CN1764619A - Extraction of oxygenates from a hydrocarbon stream - Google Patents
Extraction of oxygenates from a hydrocarbon stream Download PDFInfo
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- CN1764619A CN1764619A CN200480006726.0A CN200480006726A CN1764619A CN 1764619 A CN1764619 A CN 1764619A CN 200480006726 A CN200480006726 A CN 200480006726A CN 1764619 A CN1764619 A CN 1764619A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
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Abstract
The invention relates to a commercially feasible process for extracting oxygenates from a hydrocarbon stream, typically a fraction of the condensation product of a Fischer-Tropsch reaction, while preserving the olefin content of the condensation product. The oxygenate extraction process is a liquid-liquid extraction process that takes place in an extraction column using a mixture of methanol and water as the solvent, wherein an extract from the liquid-liquid extraction is sent to a solvent recovery column from which a top product comprising methanol, olefins and paraffins is recycled to the extraction column, thereby enhancing the overall recovery of olefins and paraffins.
Description
Background of invention
The present invention relates to a kind of from hydrocarbon stream the method for extraction of oxygenates.
Known have many from hydrocarbon stream the method for extraction of oxygenates.Such extracting process comprises hydrogenation, component distillation, extractive distillation, vapour phase dehydration, liquid-phase dehydration and liquid-liquid extraction.
California Research Corporation English Patent 669,313 under one's name discloses the hydrocarbon condensate (hydrocarbon condensate) made with Fischer-Tropsch process as the purposes of raw material in making alkylbenzene.This piece reference only limits to use " high temperature " Fischer-Tropsch process to make the hydrocarbon condensate, and wherein Fischer-Tropsch reaction is to carry out under about 300 ℃ and higher temperature.This reference shows that the fischer-tropsch raw material of manufacturing owing to carbonyl in smell and the fischer-tropsch raw material is oxygenate (oxygenate) moisture issues that content caused, causes LINEAR ALKYL BENZENE (LAB) of poor quality.The method of removing oxygenate of being advised comprises with hot caustic solution or sodium bisulfite handles raw material, extract with for example methanol solvent subsequently, and perhaps with the boric acid solution processing, the ester that formation can be removed by distillation.The preferred method of handling this problem is to use activated carbon and silica gel adsorption of oxygenates from the fischer-tropsch raw material.This method is practicable to the raw material of low oxygenate concentration just.And olefin recovery does not promptly keep olefin(e) centent less than 25% in embodiment.
Naamlooze Vennootschap De Batafsche Petroleum Maatschappij English Patent 661 under one's name, 916 relate to and a kind ofly extracting by liquid sulfur dioxide and the paraffinic hydrocarbons that uses mutual countercurrent flow, separate the method for oxygenatedchemicals from the reaction product of Fischer-Tropsch reaction.This reference provides with single solvent of planting, and for example liquid sulfur dioxide or methanol aqueous solution extract the method for separating oxygenatedchemicals, this method is verified be in practice difficulty and uneconomical.
The present invention relates to a kind of extraction or separate the method for the viable commercial of the olefin(e) centent that oxygenate keeps this stream simultaneously from the hydrocarbon stream that comprises alkene and paraffins, described hydrocarbon stream is the condensate product of Fischer-Tropsch reaction typically.
Summary of the invention
According to the present invention, provide a kind of from hydrocarbon stream extraction of oxygenates keep the method for viable commercial of the olefin(e) centent of condensate product, a kind of fraction of described hydrocarbon stream Fischer-Tropsch reaction condensate product typically simultaneously.
This oxygenate extracting process is the liquid-liquid extraction method, this method is preferably carried out in extraction tower, described extraction tower uses the mixture of first alcohol and water as solvent, wherein the extraction liquid of liquid-liquid extraction can be delivered to solvent recovery tower, the overhead product that will comprise methyl alcohol, alkene and paraffins in recovery tower is recycled to extraction tower, thereby improves the total yield of alkene and paraffins.Bottom product from the solvent recovery tower can also be recycled to extraction tower.
