• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A continuous process is disclosed for removing mercaptans from highly olefinic feed streams (1) by extraction with a regenerated aqueous alkaline solution (4). The aqueous extract solution is preferably regenerated (13) by oxidation of extracted mercaptans to disulfides. The invention employs an extraction step (6, 7, 8) performed on the aqueous extract solution (5) to limit the passage of olefins or acetylenes into the mercaptan conversion zone (13) and preferably an extraction step (20, 21, 22, 23) performed on the regenerated solution to limit the passage of mercaptans and/or oxygenates into the primary extraction zone (2).
    公开号:SU1634140A3
    申请号:SU864028699
    申请日:1986-12-22
    公开日:1991-03-07
    发明作者:Верачтерт Томас
    申请人:Юоп Инк. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for the purification of hydrocarbons, in which the hydrocarbon feed stream is contacted with an aqueous alkali solution, which extracts the mercaptans from the hydrocarbon feedstock.
    The purpose of the invention is the removal of mercaptans from raw materials while removing diolefin and acetylene
    hydrocarbons from an aqueous alkaline solution.
    The method is carried out as follows.
    g
    The flow of raw materials containing a mixture of C9 and C, .- paraffins, C-olefins and Cf-acetylene hydrocarbons, enters the lower part of the extraction
    ABOUT
    Noah columns. The hydrocarbon stream passes upward through the liquid-liquid extraction plates, rising in countercurrent to the descending stream of aqueous alkaline solution. When passing through the extraction column, the mercaptans, initially present in the feed stream, pass into the descending caustic, thereby removing the mercaptans to a very low residual content in the treated stream withdrawn from the process. The regenerated caustic is introduced onto the top of the extraction column, and the saturated or mercapty-containing caustic is removed from the bottom of the column. Saturated caustic is mixed with a hydrocarbon stream. To ensure close contact between the caustic and the hydrocarbon stream, a mixer is provided before feeding this mixture to the sump. The sump works as a phase separation zone where the less dense hydrocarbon phase is separated from the more dense aqueous alkaline solution. During the period of contact, the concentration of unsaturated hydrocarbons in a saturated caustic solution is greatly reduced. These unsaturated hydrocarbons and a certain amount of mercaptans enter the naphtha stream and form a spent naphtha stream that is withdrawn from the process.
    The aqueous alkaline solution saturated with mercaptans is removed from the second stage of extraction after the phase separation zone and is mixed with air before being fed into the oxidation reactor. A preferred form of mercaptan conversion is a catalytic oxidation reaction. Due to the reaction that takes place in the reactor, the mercaptan compounds in the saturated caustic solution are converted to hydrocarbon-disulfide compounds. The effluent from the oxidation reactor, which is a mixture of some residual oxygen or other vapors, aqueous alkaline solution and cisulfide compounds, is sent to a three-phase separator. In the separator, gases, such as residual oxygen and air ach, are discharged into the atmosphere. Disulfides are relatively unsoluble in aqueous alkaline solution and therefore can be separated.
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    be decanted (settled) and removed from the process.
    A more dense mercaptan-depleted aqueous alkaline solution remains, which is withdrawn from the separator and mixed with the net naphtha stream in the stationary mixer and during the passage of the mixture through the pipeline. This site is a third extraction step for removing disulfides from caustic. The resulting mixture of naphtha and the regenerated caustic solution is sent to a settling tank operating as a separation zone. Due to the correct choice of an appropriate settling time, together with the calm conditions maintained in the settling tank, and with the possible installation of internal coalescing devices in this apparatus, naphtha can be almost completely separated from the aqueous alkaline solution. The result is a regenerated aqueous alkaline solution, which is then sent to the mercaptan extraction column.
    The yafta is mixed with a poor aqueous alkaline solution discharged from the separator to remove residual disulfide compounds from the aqueous alkaline solution. This technique is called naphtha washing to remove return sulfur from the aqueous alkaline solution. The removal of disulfides from caustic in this way prevents the dissolution of disulfides in the purified product stream and thereby reduces the total sulfur content in the product.
    A stream of clean naphtha can pass through a mixing-settling stage designed to remove disulfide compounds from a poor caustic solution, and then go through a mixing-drying stage sequentially designed to extract unsaturated hydrocarbons from a saturated caustic soda. Therefore, the same hydrocarbon stream is used in both extraction steps. However, different hydrocarbon streams may be used at each extraction step. This may occur depending on factors such as the availability of certain hydrocarbons and the methods chosen for their treatment or discharge. The composition of the hydrocarbon stream (s),
    used in the extraction steps should be determined by a number of factors, such as the availability of hydrocarbon streams at the location of the process, the availability of means for treating hydrocarbon streams contaminated with disulfides and / or mercaptan compounds, and the desirability of using various hydrocarbon distillates .
