WO2004080927A2 - Extraction de composes oxygenes d'un courant d'hydrocarbure - Google Patents
Extraction de composes oxygenes d'un courant d'hydrocarbure Download PDFInfo
- Publication number
- WO2004080927A2 WO2004080927A2 PCT/IB2004/000654 IB2004000654W WO2004080927A2 WO 2004080927 A2 WO2004080927 A2 WO 2004080927A2 IB 2004000654 W IB2004000654 W IB 2004000654W WO 2004080927 A2 WO2004080927 A2 WO 2004080927A2
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- extraction
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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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- 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in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
Definitions
- This invention relates to a process for extracting oxygenates from a hydrocarbon stream.
- Fischer Tropsch feedstock produced results in poor quality Linear Alkyl Benezene due to odour and wetting problems caused by carbonyl i.e. oxygenate content of the Fischer Tropsch feedstock.
- Methods suggested for removing the oxygenates include treating the stocks with hot caustic solution or sodium bisulphite followed by extraction with solvents such as methanol, or treatment with boric acid solution to form esters which can be removed by distillation.
- the preferred method for addressing this problem is by adsorption of carbonyl compounds from the Fischer Tropsch feedstock using activated carbon and silica gel. This process is only feasible for feeds with low oxygenate concentrations. Also, in the example the olefin recovery is less than 25%, i.e. the olefin content is not preserved.
- United Kingdom Patent No. 661 ,916 in the name of Naamlooze Vennootschap De Batafsche Petroleum Maatschappij relates to a method of separating oxygenated compounds from the reaction product of a Fischer-Tropsch reaction by extraction using liquid sulphur dioxide and a paraffinic hydrocarbon flowing in countercurrent to each other.
- This reference provides that the separation of the oxygenated compounds by extraction with a single solvent, such as liquid sulphur dioxide or aqueous methanol has proved difficult and uneconomic in practice.
- This invention relates to a commercially viable process for extracting or separating oxygenates from a hydrocarbon stream containing olefins and paraffins, typically the condensation product of a Fischer-Tropsch reaction, while preserving the olefin content of the stream.
- a commercially viable 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 preferably takes place in an extraction • column using a polar organic solvent, preferably methanol, and water as the solvent, wherein the polar organic solvent and water are added separately to the extraction column.
- a polar organic solvent preferably methanol
- the hydrocarbon stream is fed into the extraction column at, or near, the bottom thereof, a polar organic solvent stream is fed into the extraction column at, or near, the top thereof, and a water stream is fed into the extraction column between the hydrocarbon stream and polar organic solvent stream.
- An extract from the liquid-liquid extraction may be sent to a solvent recovery column from which a tops product comprising polar organic solvent, olefins and paraffins is recycled to the extraction column, thereby enhancing the overall recovery of olefins and paraffins.
- a bottoms product from solvent recovery column may also be recycled to the extraction column.
- a raffinate stream from the extraction column is preferably sent to a stripper column from which a hydrocarbon stream containing more than 90% by weight olefins and paraffins and typically less than 0.2% by weight, preferably less than 0.02% by weight, most preferably less than 0.01% by weight oxygenates exits as a bottoms product.
- the recovery of olefins and paraffins over the oxygenate extraction process is preferably greater than 70%, more preferably greater than 80%, while the olefin/paraffin ratio is at least substantially preserved.
- the solvent preferably has a water content of more than 3% by weight, more preferably a water content of about 5% - 15% by weight.
- the hydrocarbon stream may be the condensation product of a low temperature Fischer-Tropsch reaction carried out at a temperature of 160°C - 280°C, preferably 210°C - 260°C, and a Fischer-Tropsch catalyst, preferably in the presence of a cobalt catalyst to provide a hydrocarbon condensate containing 60 to 80% by weight paraffins and 10 to 30% by weight, typically less than 25% by weight, olefins.
- the olefins so produced have a high degree of linearity of greater than 92%, typically greater than 95%.
- the paraffins so produced have a degree of linearity of greater than 92%.
- the hydrocarbon condensate product is typically fractionated into the C 8 to C- I 6 detergent range, preferably into the C 10 to C ⁇ 3 range prior to extraction.
- the hydrocarbon stream is a fractionated hydrocarbon condensate product from a low temperature Fischer-Tropsch reaction in the C-io to Ci 3 range containing 10 to 30%, typically less than 25%, by weight olefins with a high degree of linearity of greater than 92%, typically greater than 95%, 60% to 80% by weight paraffins and 5% to 15% by weight oxygenates.