The water-content of preferred solvent surpasses 3 weight %, and more preferably water-content is 5 weight %-15 weight %.
Preferably will deliver to stripping tower from the extract remainder of extraction tower, and hydrocarbon feed stream is drawn from stripping tower as bottom product, described hydrocarbon feed stream contains alkene and the paraffins that surpasses 90 weight %, and typically less than 0.2 weight %, preferably less than the oxygenate of 0.02 weight %.Be preferably greater than 70% through the alkene after the oxygenate extraction process and the rate of recovery of paraffins,, keep the ratio of olefin/paraffin simultaneously at least substantially more preferably greater than 80%.
According to another aspect of the present invention, solvent recovery tower comprises extraction liquid inlet, top overhead product outlet and following bottom product outlet, wherein side line be positioned at that the top and overhead product of extraction liquid feed points exports below.
Hydrocarbon stream can be the condensate product of low temperature Fischer-Tropsch reaction, described low temperature Fischer-Tropsch reaction is under 160 ℃-280 ℃, preferred 210 ℃-260 ℃ temperature, in the presence of Fischer-Tropsch catalyst, preferably in the presence of cobalt catalyst, carry out, contain 60 to 80 weight % paraffinss and 10 to 30 weight % to provide, typically less than the hydrocarbon condensate of the alkene of 25 weight %.The alkene of Zhi Zaoing has greater than 92%, is typically greater than 95% high linearity like this.So the linear lag of the paraffins of making is greater than 92%.
Before extraction, the hydrocarbon condensate product typically is fractionated to C
8To C
16Scope preferably is fractionated to C
10To C
13Scope.Typically, hydrocarbon stream is C
10To C
13The fractionated hydrocarbon condensate product from the low temperature Fischer-Tropsch reaction in the scope, this hydrocarbon condensate product contain 10 to 30 weight %, having greater than 92%, be typically greater than the alkene of 95% the linear lag less than 25 weight % typically.
The accompanying drawing summary
Fig. 1 is the graphic representation that is presented under different solvents and the feed ratio alkene and the paraffins per-cent rate of recovery in the recovery tower, and use therein solvent is the solvent that contains methyl alcohol and 0,3 and 5% water;
Fig. 2 is the graphic representation that is presented under different solvents and the feed ratio C10/11 alkene and paraffin recovery in the recovery tower, and use therein solvent is the solvent that contains methyl alcohol and 0,3 and 5% water; With
Fig. 3 is the skeleton diagram of the present invention's method of extraction of oxygenates from hydrocarbon stream.
Preferred embodiment is described
The present invention relates to the always method of extraction of oxygenates in the hydrocarbon condensation logistics of Fischer-Tropsch reaction. Can be with the hydrocarbon stream of oxygenate content with suitable reduction for the production of other chemicals, for example linear alkyl benzene feedstock can be prepared by low temperature Fischer-Tropsch condensate in the application of the invention.
In Fischer-Tropsch process, will react at Fischer-Tropsch catalyst by the synthesis gas (carbon monoxide and hydrogen) that coal gasification or gas renormalizing obtain, produce the mixture of the hydro carbons contained from methane to wax and a small amount of oxygenate.
In the low temperature Fischer-Tropsch reaction, reaction is at slurry bed reactor or fixed bed reactors, preferably in slurry bed reactor, under 160 ℃-280 ℃, preferred 210 ℃-260 ℃ temperature, under the pressure in 18-50 bar (gauge pressure), preferred 20-30 bar (gauge pressure) scope, in the presence of catalyst, carry out. Catalyst can comprise iron, cobalt, nickel or ruthenium. But, for the preferred cobalt of low-temp reaction-catalyst based. Usually Co catalysts is carried by alumina support.
In low temperature Fischer-Tropsch reaction process, hydrocarbon vapour phase that will be lighter is separated from the liquid phase that comprises heavier liquid hydrocarbon product. Heavier liquid hydrocarbon product (wax-like product) is the primary product of reaction, and can be by for example hydrocrack, to make diesel oil and naphtha.
