AU2004220263B2 - Extraction of oxygenates from a hydrocarbon stream - Google Patents
Extraction of oxygenates from a hydrocarbon stream Download PDFInfo
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- AU2004220263B2 AU2004220263B2 AU2004220263A AU2004220263A AU2004220263B2 AU 2004220263 B2 AU2004220263 B2 AU 2004220263B2 AU 2004220263 A AU2004220263 A AU 2004220263A AU 2004220263 A AU2004220263 A AU 2004220263A AU 2004220263 B2 AU2004220263 B2 AU 2004220263B2
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- 238000000605 extraction Methods 0.000 title claims description 71
- 229930195733 hydrocarbon Natural products 0.000 title claims description 56
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 56
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 153
- 239000002904 solvent Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 150000001336 alkenes Chemical class 0.000 claims description 61
- 238000011084 recovery Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 24
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 18
- 238000000638 solvent extraction Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012188 paraffin wax Substances 0.000 claims description 15
- 239000007859 condensation product Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000004996 alkyl benzenes Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
WO 2004/080927 PCT/IB2004/000654 EXTRACTION OF OXYGENATES FROM A HYDROCARBON STREAM BACKGROUND OF THE INVENTION This invention relates to a process for extracting oxygenates from a hydrocarbon stream. Many processes for extracting oxygenates from hydrocarbon streams are known. Such extraction methods include hydrogenation, azeotropic distillation, extractive distillation, vapour phase dehydration, liquid phase dehydration and liquid-liquid extraction.
WO 2004/080927 PCT/IB2004/000654 -2 United Kingdom Patent No. 669,313 in the name of California Research Corporation. discloses the use of a hydrocarbon condensate from the Fischer-Tropsch process as a feedstock in the production of alkyl benzene. This reference is limited to the use of "high temperature" Fischer-Tropsch processes wherein the Fischer-Tropsch reaction is carried out temperatures of approximately 300"C and higher, for the production of the hydrocarbon condensate. This reference states that 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.
SUMMARY OF THE INVENTION According to the invention there is provided a commercially viable process for extracting oxygenatesi from a hydrocarbon stream, typically a fraction of the condensation produce 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 e.n extraction column using methanol and water as the solvent, wherein the methanol and-water are added separately to the extraction column. The hydrocarbon stream "s fed into the extraction column at, or near, the bottom thereof, a methanol 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 methanol stream. An extract from the liqu:d-liquid extraction may be sent to a solvent recovery column from wnich 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 theextraction column is preferably sent to a stripper column from which a hydrocarbon stream containing more than 90% by weight olefins and paraff ins 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 preserve.
WO 2004/080927 PCT/IB2004/000654 -4 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 1600C - 2800C, preferably 2100C - 2600C, 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 to C16 detergent range, preferably into the C10 to C13 range prior to extraction. Typically, the hydrocarbon stream is a fractionated hydrocarbon condensate product from a low temperature Fischer-Tropsch reaction in the C10 to C13 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. BRIEF DESCRIPTION OF THE DRAWING 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 WO 2004/080927 PCT/IB2004/000654 -5 Figure 3 is a block diagram of a process of the invention for extracting oxygenates from a hydrocarbon stream. DESCRIPTION OF PREFERRED EMBODIMENTS 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. In the Fischer-Tropsch process, synthesis gas (carbon monoxide and hydrogen) obtained either from the gasification of coal or the reforming of natural gas, is reacted over a Fischer Tropsch catalyst to produce a mixture of hydrocarbons ranging from methane to waxes and smaller amounts of oxygenates. In 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 1600C - 2800C, preferably 210*C - 2600C, 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. During the low temperature Fischer-Tropsch reaction, a lighter hydrocarbon vapour phase is separated from a liquid phase comprising heavier liquid hydrocarbon products. The heavier liquid hydrocarbon product (waxy products) 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 WO 2004/080927 PCT/IB2004/000654 6 provide a "condensation product" which comprises an aqueous phase and a hydrocarbon condensation product phase. The hydrocarbon condensation product includes olefins, paraffins in the C4 to C26 range, and oxygenates including alcohols, esters, aldehydes, ketones and acids. Typically, 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. For the production of linear alkyl benzene, the hydrocarbon condensate product is fractionated into a CO - C13 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 CI - C13 cut can be as high as 15%. In the prior art, many methods of extracting oxygenates from hydrocarbon streams are suggested. Such removal methods include hydrogenation, azeotropic distillation, extractive distillation, vapour phase dehydration, liquid phase dehydration and liquid-liquid extraction. It has been found that liquid-liquid extraction is a preferred method of oxygenate extraction because, if the correct solvent is selected, the olefin concentent can be preserved. In liquid-liquid extraction, 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.