- Figure 1 is a graph showing the percent recovery of olefins and paraffins in a solvent recovery column at different solvent to feed ratios for solvents containing methanol and 0, 3 and 5% water;
- Figure 2 is a graph showing the C10/11 olefin and paraffin recovery in a solvent recovery column at different solvent to feed ratios for solvents containing methanol and 0, 3 and 5% water; and
- Figure 3 is a block diagram of a process of the invention for extracting oxygenates from a hydrocarbon stream.
- This invention relates to a process for extracting oxygenates from a hydrocarbon condensate stream from a Fischer-Tropsch reaction.
- the substantially oxygenate-free hydrocarbon stream can be used in the production of linear alkyl benzene.
- synthesis gas carbon monoxide and hydrogen
- a Fischer Tropsch catalyst to produce a mixture of hydrocarbons ranging from methane to waxes and smaller amounts of oxygenates.
- a low temperature Fischer-Tropsch reaction the reaction takes place in a slurry bed reactor or fixed bed reactor, preferably a slurry bed reactor, at a temperature in the range of 160°C - 280°C, preferably 210°C - 260°C, and a pressure in the range of 18-50 bar (gauge), preferably between 20-30 bar (gauge), in the presence of a catalyst.
- the catalyst may include iron, cobalt, nickel or ruthenium. However, a cobalt-based catalyst is preferred for the low temperature reaction. Usually, the cobalt catalyst is supported on an alumina support.
- lighter hydrocarbon vapour phase is separated from a liquid phase comprising heavier liquid hydrocarbon products.
- the heavier liquid hydrocarbon product is the major product of the reaction and may, for example, be hydrocracked to produce diesel and naphtha.
- the lighter hydrocarbon vapour phase which comprises gaseous hydrocarbon products, unreacted synthesis gas and water is condensed to provide a "condensation product" which comprises an aqueous phase and a hydrocarbon condensation product phase.
- the hydrocarbon condensation product includes olefins, paraffins in the C to C- 2 6 range, and oxygenates including alcohols, esters, aldehydes, ketones and acids.
- a hydrocarbon condensation product for a low temperature Fischer-Tropsch reaction contains 10%-30% by weight olefins, " 60%-80% by weight paraffins, and 5%-10% by weight oxygenates. It has, surprisingly, been found that even though this condensation product contains oxygenates and has a low olefin content, it can be used in the production of linear alkyl benzene. However, it is necessary to first extract the oxygenates as these species have a negative effect on the alkylation reaction. There is therefore a need to find a process for extracting oxygenates, but at the same time preserve the olefin concentent.
- the hydrocarbon condensate product is fractionated into a do - C 13 cut which, by way of example, contains 25%) by weight olefins, 68% by weight paraffins and 7% by weight oxygenates.
- the oxygenate content of this C 10 - C 13 cut can be as high as 15%.
- liquid-liquid extraction is a preferred method of oxygenate extraction because, if the correct solvent is selected, the olefin concentent can be preserved.
- the solvent can be any polar material that has partial miscibility with the feed stream 14, such as tri-ethanol amine, tri-ethylene glycol with between zero and 20% water, acetonitrile with between 5% and 20% water, acetol, diols, methanol, or ethanol and water.
- a preferred solvent in a liquid-liquid extraction column is a polar organic solvent and water.
- the polar organic solvent needs to be low-boiling and either preferably non- azeotroping with water, or form an azeotrope with water that has low water content.
- a suitable polar organic solvent is methanol.
- this type of solvent would be added as a mixture at the top of the liquid-liquid extraction column. It has been found that it is possible to obtain a higher recovery of olefins and paraffins, with a lower oxygenate content (i.e. a purer product) by adding the polar organic solvent and the water separately to the liquid- liquid extraction column.
- Another aspect of the invention is that, normally, a high-boiling point solvent is preferred because the solvent recovery steps after extraction require less energy than will be the case for a low-boiling point solvent.
- a mixture of methanol and water which is a low-boiling point solvent, need not suffer from this drawback, because it can be effective at low solvent to feed ratios (this can be lower than 1 if the required oxygenate extraction is not too severe).
- a further aspect of the invention is that is has been found that a water/methanol solvent, preferably with greater than 3% by weight water content in the liquid-liquid extraction column leads to better recovery of desired products in the solvent recovery column than a dry methanol solvent or a water/methanol solvent with less than 3% by weight water in the liquid-liquid extraction column.
- Figure 1 shows that a methanol/water solvent with 5% by weight water provides as much as 80% recovery of olefins and paraffins in the solvent recovery column.
- Figure 2 shows that almost a 100% recovery of C10/C11 olefins and paraffins in the solvent recovery column is possible.
- olefins and paraffins typically 90% of the olefins and paraffins are recovered from the liquid-liquid extraction column.