To comprise the lighter hydrocarbon vapour phase condensation of gaseous hydrocarbon product, unreacted synthetic G﹠W, and obtain " condensate product ", this condensate product comprises water and hydrocarbon condensate product mutually.
The hydrocarbon condensate product comprises C4To C26Alkene, alkane in the scope, and the oxygenate that comprises alcohol, ester, aldehyde, ketone and acid.
Typically, the hydrocarbon condensate product of low temperature Fischer-Tropsch reaction contains the alkene of 10-30 % by weight, the oxygenate of the alkane of 60-80 % by weight and 5-10 % by weight. Although it has surprisingly been found that this condensate product contains oxygenate and olefin(e) centent is low, can be for the manufacture of linear alkyl benzene. But, at first must extract oxygenate, because these species have negative effect to alkylated reaction. Therefore, need to find a kind of extraction of oxygenates and keep simultaneously the method for olefin(e) centent. In order to make linear alkyl benzene, be C with the fractionation of hydrocarbon condensate product10-C
13Fraction, this fraction contain for example alkene of 25 % by weight, the oxygenate of the alkane of 68 % by weight and 7 % by weight. This C10-C
13The oxygenate content of fraction can be up to 15%.
In the prior art, proposed many from hydrocarbon stream the method for extraction of oxygenates.Such removal method comprises hydrogenation, component distillation, extractive distillation, vapour phase dehydration, liquid-phase dehydration and liquid-liquid extraction.Have been found that liquid-liquid extraction is the preferred method of oxygenate extraction, because if select suitable solvent, can keep olefin(e) centent.In liquid-liquid extraction, solvent can be any polar material that has partial miscibility with feedstream 14, and trolamine for example contains the triglycol of 0 to 20% water, contains acetonitrile, hydroxyacetone, dibasic alcohol, methyl alcohol or the second alcohol and water of 5% to 20% water.Usually, preferred high boiling solvent, because compare with low boiling point solvent, the solvent recovery step after the extraction needs less energy.But, have been found that the mixture of first alcohol and water, this mixture is a low boiling point solvent, does not but have this shortcoming, because this low boiling point solvent can be effectively (if the extraction of required oxygenate is not too strict, its ratio can less than 1) under the low situation of solvent and feed ratio.
In addition, people will can not expect and can use the first alcohol and water to come extraction of oxygenates from above-mentioned hydrocarbon condensate as the solvent in the liquid-liquid extraction tower, because will cause following expection with the research of different azeotropes of water in being present in the hydrocarbon condensate: distilled water in solvent recovery tower and not make oxygenate overhead product azeotropic simultaneously be impossible.Surprisingly, true really not so.
Therefore, one side more of the present invention is, have been found that the water/methanol solvate in the liquid-liquid extraction tower, water/the methanol solvate that preferably contains the water-content that surpasses 3 weight %, with anhydrous methanol solvent in the liquid-liquid extraction tower or contain less than the water/methanol solvate of 3 weight % water and compare, cause the better rate of recovery of required product in the solvent recovery tower.Fig. 1 has shown this point, and from Fig. 1 as seen, the methanol solvent that contains 5 weight % water provides in the solvent recovery tower alkene and the paraffin recovery up to 80%.Fig. 2 shows in the solvent recovery tower that the rate of recovery of C10/11 alkene and paraffins can reach almost 100%.
Therefore, according to the present invention, typically, from the alkene and the paraffins of liquid-liquid extraction tower recovery 90%.10% alkene and the paraffins that do not reclaim are delivered to solvent recovery tower with the extraction liquid form from the liquid-liquid extraction tower.In the solvent recovery tower, alkene and the paraffins that is up to 60% in the solvent recovery tower reclaimed with the overhead product form from solvent tower, and be recycled to the liquid-liquid extraction tower.This causes the total yield of alkene and paraffins to surpass 90%.