WO 2004/080927 PCT/IB2004/000654 -7 According to the invention, a preferred solvent in a liquid-liquid extraction column is a polar organic solvent and water. To be useful in this invention, 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. Usually, 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. However, it has been found that 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 I if the required oxygenate extraction is not too severe). Furthermore, one would not expect to be able to use methanol and water as a solvent in a liquid liquid extraction column to extract oxygenates from the abovementioned hydrocarbon condensate because a study of the different azeotropes with water that exist in the hydrocarbon condensate would lead one to expect that it would not be possible to distil water in a solvent -recovery column without azeotroping oxygenates overhead as well. Surprisingly, this turns out not to be the case. Thus, 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. This is shown in Figure 1, from which it can be seen that a methanol/water solvent with 5% by weight water provides as much as 80% recovery of olefins and paraffins in the solvent WO 2004/080927 PCT/IB2004/000654 - 8 recovery column. Figure 2 shows that almost a 100% recovery of C10/C11 olefins and paraffins in the solvent recovery column is possible. Thus, according to the invention, 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. With reference Figure 3, 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. Raffinate 22 from the top of the extraction column 20, which includes olefins and paraffins and a small amount of solvent, enters a raffinate stripper column 23 and a hydrocarbon product stream comprising more than 90% by weight olefins and paraffins and less than 0.01% by weight oxygenates exits as a bottoms product 24. The bottoms product 24, which shows an overall recovery of over 90% of the olefins and paraffins, contains more than 20% by weight a-olefins and more than 70% by weight n- WO 2004/080927 PCT/IB2004/000654 -9 paraffins. Thus, the olefin content of the hydrocarbon product (which is intended for use in the production of linear alkyl benzene) has been preserved. A solvent comprising mainly methanol (more than 90% by weight) and low concentrations of water (less than 5% by weight) and olefins/paraffins (less than 5% by weight) exits as a tops product 25 and is returned to the solvent feed stream 21. If it is desired to recover the bottoms product 24 as a vapour stream, this can be done by taking a bottoms vapour stream from the column 20. The liquid product from the column~20 will then be a very small effluent stream. 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 WO 2004/080927 PCT/IB2004/000654 - 10 compared to dry methanol. Thus, if as little water as possible is present in the upper section of 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. As mentioned above, 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. When operating a solvent recovery column 27 in the manner described above, it is to be expected that certain species may become trapped in the column. These species will tend to build up and in the process cause unstable operation of the solvent recovery column. Such species would typically be heavier olefins and paraffins or lighter oxygenates in the present case. Operating the solvent recovery column with a small side draw may prevent the build up of such species and thereby result in much improved operability of the system. After passing the CIO - C13 hydrocarbon feed stream mentioned above through the abovementioned oxygenate extraction process using a mixture WO 2004/080927 PCT/IB2004/000654 -11 of methanol (95% by weight) and water (5% by weight) and a solvent to feed ratio of 1.25, 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. .With reference to Comparative Example I and Examples 2 and 3 of the invention below, it is evident that the process of the invention where the water and methanol are added separately leads to a lower oxygenate content in the product stream 24. 