalyst can be metal load type catalyst;
Described metal load type catalyst is made up of carrier and metal component, and described metal component is group vib (as W and/or Mo) and/or VIII (as Ni and/or Co) base metal in the periodic table of chemical element; Described carrier is unformed aluminum oxide, as the FDW-1 that Fushun Petrochemical Research Institute produces.
In above-mentioned method, described hydroisomerizing cracking catalyst can be amorphous silicon aluminium metal supported catalyst;
Metal component in described sizing silica alumina support metal catalyst is group vib (as W and/or Mo) and/or VIII (as Ni and/or Co) metal in the periodic table of chemical element, as the ZHC-02 that Fushun Petrochemical Research Institute produces.Tool of the present invention has the following advantages:
1, the diesel cetane-number obtained through alkylated reaction, up to more than 80, is the blended diesel component of high-quality;
2, after alkylated reaction, the difficult problem that the petroleum naphtha in F-T synthesis thing utilizes not only is solved, and the application of this technique simultaneously improves the economy of overall F-T synthesis;
3, carry out alkylated reaction owing to having fractionated out virgin naphtha cut from F-T synthesis thing, obviously reduce at hydrofining unit load.Meanwhile, owing to only refining diesel oil fraction hydrogenating, raw material boiling range narrows, and therefore this technique makes Hydrofinishing conditions gentleness, work simplification;
4, alkylation operation unit, can adjust raw material or product flexibly according to processing requirement, generates gasoline alkylate or the diesel oil of high-quality.
Accompanying drawing explanation
Fig. 1 is the schema of the inventive method.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Utilize method provided by the invention to carry out production high-quality diesel oil, as shown in Figure 1, detailed process is described below idiographic flow:
Synthetic gas after purification enters Fischer-Tropsch synthesis device A through pipeline 1 and reacts, reaction product enters knockout tower B through pipeline 2, isolates dry gas that pipeline 3 obtains respectively, diesel oil that petroleum naphtha that LPG that pipeline 4 obtains, pipeline 5 obtain, pipeline 6 obtain and the heavy oil that pipeline 7 obtains.Obtained heavy oil is entered hydroisomerizing cracking case C through pipeline 8 react, generate product and enter knockout tower D through pipeline 9 again, isolate dry gas that pipeline 10 obtains respectively, diesel oil that petroleum naphtha that LPG that pipeline 12 obtains, pipeline 13 obtain, pipeline 15 obtain and pipeline 16 obtain is non-cracking heavy oil completely.Wherein, dry gas and F-T synthesis thing gained dry gas get rid of plant area through pipeline 11 in the lump, and non-cracking completely heavy oil is incorporated to pipeline 8 and carries out the cracking of circulation hydroisomerizing.The diesel oil distillate obtained mixes with the diesel oil in F-T synthesis thing, and enter hydrofining reactor F through pipeline 17 and react, refined products is discharged through pipeline 23.The LPG obtained and petroleum naphtha are mixed into pipeline 14, with enter being mixed into alkylation reactor E by the LPG of F-T synthesis thing resulting separation and petroleum naphtha and reacting of pipeline 15 ', products therefrom enters knockout tower G through pipeline 18, the LPG discharged through pipeline 19 after separation directly sends plant area, be incorporated to pipeline 14 through the isolated petroleum naphtha part of pipeline 20 through pipeline 21 and proceed alkylated reaction, the diesel oil come through the isolated diesel oil distillate of pipeline 22 and hydrofining mixes to be sent outside factory.
With overall F-T synthesis thing for raw material, its character is in 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.