With reference to Fig. 3, liquid-liquid extraction method of the present invention comprises liquid-liquid extraction tower 20.The fractionated condensation product 14 of above-mentioned low temperature Fischer-Tropsch reaction is transported in the tower at the bottom of extraction tower 20 towers or near the place at the bottom of its tower, and the solvent streams 21 that comprises methyl alcohol and water mixture is transported in the tower at the cat head of extraction tower 20 or near the place of its cat head.Preferred solvent stream 21 comprises and surpasses 5 weight % water, typically is 6 weight % water.Solvent and feed ratio in the solvent streams are low, typically less than 1.5, are generally about 1.25.
Extract remainder 22 from extraction tower 20 cats head, this extract remainder comprises alkene and paraffins and a small amount of solvent, enter extract remainder stripping tower 23, and hydrocarbon product stream is drawn as bottom product 24, described hydrocarbon product stream comprises alkene and the paraffins that surpasses 90 weight %, usually up to alkene and the paraffins of 99 weight %, and less than 0.2 weight %, preferably less than the oxygenate of 0.02 weight %.The total yield that bottom product 24, this product demonstrate alkene and paraffins surpasses 90%, comprise the alpha-olefin that surpasses 20 weight % and surpass 70 weight % just-paraffins.Thereby the olefin(e) centent that has kept hydrocarbon product (this hydrocarbon product will be used to make LINEAR ALKYL BENZENE (LAB)).Mainly comprise methyl alcohol (surpass 90 weight %) and comprise the water (less than 5 weight %) of lower concentration and the solvent of olefin/paraffin (less than 5 weight %) is drawn as overhead product 25, and turn back to solvent feed 21.If hope with vapour stream form recovery tower bottom product 24, can be drawn the bottom product vapour stream and be reclaimed from tower 20.The liquid product of tower 20 then becomes very little outflow stream.
As mentioned above, for liquid-liquid extraction, usually preferred high boiling solvent, because compare with low boiling point solvent, the solvent recovery step after the extraction needs less energy.But, have been found that the mixture of first alcohol and water, this mixture is a low boiling point solvent, does not but have this shortcoming, because this low boiling point solvent (if the extraction of required oxygenate is not too strict, its ratio can less than 1) under the low situation of solvent and feed ratio can be effective.
The research of the different azeotropes that exist between component in raw material and the water will cause people to expect: water can not be distilled out in solvent recovery tower 27 cats head and oxygenate not at the overhead product azeotropic.Surprisingly, true really not so.Methyl alcohol, it does not form azeotrope with any other species that exist, and prevents to distill under the temperature identical with alkene and paraffins water outlet/oxygenate azeotrope.This has shown the extractive distillation effect.The result is, can distill alkene and paraffins overhead product, reclaims the oxygenate as bottom product simultaneously.This has the effect of the total yield that improves this operation alkene and paraffins, because the overhead product 29 of solvent recovery tower 27 is recycled to extraction tower 20, it means that alkene and paraffins are forced in this program of disengaging in the product stream 24.
Therefore, can under the condition of not using the counter solvent in the extraction tower, obtain having the hydrocarbon stream 24 of alkene and the high total yield of paraffins.In this mode of operation, in overhead product stream 29, go back recovery part water (10-50%).
When operating solvent recovery tower 27 in the above described manner, expect that some species may be trapped within the tower.These species trend towards building up and causing the instability operation of solvent recovery tower in operation.Under situation of the present invention, such species typically are heavier alkene and paraffins or lighter oxygenate.Under the condition of a small amount of side stream, the operation solvent recovery tower can prevent the accumulation of this species, thereby causes the very big improvement of system operation.
Can also move extraction tower 20 and solvent recovery tower 27 with different methanol/water ratios.This can need, because the high water content of extraction tower 20 will cause the ratio of solvent and raw material to improve (because the solubleness of the oxygenate in the solvent descends), need a certain amount of water to reach and methyl alcohol bonded extractive distillation effect simultaneously, to reclaim all alkene and paraffins as overhead product in the solvent recovery tower 27.Guide to stream 26 by flowing 33 some water that will flow in 32, can reach in the different methanol/water ratios of two towers (20 and 27).
