WO2017000516A1 - 烷基化产物脱硫脱酸的方法与装置 - Google Patents

烷基化产物脱硫脱酸的方法与装置 Download PDF

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WO2017000516A1
WO2017000516A1 PCT/CN2015/098011 CN2015098011W WO2017000516A1 WO 2017000516 A1 WO2017000516 A1 WO 2017000516A1 CN 2015098011 W CN2015098011 W CN 2015098011W WO 2017000516 A1 WO2017000516 A1 WO 2017000516A1
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sulfuric acid
acid
pickling
separation
hydrocarbon separation
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English (en)
French (fr)
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白志山
乔伟
庞富龙
杨晓勇
王炳捷
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • 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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only

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  • the present invention relates to the field of corrosion of organic sulfur compounds and free sulfuric acid carried in alkylation products to subsequent equipment, and relates to a method and apparatus for removing organic sulfur compounds (such as sulfates) and free sulfuric acid from alkylation products. .
  • alkylation is a well-known process for the preparation of higher octane paraffins of paraffins, usually isoparaffins and olefins in the presence of strong acids.
  • the alkylation process needs to be carried out in a strong acid environment.
  • sulfuric acid is used as a catalyst. Sulfuric acid is often stirred into fine droplets or emulsions, which increases the difficulty of sedimentation separation.
  • the alkylation effluent must be carried out in a subsequent process. Separation of acid hydrocarbons, otherwise these strong acids entering the subsequent process can cause severe corrosion of the equipment.
  • Methods for separating acid hydrocarbons include physical methods, physical chemical methods, and chemical methods.
  • Chinese patent application CN102021016A discloses a method for removing acid in an alkylation reaction product by using a modified ceramic membrane module, which can achieve acid content of less than 100 mg/L in oil, followed by washing with alkali water to achieve acid removal.
  • Chinese patent application CN1803739A discloses a defogging container containing a poly-material which is adsorbed by a wet poly-material to remove sulfuric acid and sulfate in the alkylation product.
  • Chinese patent application CN1688524A discloses a process for removing sulfuric acid from an alkylation product by a mechanical agglomerator and then adding a catalyst to remove the sulfonate and sulfonate in the product in the next stage of the process.
  • the present invention provides a novel method and apparatus for desulfurization and deacidification of alkylated products, thereby solving the problems in the prior art.
  • the technical problem to be solved by the present invention is that the organic sulfur compound and free sulfuric acid carried in the alkylation product corrode the subsequent equipment.
  • the invention provides a method of desulfurization and deacidification of an alkylated product, the method comprising the steps of:
  • a separation screen filler as a light phase alkylation product entering the upper portion of the pickling separation tank, wherein more than 95% of the sulfuric acid in the light phase alkylation product is aggregated and separated on the separation screen filler Obtaining an alkylation product having a sulfuric acid content of about 0.01% to 1.0%; and separating and separating the sulfuric acid to the bottom of the pickling separation tank;
  • the obtained alkylated product having a sulfuric acid content of less than 10 mg/kg is sent to an adsorption apparatus to adsorb residual sulfuric acid having a content of less than 10 mg/kg to obtain an alkylated product from which sulfate and sulfuric acid are removed.
  • the step (a) further comprises: feeding the liquid alkylate containing sulfuric acid and sulfate and the new sulfuric acid into the pickling tank in a countercurrent or cross-flow manner. Previously, it was thoroughly mixed in the mixer.
  • the acid hydrocarbon separation section is a two-stage acid hydrocarbon separation device gradient arrangement, and the alkylation product obtained by the crude separation of the primary acid hydrocarbon separation unit is directly sent to Secondary acid
  • the hydrocarbon separation unit performs fine separation.
  • the obtained alkylation product having a sulfuric acid content of less than 10 mg/kg is sent to an adsorption device equipped with a bed of exchanged adsorption resin to have a low remaining amount of adsorption.
  • the sulfuric acid concentration was lowered to less than 1 mg/kg.
  • the present invention provides an apparatus for desulfurization and deacidification of an alkylated product, the apparatus comprising:
  • a pickling separation tank for pickling, agglomerating, and separating a liquid sulfuric acid and sulfate-containing alkylation product and a new sulfuric acid material fed therein;
  • the pickled wire mesh filler in the lower part of the pickling separation tank is used for making the sulfate ester and the fresh sulfuric acid sufficiently contact and mutually extracting and extracting, and simultaneously collecting and separating;
  • the separation screen filler in the upper part of the pickling separation tank is used to collect and separate more than 95% of the sulfuric acid in the alkylation product after the pickled screen filler (2), thereby obtaining a sulfuric acid content of about 0.01% to 1.0. % alkylation product;
  • An acid hydrocarbon separation section connected to the pickling separation tank, wherein the acid hydrocarbon separation section is a single-stage or multi-stage acid hydrocarbon separation unit for alkylation of the sulfuric acid content of about 0.01% to 1.0%.