    For use as a flush hydrocarbon stream, preference should be given to a hydrocarbon stream or a mixture of hydrocarbons with a higher average molecular weight than that of the feed stream being treated. Thus, substances selected from a wide variety of hydrocarbons, including Cj hydrocarbons, mixtures and C4 hydrocarbons, fractions of naphtha, and various hydrocarbons can be used as hydrocarbon streams that can be used in the second and third stages of extraction. mixtures of intermediate hydrocarbons.
    i
    In this extraction process, any alkaline reagent capable of extracting mercaptans under given operating conditions can be used and which can be regenerated by the proposed method. A preferred alkaline reagent is an aqueous solution of an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide. Sodium hydroxide (caustic) can be used in concentrations of 1-50 wt.% With a preferred concentration range of about 5-25 wt.%. Optionally, a substance may be added to increase the solubility of the mercaptans in solution, usually methanol or ethanol, although other substances, such as phenol, cresol or butyric acid, may be used.
    The conditions in the first extraction zone can vary significantly depending on such factors as the nature of the hydrocarbon stream being treated and the content of mercaptans in it, etc. Usually, the extraction of mercatells can be carried out at an ambient temperature above 15.6 ° C and under sufficient pressure to ensure stable operation with
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    liquid phases. If the raw material stream consists of a very light material, then this can be impossible to achieve, and then the extraction is carried out from the vapor-phase stream of the raw material. The pressure can vary from atmospheric to 6395 kPa or higher, with a preferred pressure in the range of 1000 to 2400 kPa.
    The temperature in the mercaptan extraction zone is limited to 10 -. 121 C, preferably 27 to 49 ° C. The ratio of the volume of the alkaline solution to the volume of the feed stream depends on the content of mercaptans in the raw material. Typically, this ratio is between 0.01: 1 and 1: 1, although other ratios may be used. The alkali solution consumption is typically about 1 to 3% of the flow rate of LPG (liquid petroleum gas) and can be up to 20% of the straight run light naphtha flow.
    The extraction zone is a vertical plate column, and the plate has a large number of round holes. Optimum extraction in this fluid system is achieved at speeds in the holes of about 1.5-3 m / s. Packed columns and other types of extraction equipment can be used if necessary. The preferred type of contact devices are fiber-film contact systems. Virtually all extractable mercaptans must pass into the alkaline solution from the feed stream (at least 85%, and preferably 95% of the total material available).
    The operation of the extraction zone leads to the formation of mercaptans or an enriched stream of caustic. This stream is mixed with a stream of air supplied in such an amount that it at least provides the stoichiometric amount of oxygen required to oxidize the mercaptans in the alkali stream. Air or another oxidizing agent mixes well with the alkaline liquid stream and this mixture is then sent to the oxidation zone. The oxidation of mercaptans is accelerated by the presence of a catalytically effective amount of oxidation catalyst capable of operating under conditions maintained in the oxidation zone. The preferred catalyst is metal phthalocyanine, e.g. cobalt phthalocyanine or vanadium phthalocynine, etc. Higher catalytic activity can be obtained by using a polar derivative of the metal phthalocyanine, in particular monosulfur, disulfophenes, trisulfonos and tetrasulfur derivatives.
    Oxidation catalysts can be applied in the form of a solution or suspension in an alkaline solution or can be applied to a solid carrier. If the catalyst is in solution, then it must be phthalocyanine cobalt or vanadium disulfonate at a concentration of about 5 to 1000 (5 - - 1000 x.%). Carriers must be well absorbed and stable in an alkaline environment. Activated carbons are suitable for this purpose, and coals of animal and vegetable origin can be used. The carrier is suspended in the form of a fixed layer, which ensures effective circulation of the alkaline solution. The metal phthalocyanine compound contains approximately O, 1 - 2.00 wt.% Of the final composition.
    The oxidation is carried out under pressure from atmospheric to 6395 kPa, this pressure is almost the same as in the subsequent zone of disulfide-caustic phase separation. Usually the pressure does not exceed 500 KPa. The temperature can vary from room temperature to 95 ° C when operating at atmospheric pressure and up to 205 ° C when operating at a pressure above atmospheric. Preferably, the temperature is in the range of 33 to 80 ° C. In the oxidation zone there is a layer of packing to ensure thorough mixing. This is the case in all cases, completely and when the catalyst is circulated with an alkaline solution.
    The phase separation zone can be of any shape, and a zone with a sump is preferred. It is desirable to maintain a minimum pressure in the phase separation zone. In this case, the transition of excess oxygen, nitrogen and water to the vapor phase is accelerated. The pressure in the phase separation zone can vary from atmospheric to 2063 kPa or higher, but a pressure in the range of 65 to 300 kPa is optimum.
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    m lny. The temperature in this zone is limited to 10–120 ° C, and preferably 26–54 ° C. The dimensions of the phase separation zone are such that a more dense alkaline solution is separated from disulfide compounds by gravity. This can be achieved by placing coalescing devices in this zone.