Diesel oil is produced by F-T synthesis thing according to the flow process shown in Fig. 1, F-T synthesis thing is separated, obtain dry gas, LPG, petroleum naphtha, diesel oil and heavy oil five part respectively, wherein heavy oil partial enters the hydroisomerizing cracking case reaction of filling ZHC-02 catalyzer, reaction conditions is: 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, unreacted heavy oil continuation completely circulation cracking in cracked reaction product, diesel oil distillate with mix from the isolated diesel oil distillate of F-T synthesis thing after enter the hydrofining reactor that FDW-1 catalyzer is housed in the lump and react, reaction conditions is: hydrogen dividing potential drop is 6.0MPa, temperature of reaction is 300 ° of C, volume space velocity is 3.0h
-1, hydrogen to oil volume ratio is 300v/v.Finally by the LPG of hydroisomerizing cracking and naphtha fraction and jointly enter alkylation reactor from the isolated LPG of F-T synthesis thing and virgin naphtha cut and react, the catalyst application 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.
Operational condition and the product slates of said process are as shown in table 2, and naphtha fraction product property is listed in table 3, and diesel oil distillate product property is listed in table 4.
As can be seen from the table, the total recovery of diesel product is up to more than 90wt%, and its cetane value, more than 80, is good diesel oil blending component; Naphtha fraction mainly normal paraffin is formed, and is good preparing ethylene by steam cracking, propylene feedstocks.
The main character of table 1 F-T synthesis thing
| 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 slates
| Hydroisomerizing cracking: | |
| Catalyzer | ZHC-02 |
| Operational condition |
| 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 slates | |
| Dry gas yield, wt% | <1 |
| LPG yield, wt% | <1 |
| Naphtha yield, wt% | 10 |
| Diesel yield, wt% | 80 |
| Tail oil yield, wt% | 8 |
| Hydrofining: | |
| Catalyzer | FDW-1 |
| Operational condition | |
| 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 slates | |
| Dry gas yield, wt% | <1 |
| 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/v | 10 |
| Acid hydrocarbon ratio, v/v | 1.5 |
| Stirring velocity, rpm | 2000 |
| Product slates | |
| LPG yield, wt% | <1 |
| Naphtha yield, wt% | 30 |
| Diesel yield, wt% | 69 |
Table 3 naphtha fraction product property
| Project | Data |
| Boiling range | <150°C |
| Total recovery | 4 |
| Density (20 ° of C), g/cm 3 | 0.6999 |
| Composition, 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. utilize F-T synthesis thing to produce a method for diesel oil, comprise the steps:
(1) F-T synthesis thing is carried out separation and obtain LPG, petroleum naphtha, straight-run diesel oil and heavy oil;
(2) described heavy oil is carried out hydroisomerizing cracking;
The described LPG obtained in LPG in the synthetic oil obtain described hydroisomerizing cracking and naphtha fraction and step (1) and petroleum naphtha carry out alkylated reaction; Described alkylated reaction carries out under the catalysis of the vitriol oil or hydrofluoric acid;
The described straight-run diesel oil that diesel oil distillate in the synthetic oil obtain described hydroisomerizing cracking 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 obtain is carried out mixing namely realize utilizing F-T synthesis thing to produce the object of diesel oil.
2. method according to claim 1, is characterized in that: in step (2), and the temperature of described hydroisomerizing cracking is 300 ~ 450 DEG 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, is characterized in that: in step (2), and the temperature of described alkylated reaction is-30 ~ 50 DEG C, and pressure is 0 ~ 0.5MPa, and alkane alkene volume ratio is 1 ~ 15:1;
Described sour hydrocarbon volume ratio is 0.5 ~ 1.5:1, and stirring velocity is 1000 ~ 5000rpm.
4. method according to claim 1, is characterized in that: in step (2), and the temperature of described hydrofining reaction is 300 ~ 450 DEG 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. method according to claim 1, is characterized in that: described Hydrobon catalyst is metal load type catalyst;
Described metal load type catalyst is made up of carrier and metal component, and described metal component is group vib and/or VIII base metal in the periodic table of chemical element, and described carrier is unformed aluminum oxide.
6. method according to claim 1, is characterized in that: described hydroisomerizing cracking catalyst is amorphous silicon aluminium metal supported catalyst;
Metal component in described amorphous silicon aluminium metal supported catalyst is group vib and/or group VIII metal in the periodic table of chemical element.
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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 |
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