  • the sulfuric acid entrained in the product is subjected to crude separation and fine separation to obtain an alkylation product having a sulfuric acid content of less than 10 mg/kg;
  • An adsorption device connected to the acid hydrocarbon separation section for adsorbing residual sulfuric acid having a content of less than 10 mg/kg to obtain an alkylated product from which sulfate and sulfuric acid are removed.
  • the apparatus further comprises: a mixer connected to the pickling separation tank for separating the liquid alkylate containing sulfuric acid and sulfate and the new sulfuric acid into the pickling separation Mix well before the can.
  • the acid hydrocarbon separation section is a two-stage acid hydrocarbon separation unit gradient arrangement, and the alkylation product obtained by the crude separation of the primary acid hydrocarbon separation unit is directly sent to the secondary acid hydrocarbon connected thereto.
  • the separation device performs fine separation.
  • the adsorption unit is provided with a bed of exchange adsorbent resin for adsorbing residual sulfuric acid having a content of less than 10 mg/kg to reduce the sulfuric acid concentration to less than 1 mg/kg.
  • the pickled wire mesh filler has a void ratio of more than 90%, a mesh fiber diameter of 0.3 to 4 mm, a thickness of 100 to 300 mm, and is woven from polytetrafluoroethylene and metal fibers;
  • the separation screen filler has a void ratio of 80% to 90%, a mesh fiber diameter of 0.1 to 3 mm, and a thickness of more than 200 mm.
  • the first half is woven from polytetrafluoroethylene and metal fibers, and the second half is made of poly Propylene and metal fibers are woven; and the shortest distance between the pickled wire mesh filler and the separation wire mesh filler is 0.3 to 4D, And not less than 500 mm, wherein D is the inner diameter of the pickling separator tank; the mixed liquid feed port or the new sulfuric acid feed port is located at a middle of the gap between the pickled wire mesh packing and the separating wire mesh packing; A surge rectifier is disposed at the material port, and the impact rectifier is selected from the group consisting of a porous pipe, a branch pipe, a blanking plate, a swash plate, and a row of blades.
  • the first acid hydrocarbon separation device is equipped with a two-stage fiber membrane bed having a porosity of 80% to 90%, a fiber diameter of less than 200 ⁇ m, and a thickness of more than 200 mm.
  • the first half of each fiber membrane bed is woven from polytetrafluoroethylene fibers, and the second half is made of one or more selected from the group consisting of metal fibers, polytetrafluoroethylene fibers, polypropylene fibers, and polyester fibers.
  • the second acid hydrocarbon separation device is equipped with two fiber membrane filter elements made of super-hydrophilic or super-lipophilic modified nanofiber membrane, the porosity of the fiber membrane is less than 80 %, the fiber diameter is less than 100 ⁇ m, and the thickness is greater than 50 mm; wherein the nanofiber membrane is modified by one or more selected from the group consisting of metal fibers, polytetrafluoroethylene fibers, polypropylene fibers, and polyester fibers.
  • the shortest distance between the fiber membrane beds inside the primary acid hydrocarbon separation device and the fiber membrane filtration filter inside the secondary acid hydrocarbon separation device is 0.1 to 0.5D, and is not less than 500mm; primary acid hydrocarbon The shortest distance between the device and the secondary sedimentation section of the secondary acid hydrocarbon separation device is 0.3-2D, and not less than 1000 mm, wherein D' is the inner diameter of the first acid hydrocarbon separation device and the secondary acid hydrocarbon separation device;
  • the internal inlets of the acid hydrocarbon separation device and the secondary acid hydrocarbon separation device respectively have a fluid uniform rectifying plate and the fluid homogenizing rectifying plate and the porous plate which is porous and uniformly distributed.
  • FIG. 1 is a schematic view showing a process flow of desulfurization and deacidification of an alkylation product according to an embodiment of the present invention.
  • FIG. 2 is a schematic flow chart of a process for desulfurization and deacidification of an alkylation product according to another embodiment of the present invention.
  • FIG 3 is a schematic view showing a process flow of desulfurization and deacidification of an alkylation product according to still another embodiment of the present invention.
  • Fiber membrane separation technology is a new type of heterogeneous separation technology developed in recent years. Its working principle mainly includes: (1) fiber modification technology: by modifying the surface characteristics, the material is super-hydrophilic/super-lipophilic; (2) The principle of fiber capture and aggregation: nano-parent fiber can destroy the emulsion film layer around the fine acid drop in the alkylation product, capture the fine acid droplets in the emulsified oil package, and achieve the demulsification effect; (3) The principle of induced separation of fiber configuration : Inductive separation benefits from the special fiber configuration, the fine acid droplets on the fibers collide through the nodes and form larger acid droplets; (4) The heterogeneous filtration characteristics of the fiber membrane: in the macroscopic aspect, it appears as two-phase The difference in fiber membrane transmission resistance is good for the oil phase, and the acid phase is difficult to pass through the fiber membrane quickly.