    Equipment used to extract compounds from the caustic stream, i.e. in the second and third extraction zones, it can also be different. The equipment includes a fixed mixer to provide a continuous mixing of the hydrocarbon stream with the caustic stream. After this mixing stage, the two liquid phases are separated in a sump. Such a contacting-separation process may be performed in a number of different types of equipment, including various single-stage and multi-stage equipment. Thus, packed columns or tray-type extraction columns can be used to extract the mercaptans. The two liquid phases can also be brought into contact with mechanical agitators or mixers.
    Example 1. A feedstock is processed without high concentrations of diolefin and acetylene hydrocarbons. Raw material contains, mol.%: Paraffins. 14.5; olefins 10.5; diolefins 38.6; acetylene hydrocarbons 36.4.
    This feed stream contains about 300 ppm weight. mercaptan sulfur and is processed by countercurrent contacting in a plate extraction column according to the previously described method. The obtained enriched caustic contains about 4200 (0.42 wt.%) Mercaptan sulfur and about 1.0% by volume of dissolved reactive acetylene-rich hydrocarbons. The rich caustic enters the second contactor, where it contacts a clean stream containing 50% by volume of butane-butylenes. The content of hydrocarbons in the enriched caustic decreases to 0.1% by volume, mainly from butanes and butylenes from the washing hydrocarbon stream, and the content
    the mercaptan sulfur in the caustic decreases to 0.39% by weight. The Cd-hydrocarbon stream receives about 0.008% by weight of mercaptan sulfur and 2 mol.% Of hydrocarbons enriched with high olefin acetylenes. The resulting carbon wash stream containing 400 (0.04 wt.%) Disulfide sulfur and 2% by volume of dienes and acetylenes is then sent to the appropriate storage devices for the product or returned back to the point before the fractionation plant for recovery.
    The enriched caustic, which is practically free of dienes and acetylenes, but carrying some hydrocarbons such as butane and butylene, in an amount of 0.1% by volume, 2, is sent to the oxidative regeneration section. The regenerated caustic that is withdrawn from this conversion zone is treated in the third contactor with a sweet hydrocarbon stream containing 50% by volume of butanbutylene. The content of extracted sulfur in the regenerated or depleted caustic stream decreases to trace amounts, while the content of disulfide sulfur in the hydrocarbon stream increases. The caustic stream then enters the extraction section of the mercaptans, and the hydrocarbon stream is then used in the third extraction zone to remove acetylenic hydrocarbons.
    PRI mme R 2. Data were obtained in the first and second stages of extraction in a pilot processing plant. The feed for the plant consists of highly-substituted lightweight products of a catalytic cracking process with a weighted catalyst. The composition of the hydrocarbon feedstock for the first extraction column is as follows, mol%: paraffins C.-C. 45.6; olefins Cj-C. 27.2; diolefins 20.9; acetylene hydrocarbons 6.3.
    The feed rate of the hydrocarbons in the first extraction column is 9.9. The hydrocarbon stream contains 230 million mercaptan sulfur. Hydrocarbons in contact in countercurrent with 0.28 m / h of a weak solution of caustic soda (alkaline). The extracted hydrocarbon stream has a content of 40 million soda mercaptan, while about
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    The thickened alkaline solution has a mercaptan content of approximately 6,700 million. In addition, enriched caustic soda contains 0.68% by volume of rich reactive acetylene hydrocarbons.
    The enriched caustic soda is contacted with a 0.15 m2 / h stream of sweet hydrocarbons containing butanes and butylenes in a second extraction stage. 3, as a result of the second extraction stage, the hydrocarbon content in the enriched alkaline solution is reduced to less than 0.07% by volume and contains mainly butane and butylenes from the extraction stream of hydrocarbons. The alkaline solution is then oxidized and further processed as described.
    Thus, the proposed method allows the removal of not only mercaptans with a sufficiently high degree of efficiency, but also diolefins and acetylenes. i
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A continuous purification process for mercaptan-containing hydrocarbon feedstock containing Cj-C paraffinic and unsaturated hydrocarbons, including contacting the feedstock with an aqueous alkaline solution in the first extraction zone to produce a split hydrocarbon product and an aqueous alkaline solution enriched with hydrocarbons and alkaline solution to the oxidation zone mercaptan in the presence of a fixed layer of phthalocyanine cobalt to produce a stream containing sulfur compounds and water an aqueous solution, separation of sulfur compounds contained in this stream from an aqueous alkaline solution by separation and feeding the latter into the first extraction zone, characterized in that, in order to remove mercaptans from the raw material while simultaneously removing diolefinic and acetylene hydrocarbons from the aqueous alkaline solution, hydrocarbons containing 27.2-75 mol.% of diolefins and acetylene hydrocarbons, 14.5-45.6 mol.% of paraffins and 10.5-27.2 mol.% of olefinic hydrocarbons, and process lead
    I1634140 2
    with the supply of an aqueous alkaline solution stream containing butane
    after the first extraction zone and butylene, with separation from water
    into the second extraction zone, in a co-alkaline solution of diolefinic and
     the second is brought into contact with carbon-acetylene hydrocarbons.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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