- the 10% of olefins and paraffins not recovered are sent to the. solvent recovery column in the extract from the liquid-liquid extraction column.
- Up to 60% of the olefins and paraffins in the solvent recovery column are recovered in the overheads product from the solvent recovery column and recycled to the liquid-liquid extraction column. This results in an over-all recovery of olefins and paraffins of more than 90%.
- the olefin/paraffin ratio is also substantially preserved.
- a liquid-liquid extraction process of the invention includes a liquid-liquid extraction column 20.
- the fractionated condensation product of a low temperature Fischer-Tropsch reaction described above 14 is fed into the extraction column 20 at, or near, the bottom thereof.
- the solvent for the extraction column 20 is water and methanol. According to the invention, the water and methanol are added to the extraction column 20 separately. Methanol is added to the extraction column 20 via a methanol stream 21 at, or near, the top of the extraction column 20. Water is added to the extraction column 20 via a water stream 34 located between the hydrocarbon stream 14 and methanol stream 21. The flow of methanol and water is controlled to provide a solvent in the column with more than 5% by weight water.
- the solvent to feed ratio in the extraction column 20 is low, typically less than 1.5.
- the olefin content of the hydrocarbon product (which is intended for use in the production of linear alkyl benzene) has been preserved.
- An extract 26 is drawn from the bottom of the extraction column 20 and is fed to a solvent recovery column 27.
- a tops product 29 from the solvent recovery column 27 comprises over 90% by weight methanol and 2% by weight olefins and paraffins. Up to 60% of the olefins and paraffins from the extract 26 are recovered to the tops product 29. The tops product is then recycled to the solvent stream 21.
- the oxygenate content of the tops product 29 can be as low as 50 ppm, depending on the solvent to feed ratio used in the extraction column 20.
- a bottoms product 28 from the solvent recovery column 27 comprises mainly water, oxygenates and olefins/paraffins. This bottoms product 28 forms two liquid phases that can be decanted in a decanter 30.
- the organic phase is an oxygenate, olefin and paraffin stream 31 , which leaves the process as a product.
- the aqueous phase is a stream 32, which is recycled to the extraction column 20 via the water stream 34.
- the presence of water in the extraction column 20 improves the recovery of paraffins and olefins in the raffinate stream 22. Although it is important for the water to be present in the lower section of the extraction column 20, including the point where the extract 26 is drawn from the extraction column 20, it has been found that it is not necessary for the water to be present throughout the extraction column 20. It has also been found that it is beneficial to have as little water as possible at the top of the extraction column 20 as the presence of water lowers the methanol's ability to take up oxygenates which would result in a higher solvent to feed ratio when compared to dry methanol.
- the extraction column 20 it is beneficial in that it is possible to use a lower solvent to feed ratio than when water is added as a mixture together with methanol. Adding the water separately into the extraction column 20 between the hydrocarbon stream 14 and methanol stream 21 results in an improved paraffin and olefin recovery with better raffinate 22 purity than if the water and methanol were added as a mixture.
- the aqueous phase stream 32 recovered from the decanter 30 is recycled to the water stream 34 into the extractor column 20.
- the stream 32 may contain oxygenates and the addition of this water at a different point to the methanol stream 21 lower down the extraction column 20 ensures that oxygenates are cleaned from the stream in the column, before they can appear in the raffinate stream 22.
- This invention has the added benefit that the solvent recovery column 27 and decanter 30 results in a water-enriched solvent stream 32 that can be fed lower down the extraction column 20.
- the solvent recovery column 27 overheads and raffinate column 23 overheads forms a suitable methanol- enriched solvent stream 21 that can be fed to near the top of the extraction column 20. This is advantageous, since no additional work-up of the solvent is required to produce methanol- and water-enriched solvent streams.
- the purified hydrocarbon feed stream contains 22% by weight olefins, 76% by weight paraffins and less than 0.02% by weight oxygenates. Not only does the extraction process extract oxygenates, it also preserves the olefin content of the hydrocarbon feed.
- the purified hydrocarbon feed stream containing olefins is particularly useful in the production of linear alkyl benzene.
- Example 2 provides an oxygenate content of 0.0094% by weight in the product stream 24, while comparative Example 1 provides an oxygenate content of 0.0145% by weight in the product stream 24.
- Example 2 of the invention provides a more suitable hydrocarbon feed stream for use in the production of linear alkyl benzene, than the product of comparative Example 1.
- Example 2 of the invention also shows a higher overall olefin and paraffin recovery than comparative Example 1.
- Example 3 of the invention is of an oxygenate removal process for a feed stream 14 which has a relatively high oxygenate content, of approximately 13% by weight.
- This example shows a comparative process where the water and methanol are introduced to the extraction column together in the solvent feed stream 21 , and the stream 32 is recycled to the solvent feed stream 21.