  • the two phases produce a speed slip characteristic and strengthen the emulsion breaking. Therefore, the fiber membrane separation technology not only based on the principle of droplet aggregation, but also achieves rapid separation of liquid-liquid two phases, and also has a strong demulsification effect.
  • the separation device is used to remove the acid in the alkylation product, so that this process does not require water washing and alkali washing, and does not require the addition of any catalyst, thereby overcoming the problems of water washing, caustic washing and catalyst addition to the lower process equipment.
  • the present invention performs mixed pickling in a pickling tank by countercurrent or cross-flow of a liquid alkylation product and its entrained material and fresh sulfuric acid, and performs initial separation of the acidified alkylation reaction product;
  • the alkylated product after washing and separation is subjected to crude separation by a primary acid hydrocarbon separation device to obtain a primary oil phase and a primary acid phase; the primary oil phase is separated into a secondary acid hydrocarbon separation device for fine separation to obtain a secondary oil phase.
  • the obtained secondary oil phase contains very low acid content;
  • the alkylation product containing a very small amount of sulfuric acid will be sent to the adsorption equipment for final treatment, and the sulfuric acid in the treated alkylated product is basically After the depletion, the purified alkylated product is sent to the deisobutane column or the next stage process; the sulfuric acid and sulfate separated by the pickling separation tank and the primary acid phase and the secondary acid phase are re-enriched. Returning to the alkylation reactor or in the pickling tank to continue participating in the reaction saves the amount of sulfuric acid used.
  • the method of the invention has the advantages of reliable effect, the free sulfuric acid content in the alkylation product after the adsorption device is not more than 1 mg/kg, and the sulfate removal rate is as high as 99.9%, thereby eliminating the subsequent alkali washing, water washing and the like, and shortening the process. Reduced investment and saved energy.
  • a method of desulfurization and deacidification of an alkylated product comprising the steps of:
  • an alkylation product having a sulfuric acid content of about 0.01% to 1.0% is sent from the top of the pickling tank to the acid hydrocarbon separation section for acid hydrocarbon separation;
  • the acid hydrocarbon separation section is a single-stage or multi-stage acid hydrocarbon separation unit, preferably a two-stage acid hydrocarbon separation unit; in the acid hydrocarbon separation unit, the sulfuric acid entrained by the alkylation product is subjected to coarse separation and fine separation to obtain sulfuric acid.
  • the alkylation product having a sulfuric acid content of less than 10 mg/kg is sent to an adsorption unit to adsorb the remaining, extremely small amount of sulfuric acid to obtain an alkylation product for removing sulfate and sulfuric acid;
  • the butane column is deisobutane or sent to the next stage of processing.
  • the new sulfuric acid and the liquid alkylate containing sulfuric acid and sulfate enter the pickling tank in countercurrent or cross-flow form, due to the special, narrow, non-standard pore structure of the screen packing.
  • the pickled wire mesh filler is dispersed into droplets or fine streams, which increases the contact area and contact probability of the new sulfuric acid and sulfate, so that it is sufficiently contacted for dissolution, extraction, or in the mixer before being sent to the pickling tank. Mix well to remove organic sulfur compounds such as sulfates in the alkylation product.
  • the pickling screen filler can disperse two materials, such as new sulfuric acid and alkylated product with sulfate ester, into droplets or trickles, and provide a contact carrier, which greatly increases the contact area and contact probability of the new sulfuric acid and sulfate. It is fully contacted and dissolved, which greatly increases the extraction amount of sulfuric acid from new sulfuric acid; sufficient mixing can increase the extraction amount of sulfuric acid from new sulfuric acid; countercurrent or cross-flow can also increase the contact chance of new sulfuric acid and sulfate It can also have a beneficial effect on the extraction of sulfate.
  • the screen filler is used as the carrier, which not only enhances the pickling effect, but also can be combined and separated during pickling, which greatly increases the alkyl group.
  • the removal rate of entrained sulfate in the product is used as the carrier, which not only enhances the pickling effect, but also can be combined and separated during pickling, which greatly increases the alkyl group.
  • the acidified alkylated product enters the separation screen packing in the upper portion of the pickling separation tank; on the separation screen packing, more than 95% of the sulfurized product in the alkylation product is aggregated and separated to obtain a sulfuric acid content. About 0.01% to 1.0% of the alkylation product; the separated sulfuric acid settles to the bottom of the pickling tank.
  • the separation screen packing can effectively intercept, collect and separate more than 95% of sulfuric acid and sulfuric acid solute.
  • the remaining undepleted sulfuric acid is sent to the acid hydrocarbon separation section through the pipeline for fiber membrane separation, thereby achieving the purpose of removing sulfuric acid from the alkylation product.