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. Thus the product of 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. The invention will now be described in more detail with reference to the following non-limiting Examples 2 and 3 and comparative Example 1. Comparative Examplel 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 500C. The overall olefin/paraffin recovery in the stream 24 was 89.9% with a remaining oxygenate content of 0.0145%. The olefin/ WO 2004/080927 PCT/IB2004/000654 - 12 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 14 21 22 26 Stream Flow Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Cmp (wt%) (ka/hr) Total 100 3000 100 3750 100 2530 100 4220 Total C1O-C13 P/O 92.7 2779.7 2.16 81.0 99.1 2507.9 6.20 261.7 Total Oxygenates 7.3 217.7 0.000 0.000 0.0144 0.365 5.78 243.7 Lights and -eavies 0.057 1.7 0.004 0.144 .0.01~04 0.263 0.00480 . 0.202 Water 0.031 0.934 6.01 225.6 0.0073 0.184 5.74 242.4 Methanol 0.000 0.000 91.7 3443.3 0.842 21.31 82.3 3472.0 Raffinate Stripper column 23 22 25 24 Stream Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Total 100 2530 100 30 100 2500 Total C10-C13 P/O 99.1 2507.9 2.63 0.793 99.97 2499.4 Total Oxygenates 0.0144 0.365 0.00163 0.000491 0.0145 0.363 Lights 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 Methanol 0.842 21.31 95.4 28.7 0.000 0.000 Solvent Recovery column 27 26 29 28 Stream Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Total 100 4220 100 3584 100 636 Total C1O-C13 P/O 6.20 261.7 2.37 85.1 27.6 175.81 Total Oxygenates 5.78 243.7 0.00140 0.0503 42.0 267.0 Lights 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 Methanol 82.3 3472.0 96.2 3451.9 1.04 6.63 Example 2 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.
WO 2004/080927 PCT/IB2004/000654 - 13 Extraction column 20 14 34 21 22 26 Stream Comp Flow Comp Flow Comp Flow Comp Flow Comp Flow (kg/hr) (wt%) (kg/hr) (wt%) (kg/hr) (wt%) (kg/hr) (wt%) (kg/hr) (wt%) Total 100 3000 100 179 100 3334 100 2599 100 3914 Total C1O-C13 P/O 92.6 2778.8 0.000 0.000 2.11 70.3 99.0 2572.1 7.89 308.8 Total Oxygenates 7.34 220.3 0.000 0.000 0.000 0.000 0.00937 0.244 6.00 234.9 Lights and Heavies 0.0156 0.470 0.000 0.000 0.009 0.298 0.00292 0.0758 0.00813 0.318 Water 0.0164 0.492 94.9 169.9 0.29 9.7 0.00270 0.0702 4.89 191.4 Methanol 0.000 0.000 5.07 9.07 97.6 3253.7 1.02 26.5 81.2 3178.6 Raffinate stripper column 23 22 25 24 Stream Comp Flow Comp Flow Comp Flow (wt%) l(kg/hr) (wt%) (kg/hr) (wt%) (kg/hr) Total 100 2599 100 33 100 2566 Total C10-C13 P/O 99,0 2572.1 2.01 0.663 99.98 2565.733 Total Oxygenates 0.00937 0.244 0.00647 0.00213 0.0094 0.24122 Lights and Heavies 0.00292 0.0758 0.0708 0.0234 0.000488 0.0125 Water 0.00270 0.0702 0.210 0.0693 0.000500 0.0128 Methanol 1.02 26.5 97.7 32.2 0.000 0.0 Solvent Recovery column 27 26 29 28 Stream Comp Flow Comp Flow Comp Flow (wt%) (kg/hr) (wt%) (kg/hr) (wt%) (kg/hr) Total 100 3914 100 3171 100 743 Total C10-C13 PlO 7.89 308.8 2.01 63.8 34.8 258.4 Total Oxygenates 6.00 234.9 0.00335 0.1 32.9 244.8 Lights and Heavies 0.00813 0.318 0.00237 0.075 0.00869 0.0646 Water 4.89 191.4 0.22 7.0 28.7 213.6 Methanol 81.2 3178.6 97.8 3100.0 3.51 26.09 Example 3 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 500C. The overall olefin/paraffin recovery in the stream 24 was 91.4%. Once again the olefin/paraffin ratio was substantially preserved.