At above-mentioned C
10-C
13Hydrocarbon feed stream by above-mentioned oxygenate extraction process after, it is 1.25 that this operation is used methyl alcohol (95 weight %) and water (5 weight %) mixture and solvent/raw material ratio, the hydrocarbon feed stream 24 of purifying comprise 22 weight % alkene, 76 weight % paraffins and be less than the oxygenate of 0.02 weight %.This extracting process is extraction of oxygenates not only, but also has kept the olefin(e) centent in the hydrocarbon feed.The purified hydrocarbon feed stream that contains alkene is particularly useful in the manufacturing of LINEAR ALKYL BENZENE (LAB).
Now by the following unrestricted embodiment more detailed description the present invention of reference.
Embodiment 1
This embodiment has shown a kind of the method according to this invention, wherein the C from the hydrocarbon condensate product of producing by the low temperature Fischer-Tropsch reaction
10-C
13Fraction is removed oxygenate and is reached low-level.It in solvent/raw material ratio operation extraction tower 20 under 1.25 and 50 ℃ the temperature.Olefin/paraffin recovery always is 89.9% in the stream 24.Olefin/paraffin ratio in the raw material is 1: 3.7, is 1: 3.6 after the oxygenate extraction.Therefore kept olefin/paraffin ratio basically.Oxygenate content in the stream 24 only is 0.0145%.
| | 14 | 21 | 22 | 26 | ||||
| Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | |||||
| Add up to | 100 | 3000 | 100 | 3750 | 100 | 2530 | 100 | 4220 |
| Total C10-C13P/O | 92.7 | 2779.7 | 2.16 | 81.0 | 99.1 | 2507.9 | 6.20 | 261.7 |
| Total oxygenate | 7.3 | 217.7 | 0.000 | 0.000 | 0.0144 | 0.365 | 5.78 | 243.7 |
| Lightweight thing and heavies | 0.057 | 1.7 | 0.004 | 0.144 | 0.0104 | 0.263 | 0.00480 | 0.202 |
| Water | 0.031 | 0.934 | 6.01 | 225.6 | 0.0073 | 0.184 | 5.74 | 242.4 |
| Methyl alcohol | 0.000 | 0.000 | 91.7 | 3443.3 | 0.842 | 21.31 | 82.3 | 3472.0 |
Extract remainder stripping tower 23
| | 22 | 25 | 24 | |||
| Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | ||||
| Add up to | 100 | 2530 | 100 | 30 | 100 | 2500 |
| Total C10-C13P/O | 99.1 | 2507.9 | 2.63 | 0.793 | 99.97 | 2499.4 |
| Total oxygenate | 0.0144 | 0.365 | 0.00163 | 0.000491 | 0.0145 | 0.363 |
| Lightweight thing and heavies | 0.0104 | 0.263 | 0.0887 | 0.0267 | 0.00808 | 0.202 |
| Water | 0.0073 | 0.184 | 1.52 | 0.456 | 0.00115 | 0.0288 |
| Methyl alcohol | 0.842 | 21.31 | 95.4 | 28.7 | 0.000 | 0.000 |
| | 26 | 29 | 28 | |||
| Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | ||||
| Add up to | 100 | 4220 | 100 | 3584 | 100 | 636 |
| Total C10-C13P/O | 6.20 | 261.7 | 2.37 | 85.1 | 27.6 | 175.8 |
| Total oxygenate | 5.78 | 243.7 | 0.00140 | 0.0503 | 42.0 | 267.0 |
| Lightweight thing and heavies | 0.00480 | 0.202 | 0.00747 | 0.268 | 0.00279 | 0.0177 |
| Water | 5.74 | 242.4 | 1.30 | 46.8 | 29.3 | 186.6 |
| Methyl alcohol | 82.3 | 3472.0 | 96.2 | 3451.9 | 1.04 | 6.63 |
Embodiment 2
This embodiment has shown a kind of the method according to this invention, wherein the C from the hydrocarbon condensate product of producing by the low temperature Fischer-Tropsch reaction
10-C
13Fraction is removed oxygenate and is reached low-level, and it has higher oxygenate material concentration (12.36 weight %) than embodiment 1.It in solvent/raw material ratio operation extraction tower 20 under the temperature of 2: 1 and 50 ℃.The total yield of olefin/paraffin is 91.4% in the stream 24.Once more, kept olefin/paraffin ratio basically.Oxygenate content in the stream 24 only is 0.0154%.