  • the two-stage acid hydrocarbon separation device is arranged in a gradient to achieve crude separation and fine separation of the sulfuric acid entrained in the alkylation product; wherein the alkylation product obtained by crude separation of the primary acid hydrocarbon separation device is directly It is sent to a secondary acid hydrocarbon separation unit for fine separation. Due to the high content of sulfuric acid from the top of the pickling tank, there are many other impurities, and the nanofiber membrane filter element for fine separation has limited separation ability and small pores. If it is directly separated, it is likely to clog. The acid hydrocarbon separation device or the separation effect is not good, so it is necessary to add coarse separation before fine separation to remove large particles of sulfuric acid and other impurities, so a two-stage acid hydrocarbon separation device is preferred.
  • the alkylation product from the top of the pickling separation tank is piped into the first-stage acid hydrocarbon separation device, and after being re-distributed through the fluid uniformizing plate, the fiber membrane bed inside the first-acid acid hydrocarbon separation device is subjected to coarse separation to obtain coarse
  • the separated alkylated product is then directly sent to the secondary acid hydrocarbon separation device via the pipeline, and then redistributed through the fluid uniformizing plate, and then enters the nanofiber membrane filter element inside the secondary acid hydrocarbon separation device for fine separation.
  • An alkylation product having a sulfuric acid content of less than 10 mg/kg is obtained.
  • the primary acid phase and the secondary acid phase separated by the primary and secondary acid hydrocarbon separation devices are enriched and sent to a pickling tank or an alkylation reactor through a pipeline for recycling or efflux.
  • the separated alkylation product having a sulfuric acid content of less than 10 mg/kg enters an adsorption device equipped with a bed of exchanged adsorption resin, and the exchange adsorption resin can adsorb sulfuric acid entrained in the alkylation product to lower the sulfuric acid concentration. Up to 1mg/kg.
  • an apparatus for desulfurization and deacidification of an alkylation product comprising:
  • a mixer for thoroughly mixing the fresh sulfuric acid with the alkylation product containing the sulfate and sulfuric acid
  • a pickling separation tank connected to a mixer for separating sulfuric acid esters and sulfuric acid entrained in most of the alkylation products
  • a single-stage or multi-stage acid hydrocarbon separation device for achieving gradient separation preferably a two-stage acid hydrocarbon separation device, that is, a primary acid hydrocarbon separation device connected to the top of the pickling separation tank and an oil phase outlet with the primary acid hydrocarbon separation device a connected secondary acid hydrocarbon separation device, wherein the primary acid hydrocarbon separation device is used for crude separation of sulfuric acid entrained in the alkylation product to remove sulfuric acid having a large particle size; the secondary acid hydrocarbon separation device is used for Alkylation product A small amount of sulfuric acid is entrained for fine separation to remove sulfuric acid having a smaller particle size;
  • the adsorption device connected in series with the acid hydrocarbon separation section is provided with an exchange adsorption resin bed for adsorbing a trace amount of sulfuric acid in the alkylation product to reduce the sulfuric acid concentration in the alkylation product to less than 1 mg/kg.
  • the acid-washed wire mesh packing in the lower portion of the pickling separation tank has a void ratio of more than 90%
  • the wire mesh fiber has a diameter of 0.3 to 4 mm
  • the thickness is 100 to 300 mm
  • a certain preparation method is woven; the space of the separation screen filler in the upper part of the pickling separation tank is 80% to 90%, the diameter of the screen fiber is 0.1 to 3 mm, the thickness is 200 mm or more, and the first half is composed of poly four.
  • the fluoroethylene fiber and the metal fiber are woven according to a certain preparation method, and the latter half is woven by polypropylene fiber and metal fiber according to a certain preparation method, which can effectively intercept, collect and separate more than 95% of sulfuric acid and dissolve it.
  • the remaining undepleted sulfuric acid will be sent to the acid hydrocarbon separation section for multi-stage fiber membrane separation to achieve the purpose of removing sulfuric acid from the alkylation product.
  • the shortest distance between the pickled wire mesh packing and the separating wire mesh packing in the pickling separation tank is 0.3 to 4D, and not less than 500 mm (D is the inner diameter of the pickling separator tank); a mixed liquid feed port or a new sulfuric acid feed port is located at a middle of a gap between the pickled wire mesh filler and the separation wire mesh filler; a punching rectifier is disposed at the feed port, and the impact rectifier is selected from the group consisting of porous One of a tube, a branch tube, an impact baffle, a swash plate, and a row of blades.
  • a two or more stage acid hydrocarbon separation unit for effecting gradient separation is provided, preferably a two stage acid hydrocarbon separation unit.
  • the first acid hydrocarbon separation device is equipped with two fiber membrane beds having a special structural structure to separate large-sized sulfuric acid particles.
  • the secondary acid hydrocarbon separation device is internally provided with two filter cartridges made of a super-hydrophilic or super-lipophilic modified nanofiber membrane, which can effectively separate sulfuric acid particles having a smaller particle size.
  • the beneficial effect is that gradient separation of the acid entrained in the effluent is achieved, and in particular, the modified nanofiber material has better separation ability for acid.