- the extraction column 20 was run at a solvent to feed ratio of 1.25 and a temperature of 50°C.
- the overall olefin/paraffin recovery in the stream 24 was 89.9% with a remaining oxygenate content of 0.0145%.
- the olefin/ paraffin ratio in the feed was 1 :3.7 and 1 :3.6 post oxygenate extraction. The olefin/paraffin ratio was therefore substantially preserved.
- This example shows a process according to the invention where the methanol and water are introduced to the extraction column in separate streams 21 and 34 respectively.
- the extraction column 20 was run at a solvent to feed ratio of 1.2 and a temperature of 50°C.
- the overall olefin/paraffin recovery in the stream 24 was 92.3% with a remaining oxygenate content of 0.0094%.
- the olefin/ paraffin ratio in the feed was 1 :3.7 and 1 :3.6 post oxygenate extraction. The olefin/paraffin ratio was therefore substantially preserved.
- Extraction column 20 was run at a solvent to feed ratio of 1.2 and a temperature of 50°C.
- the overall olefin/paraffin recovery in the stream 24 was 92.3% with a remaining oxygenate content of 0.0094%.
- the olefin/ paraffin ratio in the feed was 1 :3.7 and 1 :3.6 post oxygenate extraction. The olefin/paraffin ratio was therefore substantially preserved.
- Extraction column 20 was run at
- This example shows a process according to the invention where the methanol and water are introduced to the extraction column in separate streams 21 and 34 respectively.
- the extraction column 20 was run at a solvent to feed ratio of 2:1 and a temperature of 50°C.
- the overall olefin/paraffin recovery in the stream 24 was 91.4%o. Once again the olefin/paraffin ratio was substantially preserved.
- Extraction column 20
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Abstract
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EA200501389A EA007711B1 (ru) | 2003-03-10 | 2004-03-10 | Экстракция кислородсодержащих веществ из потока углеводородов |
US10/549,766 US7465846B2 (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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US45341803P | 2003-03-10 | 2003-03-10 | |
ZA2003/1937 | 2003-03-10 | ||
ZA200301937 | 2003-03-10 | ||
US60/453,418 | 2003-03-10 | ||
US49685403P | 2003-08-21 | 2003-08-21 | |
ZA2003/6523 | 2003-08-21 | ||
ZA200306523 | 2003-08-21 | ||
US60/496,854 | 2003-08-21 |
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WO2004080927A2 true WO2004080927A2 (fr) | 2004-09-23 |
WO2004080927A3 WO2004080927A3 (fr) | 2004-11-11 |
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PCT/IB2004/000654 WO2004080927A2 (fr) | 2003-03-10 | 2004-03-10 | Extraction de composes oxygenes d'un courant d'hydrocarbure |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1313572C (zh) * | 2005-09-12 | 2007-05-02 | 中国石油天然气股份有限公司 | 低硫低芳铝箔轧制基础油的制备方法 |
WO2023285472A2 (fr) | 2021-07-13 | 2023-01-19 | Indaver Plastics2Chemicals | Procédé de production de fractions purifiées d'une huile de pyrolyse brute liquide à partir de déchets plastiques à base d'hydrocarbures |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
DE19911910A1 (de) * | 1999-03-17 | 2000-09-21 | Linde Ag | Verfahren zur Abtrennung von Oxygenaten aus einem Kohlenwasserstoff-Strom |
WO2002031085A2 (fr) * | 2000-10-09 | 2002-04-18 | Sasol Technology (Pty) Ltd. | Separation de composes oxygenes d'un flux d'hydrocarbures |
-
2004
- 2004-03-10 WO PCT/IB2004/000654 patent/WO2004080927A2/fr active Search and Examination
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
DE19911910A1 (de) * | 1999-03-17 | 2000-09-21 | Linde Ag | Verfahren zur Abtrennung von Oxygenaten aus einem Kohlenwasserstoff-Strom |
WO2002031085A2 (fr) * | 2000-10-09 | 2002-04-18 | Sasol Technology (Pty) Ltd. | Separation de composes oxygenes d'un flux d'hydrocarbures |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1313572C (zh) * | 2005-09-12 | 2007-05-02 | 中国石油天然气股份有限公司 | 低硫低芳铝箔轧制基础油的制备方法 |
WO2023285472A2 (fr) | 2021-07-13 | 2023-01-19 | Indaver Plastics2Chemicals | Procédé de production de fractions purifiées d'une huile de pyrolyse brute liquide à partir de déchets plastiques à base d'hydrocarbures |
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Publication number | Publication date |
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WO2004080927A3 (fr) | 2004-11-11 |
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