WO 2004/080927 PCT/IB2004/000654 - 14 Extraction column 20 Stem14 32 21 22 26 Stream 1Flow Flow Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Total 100 3000 100 600 100 5400 100 2413 100 6587 Total C1O-C13 P/O 86.9 2606.9 0.000 0.001 6.57 355.0 98.8 2383.2 8.79 578.7 Total Oxygenates 12.91 387.4 0.082 0.489 0.000 0.000 0.00848 0.205 5.89 387.7 Lights and Heavies 0.1913 5.739 0.000 0.000 0.000 0.013 0.20636 4.9799 0.01173 0.773 Water 0.0000 0.000 99.9 599.5 1.96 105.8 0.00316 0.0762 10.71 705.2 Methanol 0.000 0.000 ~ 0.01 0.04 91.5 4939.2 1.03 24.8 74.6 4914.5 Raffinate Stripper column 23 22 25 24 Stream Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Total 100 2413 100 26 100 2387 Total C1O-C13 P/O 98.8 2383.2 3.92 1.012 99.78 2382.148 Total Oxygenates 0.00848 0.205 0.00063 0.00016 0.0086 0.20468 Lights and Heavies 0.206 4.9799 0.0006 0.0002 0.209 4.9797 Water 0.00316 0.0762 0.294 0.0761 0.000007 0.0002 Methanol 1.03 24.8 95.8 24.7 0.001 0.0 Solvent Recovery column 27 Stem26 25 29 28 Stream 2Flow Flow Flow Flow Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Comp (wt%) (kg/hr) Total 100 6587 100 26 100 5400 100 1213 Total C1O-C13 P/O 8.79 578.7 3.92 1.012 6.57 355.0 18.5 224.7 Total Oxygenates 5.89 387.7 0.00063 0.00016 0.00000 0.0 32.0 387.7 Lights and Heavies 0.01173 0.773 0.0006 0.0002 0.00025 0.014 0.06260 0.7592 Water 10.71 705.2 0.294 0.0761 1.96 105.8 49.4 599.5 Methanol 74.6 4914.5 95.8 24.7 91.5 4939.1 0.00 0.05
Claims (18)
1. A process of extracting oxygenates from a hydrocarbon stream using an extraction solvent comprising methanol and water, wherein the methanol anc water are added separately in the extraction process.
2. The process according to claim 1, wherein the hydrocarbon stream is the fractionated -. hydrocarbon condensation product of a Fischer Tropsch reaction.
3. The process according to claim 2, wherein the hydrocarbon stream is the fractionated hydrocarbon condensation product of a low temperature Fischer-Tropsch reaction.
4. . The process according to claim 3, wherein, prior to extraction, the hydrocarbon condensation product contains 15% to 30% by weight olefins and 5% to 15% by weight oxygenates.
5. The process according to claim 1, wherein the liquid-liquid extraction takes place in a liquid extraction column and the methanol and water are added separately to the column.
6. The process according to claim 5, wherein the hydrocarbon stream is fed into the extraction column at, or near, the bottom thereof, a methanol 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 methanol stream.
7. The process according to claim 6, wherein a raffinate from the extraction column is- sent to a raffinate stripper column from which a hydrocarbon feed stream containing olefins and paraffins and less than 0.2% by weight oxygenates exits as a bottoms product, -16
8. The process according to claim 7, wherein a raffinate from the extraction column is sent to a raffinate stripper column from which a hydrocarbon feed stream containing olefins and paraffins and less than 0.02% by weight oxygenates exits as a bottoms product.
9. The process according to claim 8, wherein a raffinate from the extraction column i:; sent to a raffinate stripper column from which a hydrocarbon feed stream containing olefins and paraffins and less than 0.1 % by weight oxygenates exits as a bottoms product.
10. The process according to claim 1, wherein an extract from the liquid-liquid extraction is sent to a solvent recovery column from which a tops product comprising methanol, olefins and paraffins is recycled to the extraction step, thereby enhancing the overall recovery of olefins and paraffins.
11. The process according to claim 10, wherein the aqueous phase of a bottoms product from the solvent recovery column is recycled to the extraction step.