  • the first acid hydrocarbon separation device is internally provided with two fiber membrane beds having a special structural structure; the fiber membrane bed has a porosity of 80% to 90%, and the fibers of the fiber membrane bed
  • the diameter of the fiber membrane bed is less than 200 mm; the thickness of each fiber membrane bed is more than 200 mm; wherein the first half of each fiber membrane bed is woven from polytetrafluoroethylene fibers; the second half of each fiber membrane bed is selected from the group consisting of metal fibers and polytetra One or more of fluoroethylene fibers, polypropylene fibers, and polyester fibers are woven.
  • the second acid hydrocarbon separation device is internally provided with two filter cartridges made of a super-hydrophilic or super-lipophilic modified nanofiber membrane; the porosity of the fibrous membrane is less than 80%. a fiber diameter of less than 100 ⁇ m; the nanofiber film thickness of each of the filter elements is 50 mm or more; the nanofiber membrane It is woven by one or more selected from the group consisting of metal fibers, polytetrafluoroethylene fibers, polypropylene fibers, and polyester fibers.
  • the shortest distance between each two-stage fiber membrane bed inside the primary and secondary acid hydrocarbon separation device is 0.1 to 0.5 D', and not less than 500 mm; the sedimentation section behind the acid hydrocarbon separation device
  • the shortest distance is 0.3 to 2D', and is not less than 1000 mm (D' is the inner diameter of the acid hydrocarbon separation device).
  • the internal inlets of the primary and secondary acid hydrocarbon separation devices each have a fluid-uniform rectifying plate, and the fluid-uniform rectifying plate is a porous uniformly-opened thick plate.
  • FIG. 1 is a schematic view showing a process flow of desulfurization and deacidification of an alkylation product according to an embodiment of the present invention.
  • the pickling separation tank 1 is provided with a section of pickled wire mesh packing 2, a section of separating wire mesh packing 3 is arranged at the upper part, and the two sections of wire mesh packing are separated by at least 500 mm; the new sulfuric acid is separated from the two layers of wire mesh.
  • the filler enters between and close to the side of the separation screen packing 3, and the alkylation product enters from the bottom.
  • the two streams After being rectified by the anti-shock rectifier 4, the two streams enter the pickling separation tank 1 in a countercurrent form; the lower pickling screen
  • the filler 2 can disperse two materials, such as new sulfuric acid and the alkylated product entrained with sulfate, into droplets or a trickle, and provide a contact carrier, which greatly increases the contact area and contact probability of the new sulfuric acid and the sulfate, so that It is fully contacted and dissolved, so that the sulfate ester is dissolved in sulfuric acid, aggregates and settles down;
  • the upper separation screen filler 3 can effectively intercept and separate 95% of the sulfuric acid to obtain an alkylated product containing a small amount of sulfuric acid;
  • the separated alkylation product alkane and a small amount of sulfuric acid
  • the precipitated sulfuric acid and sulfate are concentrated in the bottom of the pickling separation tank 1, and then sent back to the pickling tank.
  • the alkylation product containing a small amount of sulfuric acid is sent to the primary acid hydrocarbon separation unit 7 for crude separation; after entering the primary acid hydrocarbon separation unit 7, the fluid is uniformly distributed to the rectification plate 8, and then passes through two stages.
  • the fiber membrane beds 8 and 9 are coarsely separated, and the acid concentration in the alkylation product is further reduced, mainly removing the entrained large-size sulfuric acid; then entering the secondary acid hydrocarbon separation device 10 to continue to collect and separate, and the fluid is uniformly distributed.
  • the rectifying plate 11 is then finely separated by two sections of the fiber membrane filter element 11 and 12, and the acid content in the alkylation product is reduced to less than 10 mg/kg, mainly removing the entrained small particle size sulfuric acid; the acid hydrocarbon separation device is separated.
  • the sulfuric acid is enriched, it is sent back to the pickling tank or the alkylation reactor or the efflux; for the remaining, extremely small amount of sulfuric acid having a smaller particle size, it is sent to the adsorption device 13 for removal, and the adsorption device 13
  • the exchange adsorption resin bed 14 is provided, and the sulfuric acid concentration can be reduced to 1 mg/kg or even lower; the sulfuric acid in the alkylation product from the adsorption device 13 is almost completely removed, and the next level of process requirements are met, and will be sent. Take off Or a debutanizer next process.
  • FIG. 2 is a schematic flow chart of a process for desulfurization and deacidification of an alkylation product according to another embodiment of the present invention.
  • the two streams of the new sulfuric acid and the liquid alkylation product containing sulfuric acid and sulfate, etc. which are pushed by the circulation pump 5, enter the mixer 6 in a cross-flow form and are thoroughly mixed, and then pass through the surge rectifier.