| | 14 | 32 | 21 | 22 | 26 | |||||
| Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kG/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | ||||||
| Add up to | 100 | 3000 | 0 | 0 | 100 | 6000 | 100 | 2430 | 100 | 6570 |
| Total C10-C13 P/O | 87.6 | 2627.2 | 0 | 0 | 5.91 | 354.9 | 98.9 | 2403.4 | 8.81 | 578.7 |
| Total oxygenate | 12.36 | 370.7 | 0 | 0 | 0.008 | 0.485 | 0.01529 | 0.4 | 5.64 | 370.7 |
| Lightweight thing and heavies | 0.0698 | 2.093 | 0 | 0 | 0.000 | 0.002 | 0.07472 | 1.8159 | 0.00425 | 0.279 |
| Water | 0.0000 | 0.000 | 0 | 0 | 11.75 | 705.3 | 0.00314 | 0.0762 | 10.73 | 705.2 |
| Methyl alcohol | 0.000 | 0.000 | 0 | 0 | 82.3 | 4939.4 | 1.02 | 24.8 | 74.8 | 4914.6 |
Extract remainder stripping tower 23
| | 22 | 25 | 24 | |||
| Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | Form flow velocity (weight %) (kg/hr) | ||||
| Add up to | 100 | 2430 | 100 | 26 | 100 | 2405 |
| Total C10-C13P/O | 98.9 | 2403.4 | 3.94 | 1.017 | 99.92 | 2402.408 |
| Total oxygenate | 0.1529 | 0.372 | 0.00113 | 0.00029 | 0.0154 | 0.37139 |
| Lightweight thing and heavies | 0.075 | 1.8159 | 0.0000 | 0.0000 | 0.076 | 1.8159 |
| Water | 0.00314 | 0.0762 | 0.294 | 0.0761 | 0.000006 | 0.0002 |
| Methyl alcohol | 1.02 | 24.8 | 95.8 | 24.7 | 0.001 | 0.0 |
| | 26 | 25 | 29 | 28 | ||||
| Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | Form flow velocity (weight (kg/hr) %) | |||||
| Add up to | 100 | 6570 | 100 | 26 | 100 | 5400 | 100 | 1195 |
| Total C10-C13P/O | 8.81 | 578.7 | 3.94 | 1.017 | 5.57 | 354.9 | 18.8 | 224.8 |
| Total oxygenate | 5.64 | 370.7 | 0.00060 | 0.00015 | 0.00000 | 0.0 | 31.0 | 370.7 |
| Lightweight thing and heavies | 0.00425 | 0.279 | 0.0000 | 0.0000 | 0.00005 | 0.002 | 0.02317 | 0.2770 |
| Water | 10.73 | 705.2 | 0.294 | 0.0761 | 1.96 | 105.8 | 50.1 | 599.5 |
| Methyl alcohol | 74.8 | 4914.6 | 95.8 | 24.7 | 91.5 | 4939.3 | 0.00 | 0.05 |
Claims (16)
1, a kind of from hydrocarbon stream the method for extraction of oxygenates, this method comprises the mixture that uses the first alcohol and water as solvent, the step of extraction of oxygenates in the liquid-liquid extraction method.