12. The process accorc ing to claim 11. wherein the extraction solvent has a water content-of more than 3% by weight.
13. The process according to claim 12, wherein the extraction solvent has a water content .f about 5% - 15% by weight.
14. The process accor-Jing to claim 12 or claim 13, wherein the hydrocarbon stream is fractioned in the Ca to C 1 5 range.
15. The process according to claim 14, wherein the hydrocarbon stream is fractionated in the C to C13 range. 009 06.05.2005 1
16. The process according to any one of the preceding claims, wherein the recovery of olefins and paraffins over the oxygenate extraction process is greater :han 70%.
17. The process according to clairn 16, wherein the recovery of blefins and paraffins over the oxygenate extraction process is greater than 80%.
18. The process according to any one of the preceding claims, wherein the olefin/paraffin~ ratio in the hydrocarbon stream over the oxygenate extraction process is substantially preserved.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US45341803P | 2003-03-10 | 2003-03-10 | |
| US60/453,418 | 2003-03-10 | ||
| ZA200301937 | 2003-03-10 | ||
| ZA2003/1937 | 2003-03-10 | ||
| US49681603P | 2003-08-21 | 2003-08-21 | |
| US60/496,854 | 2003-08-21 | ||
| ZA2003/6523 | 2003-08-21 | ||
| ZA200306524 | 2003-08-21 | ||
| PCT/IB2004/000656 WO2004080928A2 (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
Publications (2)
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| AU2004220263A1 AU2004220263A1 (en) | 2004-09-23 |
| AU2004220263B2 true AU2004220263B2 (en) | 2009-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| AU2004220263A Expired AU2004220263B2 (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
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| Application Number | Title | Priority Date | Filing Date |
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| AU2004220264A Abandoned AU2004220264A1 (en) | 2003-03-10 | 2004-03-10 | Extraction of oxygenates from a hydrocarbon stream |
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| CN (2) | CN100383096C (en) |
| AU (2) | AU2004220264A1 (en) |
| EA (1) | EA007843B1 (en) |
| EG (1) | EG24947A (en) |
| WO (1) | WO2004080928A2 (en) |
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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 | Low sulfur, low arene aluminum board hammering base oil preparation method |
| EP2490692B1 (en) | 2009-10-21 | 2016-11-16 | Merck Sharp & Dohme Corp. | Quinolinone-pyrazolone m1 receptor positive allosteric modulators |
| 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 |
| 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 |
| CN113801077B (en) * | 2021-09-16 | 2023-04-21 | 杭州泽邦科技有限公司 | Method for rapidly removing BHT antioxidant |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| AU9408101A (en) * | 2000-10-09 | 2002-04-22 | Sasol Tech Pty Ltd | Separation of oxygenates from a hydrocarbon stream |
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- 2004-03-10 AU AU2004220264A patent/AU2004220264A1/en not_active Abandoned
- 2004-03-10 EA EA200501416A patent/EA007843B1/en not_active IP Right Cessation
- 2004-03-10 WO PCT/IB2004/000656 patent/WO2004080928A2/en active Search and Examination
- 2004-03-10 AU AU2004220263A patent/AU2004220263B2/en not_active Expired
- 2004-03-10 CN CNB2004800066821A patent/CN100383096C/en not_active Expired - Lifetime
- 2004-03-10 CN CN200480006726A patent/CN100575320C/en not_active Expired - Fee Related
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| AU2004220263A1 (en) | 2004-09-23 |
| AU2004220264A1 (en) | 2004-09-23 |
| EA200501416A1 (en) | 2006-04-28 |
| CN100575320C (en) | 2009-12-30 |
| WO2004080928A2 (en) | 2004-09-23 |
| CN1764619A (en) | 2006-04-26 |
| CN1759082A (en) | 2006-04-12 |
| EA007843B1 (en) | 2007-02-27 |
| EG24947A (en) | 2011-02-13 |
| WO2004080928A3 (en) | 2004-11-11 |
| CN100383096C (en) | 2008-04-23 |
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