  • the pickling screen packing 2 in the lower part of the pickling separation tank 1 can disperse two materials such as new sulfuric acid and alkylated product entrained with sulfate into droplets or trickles, and provide Contact with the carrier greatly increases the contact area and contact probability of the new sulfuric acid and sulfate, so that it is fully contacted and dissolved, thereby facilitating the dissolution of the sulfate in sulfuric acid, accumulating and sedimenting; pickling the separation screen on the upper part of the separation tank 1
  • the filler 3 can effectively intercept and separate most of the sulfuric acid to obtain an alkylation product containing a small amount of sulfuric acid; after acid washing, the alkylated product (alkane and a small amount of sulfuric acid) is taken out from the top of the pickling and separating tank 1;
  • the sulfuric acid and sulfate are enriched at the bottom of the pickling tank 1, and sent back to the pickling tank or the alkylation reactor or efflux;
  • the fluid After entering the first-stage acid hydrocarbon separation device 7, the fluid is uniformly distributed by the rectifying plate 8, and then subjected to coarse separation through the two-stage fiber membrane bed 9, and the acid concentration in the alkylation product is further reduced, mainly removing the entrained large particles.
  • Sulfuric acid then enters the secondary acid hydrocarbon separation unit 10 to continue to collect and separate, through the fluid uniformizing plate 11, and then through two stages of fiber membrane filter 12 for fine separation, the acid content of the alkylation product is reduced to 10mg Below /kg, the small particle size sulfuric acid entrained is mainly removed; the sulfuric acid separated by the acid hydrocarbon separation device is sent back to the pickling tank or the alkylation reactor or the efflux after enrichment; for sulfuric acid having a smaller particle size It is sent to the adsorption device 13 for removal, and the adsorption device 13 is provided with an exchange adsorption resin bed 14, which can reduce the sulfuric acid concentration to 1 mg/kg or even lower; almost all of the sulfuric acid in the alkylation product from the adsorption device 13 is removed. Net, meet the next level of process requirements will be sent to the deisobutane tower or the next level of process.
  • FIG. 3 is a schematic view showing a process flow of desulfurization and deacidification of an alkylation product according to still another embodiment of the present invention.
  • two streams of a new sulfuric acid and a liquid alkylation product containing sulfuric acid and a sulfate, etc., which are driven by the circulation pump 5, are mixed into the mixer 6 in a cross-flow form, and are thoroughly mixed, and then subjected to a surge rectifier.
  • the pickling screen packing 2 in the lower part of the pickling separation tank 1 and the upper separating screen packing 3 can provide a contact carrier, increasing the contact area and contact probability of the new sulfuric acid and the sulfate , so that it is fully contacted and dissolved, thereby facilitating the dissolution of the sulfate in sulfuric acid, and removing the sulfate and most of the sulfuric acid by the polycondensation to obtain an alkylation product containing a small amount of sulfuric acid; the alkylation product after pickling and separation (alkanes and a small amount of sulfuric acid) are taken from the top of the pickling tank 1; the settled sulfuric acid and sulfate are enriched at the bottom of the pickling tank 1, and sent back to the pickling tank or the alkylation reactor or efflux The alkylation product containing a small amount of sulfuric acid is sent to the primary acid hydrocarbon separation unit 7 for crude separation; after entering the primary acid hydrocarbon separation unit 7,
  • the exchange adsorption resin bed 14 can reduce the sulfuric acid concentration to 1 mg/kg or even lower; the sulfuric acid in the alkylation product from the adsorption device 13 is almost completely removed, and the next-stage process requirement is sent off. Isobutane column or next stage process.
  • the invention effectively combines four separation methods such as gravity sedimentation, polymerization and separation, fiber membrane separation and adsorption separation and surface modification technology, and realizes the acid entrained in the alkylation product through multi-stage separation and targeted treatment.
  • the separation can adapt to different acid concentrations, has high separation efficiency and processing ability, can effectively remove the sulfuric acid and sulfate ester entrained in the alkylation product, so that the content meets the requirements of the next-level production process;
  • the need for water washing and caustic washing does not require the addition of any catalyst, which simplifies the alkylation production process, thereby overcoming the effects of washing, caustic washing and the addition of any catalyst on the lower process unit, shortening the process, reducing investment, and saving. Energy consumption.
  • a petrochemical company in Shandong has tried the desulfurization and deacidification device of the alkylation product of the present invention, and separated impurities such as sulfuric acid and sulfuric acid contained in the alkylation reaction product to ensure the safety of the downstream production device and optimize the production process. Reduce the cost.
  • the new sulfuric acid enters from between the two layers of wire mesh packing and near the side of the separating screen packing, the liquid alkylation product enters from the bottom, and the two streams enter the pickling separation tank in countercurrent.
  • the pickled wire mesh packing most of the sulfate and the new sulfuric acid are sufficiently contacted and dissolved, and together with the sulfuric acid, settle as a heavy phase to the bottom of the pickling tank.
  • the light phase alkylation product moves up to the upper separation screen packing, most of the sulfuric acid entrained in the alkylation product is aggregated and separated.