2. according to the process of claim 1 wherein that the extraction liquid with liquid-liquid extraction delivers to solvent recovery tower, the overhead product that will comprise methyl alcohol, alkene and paraffins in recovery tower is recycled to extraction step, thereby improves the total yield of alkene and paraffins.
3. according to the method for claim 2, wherein will be recycled to extraction step from the water of the bottom product of solvent recovery tower.
4. require the method for any one according to aforesaid right, wherein extraction step occurs in the extraction tower.
5. require the method for any one according to aforesaid right, the water-content that wherein is introduced to the solvent of extraction step is no more than 3 weight %.
6. according to the method for claim 5, wherein the water-content of solvent is 5 weight %-15% weight %.
7. require the method for any one according to aforesaid right, wherein the olefin/paraffin ratio in the hydrocarbon stream is maintained after extraction step basically.
8 according to any one method of claim 4-7, wherein will deliver to stripping tower from the extract remainder of extraction tower, from stripping tower, will comprise the alkene and the paraffins that surpass 90 weight %, and draw as bottom product less than the hydrocarbon feed stream of the oxygenate of 0.2 weight %.
9 according to Claim 8 methods, wherein bottom product comprises the oxygenate less than 0.02 weight %.
10. require the method for any one according to aforesaid right, wherein be higher than 70% through the alkene of oxygenate extraction step and the rate of recovery of paraffins.
11., wherein be higher than 80% through the alkene of oxygenate extraction step and the rate of recovery of paraffins according to the method for claim 10.
12. according to any one method of claim 2-11, wherein solvent recovery tower comprises extraction liquid inlet, top overhead product outlet and following bottom product outlet, wherein side line be positioned at that the top and overhead product of extraction liquid feed points exports below.
13. require any one method according to aforesaid right, wherein hydrocarbon stream is the fractionated condensation produce thing from the low temperature Fischer-Tropsch reaction.
14. require any one method according to aforesaid right, wherein hydrocarbon stream comprises the oxygenate of 5-15 weight %.
15. require any one method according to aforesaid right, wherein hydrocarbon stream be fractionated to C
8To C
16In the scope.
16 require any one method according to aforesaid right, are C with fractionated condensation produce thing wherein
10To C
13In the scope.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45341803P | 2003-03-10 | 2003-03-10 | |
| ZA200301937 | 2003-03-10 | ||
| US60/453,418 | 2003-03-10 | ||
| ZA2003/1937 | 2003-03-10 | ||
| US49681603P | 2003-08-21 | 2003-08-21 | |
| US60/496,816 | 2003-08-21 | ||
| ZA200306524 | 2003-08-21 | ||
| ZA2003/6524 | 2003-08-21 | ||
| PCT/IB2004/000656 WO2004080928A2 (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
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| Publication Number | Publication Date |
|---|---|
| CN1764619A true CN1764619A (en) | 2006-04-26 |
| CN100575320C CN100575320C (en) | 2009-12-30 |
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| CN200480006726A Expired - Fee Related CN100575320C (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from hydrocarbon stream |
| CNB2004800066821A Expired - Lifetime CN100383096C (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
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| CN (2) | CN100575320C (en) |
| AU (2) | AU2004220264A1 (en) |
| EA (1) | EA007843B1 (en) |
| EG (1) | EG24947A (en) |
| WO (1) | WO2004080928A2 (en) |