  • the base product with a small amount of sulfuric acid is sent from the top of the pickling tank to the first-stage acid hydrocarbon separation device, which is firstly rectified by a uniform rectifying plate and then passed through two fiber membrane beds to separate the sulfuric acid with a large particle size;
  • the alkylated product is separated from the oil phase outlet of the primary acid hydrocarbon separation unit into a secondary acid hydrocarbon separation unit, re-rectified by a uniform rectification plate, and then passed through two fiber membrane filter elements to separate sulfuric acid having a small particle size;
  • the alkylation product from the oil phase outlet of the secondary acid hydrocarbon separation unit enters the adsorption unit, adsorbs the remaining and traces of sulfuric acid, and then proceeds to the next stage of the process.
  • the smooth flowing liquid acid hydrocarbon mixture is rectified by a surge rectifier and then enters the pickling separation tank, and then enters the primary acid hydrocarbon separation unit and the secondary acid hydrocarbon separation unit.
  • the pickling wire packing and the upper separating wire mesh packing of the pickling separation tank are all prepared by 316L metal fiber (purchased from Baoshan Iron and Steel Group Co., Ltd.) in a certain way, except that the fiber diameter and filler thickness of the two are different.
  • the fiber membrane filter inside the first-stage acid hydrocarbon separation device and the fiber membrane filter element inside the secondary acid hydrocarbon separation device are prepared by 316L metal fiber and polytetrafluoroethylene fiber according to a certain ratio and a certain manner.
  • the top sulfuric acid content of the pickling and separating irrigation is about 0.1% to 0.4%
  • the sulfuric acid ester has been substantially removed
  • the sulfuric acid concentration in the alkylation product of the oil phase outlet of the primary acid hydrocarbon separation device is about 100 mg/kg.
  • the concentration of sulfuric acid in the alkylation product of the oil phase outlet of the secondary acid hydrocarbon separation device is less than 10 mg/kg, and almost no sulfuric acid content is detected in the alkylation product from the adsorption device, which completely meets the requirements of the downstream production process.
  • An alkylation pilot plant of a petrochemical company in Hebei province tested the desulfurization and deacidification device of the alkylation product of the present invention, and separated impurities such as sulfuric acid and sulfuric acid contained in the alkylation reaction product to ensure a downstream production device. Safety and optimized production processes to reduce costs.
  • the main parameters of the desulfurization and deacidification process of the alkylation product are: the working pressure of the pickling separation tank is 0.6 MPa, the added new sulfuric acid is 98% by weight, the alkylation product is treated with 500 L/h, and the sulfuric acid content is 18% by weight, sulfuric acid.
  • the ester is 1 to 2.5% by weight.
  • the fresh sulfuric acid and the alkylation product containing sulfuric acid and sulfate, etc. are mixed by the circulation pump into the pickling separation tank after being thoroughly mixed in the mixer.
  • On the pickled wire mesh packing most of the sulfate and new sulfuric acid are in contact with and dissolved, and together with sulfuric acid, settle as a heavy phase to the bottom of the pickling tank.
  • As the light phase alkylation product moves up to the upper separation screen packing most of the sulfuric acid entrained in the alkylation product is aggregated and separated.
  • the base product with a small amount of sulfuric acid is sent from the top of the pickling tank to the first-stage acid hydrocarbon separation device, which is firstly rectified by a uniform rectifying plate and then passed through two fiber membrane beds to separate the sulfuric acid having a large particle size;
  • the alkylation product is introduced into the secondary acid hydrocarbon separation device from the oil phase outlet of the primary acid hydrocarbon separation unit, re-rectified by the uniform rectification plate, and then passed through the two-stage fiber membrane filtration filter to separate the sulfuric acid having a small particle size;
  • the alkylation product from the oil phase outlet of the acid-acid separation unit completely meets the process requirements, and then directly enters the next-stage process.
  • the smooth flowing liquid acid hydrocarbon mixture is rectified by a surge rectifier and then enters the pickling separation tank, and then enters the primary acid hydrocarbon separation unit and the secondary acid hydrocarbon separation unit.
  • the pickling wire packing in the lower part of the pickling separation tank is prepared by a 316L wire (purchased from Baoshan Iron and Steel Group Co., Ltd.) having a diameter of 2 mm and having a thickness of 200 mm; the upper part of the pickling separation tank is separated by a wire mesh filler.
  • 1mm 316L wire and PTFE are prepared according to a certain ratio and a certain method, and the thickness is 300mm;
  • the fiber membrane bed inside the primary acid hydrocarbon separation device is made of metal fiber, polytetrafluoroethylene fiber and polypropylene fiber. It is prepared in a certain proportion and in a certain way.
  • the fiber membrane filter element inside the secondary acid hydrocarbon separation device is prepared from polypropylene and PTFE fiber in a certain proportion and in a certain way.
  • the top sulfuric acid content of the pickling and separating irrigation is about 0.5%
  • the sulfuric acid ester has been substantially removed
  • the sulfuric acid concentration in the alkylation product of the oil phase outlet of the primary acid hydrocarbon separation device is about 30-150 mg/kg.