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| CN102452888A (en) * | 2010-10-22 | 2012-05-16 | 中科合成油工程有限公司 | Method for refining 1-hexene from fischer tropsch synthetic oils |
| CN113801077A (en) * | 2021-09-16 | 2021-12-17 | 杭州泽邦科技有限公司 | Method for quickly removing BHT antioxidant |
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| CN1313572C (en) * | 2005-09-12 | 2007-05-02 | 中国石油天然气股份有限公司 | Preparation method of low-sulfur low-aromatic aluminum foil rolling base oil |
| WO2011049731A1 (en) | 2009-10-21 | 2011-04-28 | Merck Sharp & Dohme Corp. | Quinolinone-pyrazolone m1 receptor positive allosteric modulators |
| CN104073285B (en) * | 2013-03-26 | 2016-01-13 | 中国石油化工股份有限公司 | The extracting of liquid liquid is separated the method for aromatic hydrocarbons in diesel oil |
| US20150005552A1 (en) * | 2013-06-26 | 2015-01-01 | Uop Llc | Crude Butadiene Pre-Treatment for Removal of High Furan Content |
| CN106753546A (en) * | 2017-01-23 | 2017-05-31 | 洛阳和梦科技有限公司 | F- T synthesis light fraction oil refining new technology |
| CN106675625A (en) * | 2017-01-23 | 2017-05-17 | 洛阳和梦科技有限公司 | Fischer-Tropsch process light distillate oil refining unit |
| CN108341735B (en) * | 2018-01-26 | 2021-07-27 | 南京三新化工科技有限公司 | Method for producing linear alkylbenzene |
| CN111718748A (en) * | 2019-03-20 | 2020-09-29 | 国家能源投资集团有限责任公司 | Method for removing oxygen-containing compounds from Fischer-Tropsch synthetic oil |
| CN114478169A (en) * | 2020-11-12 | 2022-05-13 | 国家能源投资集团有限责任公司 | Method and device for separating and purifying 1-hexene from Fischer-Tropsch synthetic oil |
| CN114736091A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Method and apparatus for separating 1-hexene from hydrocarbon stream containing C6 olefins |
| CN115491229B (en) * | 2022-09-23 | 2024-03-22 | 上海兖矿能源科技研发有限公司 | Separation method of high-temperature Fischer-Tropsch synthesis light oil |
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| US4513156A (en) * | 1984-04-16 | 1985-04-23 | Mobil Oil Corporation | Olefin oligomerization using extracted feed for production of heavy hydrocarbons |
| US4603225A (en) * | 1985-09-11 | 1986-07-29 | Dravo Corporation | Process for separating dimethyl ether from a hydrocarbon mixture containing the same |
| US4686317A (en) * | 1985-12-31 | 1987-08-11 | Mobil Oil Corporation | Process for removing oxygenated compounds or other impurities from hydrocarbon streams |
| DE19911910B4 (en) * | 1999-03-17 | 2007-04-05 | Linde Ag | Process for the separation of oxygenates from a hydrocarbon stream |
| DE60125971T2 (en) * | 2000-10-09 | 2007-10-11 | Sasol Technology (Proprietary) Ltd. | REMOVAL OF OXYGENATES FROM A HYDROCARBON CURRENT |
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- 2004-03-10 AU AU2004220264A patent/AU2004220264A1/en not_active Abandoned
- 2004-03-10 AU AU2004220263A patent/AU2004220263B2/en not_active Expired
- 2004-03-10 WO PCT/IB2004/000656 patent/WO2004080928A2/en active Search and Examination
- 2004-03-10 EA EA200501416A patent/EA007843B1/en not_active IP Right Cessation
- 2004-03-10 CN CNB2004800066821A patent/CN100383096C/en not_active Expired - Lifetime
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452888A (en) * | 2010-10-22 | 2012-05-16 | 中科合成油工程有限公司 | Method for refining 1-hexene from fischer tropsch synthetic oils |
| CN113801077A (en) * | 2021-09-16 | 2021-12-17 | 杭州泽邦科技有限公司 | Method for quickly removing BHT antioxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2004220263A1 (en) | 2004-09-23 |
| EA007843B1 (en) | 2007-02-27 |
| CN100575320C (en) | 2009-12-30 |
| AU2004220263B2 (en) | 2009-08-27 |
| WO2004080928A2 (en) | 2004-09-23 |
| WO2004080928A3 (en) | 2004-11-11 |
| EA200501416A1 (en) | 2006-04-28 |
| CN100383096C (en) | 2008-04-23 |
| CN1759082A (en) | 2006-04-12 |
| EG24947A (en) | 2011-02-13 |
| AU2004220264A1 (en) | 2004-09-23 |
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