  • the concentration of sulfuric acid in the alkylation product of the oil phase outlet of the secondary acid hydrocarbon separation device is less than 6 mg/kg; it fully meets the requirements of the downstream production process.
  • Table 3 below shows the sulfuric acid content of the first-stage acid hydrocarbon separation unit in the industrial field pilot test. Part of the experimental data.

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Abstract

一种烷基化产物脱硫脱酸的方法与装置。所述方法包括以下步骤：（ａ）将含有硫酸和硫酸酯的烷基化产物和新硫酸送入酸洗分离罐（１）内；（ｂ）在酸洗分离罐（１）下部的酸洗丝网填料（２）中，硫酸酯和新硫酸接触、聚并分离；溶于硫酸的硫酸酯和硫酸作为重相沉降至酸洗分离罐（１）底部；（ｃ）作为轻相的烷基化产物进入酸洗分离罐（１）上部的分离丝网填料（３），得到硫酸含量降低的烷基化产物；（ｄ）所得烷基化产物从酸洗分离罐（１）顶部被送至酸烃分离段进行酸烃分离；（ｅ）得到硫酸含量低于１０㎎／㎏的烷基化产物；（ｆ）将所得烷基化产物送至吸附装置（１３）中，得到除去了硫酸酯和硫酸的产品。

Description

烷基化产物脱硫脱酸的方法与装置 技术领域
本发明属于烷基化产物中携带的有机硫化合物和游离硫酸对后续设备的腐蚀的领域，涉及一种从烷基化产物中去除有机硫化合物(如：硫酸酯)和游离硫酸的方法和装置。
背景技术
当今世界的环境污染日益严重，环境保护受到普遍受到各国的重视。在国内外，随着汽车拥有量的激增，汽车排放尾气对空气的污染日趋严重，各国的环保要求也日趋严格，这对车用油的辛烷值和清洁度提出了更高的要求。烷基化油的高辛烷值、低含硫量等优良性能特点使得它日益受到各国重视。
在石油加工工业中，烷基化是链烷烃、通常是异链烷烃与烯烃在强酸存在下制备更高辛烷值的链烷烃，这是公知的方法。烷基化过程需要在强酸环境中进行，一般以硫酸为催化剂，硫酸常被搅拌处理成微细液滴或乳化液，这增加了沉降分离的难度，一次后续工艺中必须对烷基化流出物进行酸烃分离，否则这些强酸进入后续工艺会导致设备的严重腐蚀。此外在烷基化反应中，部分烯烃和硫酸反应生成硫酸酯等含硫有机物，这些酯在酸性或高温条件下极不稳定，若不加以脱除，将在下游的脱异丁烷塔分解放出SO2(在高温条件下)，遇到水分，则会严重腐蚀设备，并在脱异丁烷塔的重沸器结垢。所以，必须予以脱除。
酸烃分离的方法有物理法、物理化学法和化学法等。中国专利申请CN102021016A公开了一种用改性陶瓷膜组件来去除烷基化反应产物中酸的方法，可实现油中含酸量低于100mg/L，随后再用碱水洗涤实现酸的脱除。中国专利申请CN1803739A公开了一种含有聚并材料的除雾容器，通过湿润聚并材料吸附除去烷基化产物中的硫酸和硫酸酯。中国专利申请CN1688524A公开了一种通过机械性的聚并器从烷基化产物中出去硫酸，然后在下一级工艺中加入催化剂除去产物中的磺酸酯和磺酸盐。
然而，上述现有技术的方法并不能有效地解决烷基化产物中携带的有机硫化合物和游离硫酸对后续设备的腐蚀问题。
因此，本领域迫切需要开发出能够有效地对烷基化产物中的硫酸与硫酸酯等 物质进行分离，使烷基化产物达到脱硫脱酸目的的方法与装置。
发明内容
本发明提供了一种新颖的烷基化产物脱硫脱酸的方法与装置，从而解决了现有技术中存在的问题。
本发明所要解决的技术问题是，烷基化产物中携带的有机硫化合物和游离硫酸对后续设备的腐蚀。
一方面，本发明提供了一种烷基化产物脱硫脱酸的方法，该方法包括以下步骤：
(a)将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料以逆流或错流方式送入酸洗分离罐内酸洗、聚并分离；
(b)在酸洗分离罐下部的酸洗丝网填料中，硫酸酯和新硫酸充分接触并相互溶解萃取，同时发生聚并分离；溶于硫酸的硫酸酯和烷基化产物中超过50％的硫酸作为重相沉降下来至酸洗分离罐底部，富集后送至酸洗沉降罐或者烷基化反应器或者外排；
(c)作为轻相的烷基化产物进入酸洗分离罐上部的分离丝网填料，其中，在分离丝网填料上，作为轻相的烷基化产物中超过95％的硫酸被聚并分离，得到硫酸含量约为0.01％～1.0％的烷基化产物；聚并分离后的硫酸沉降至酸洗分离罐底部；
(d)所得的硫酸含量约为0.01％～1.0％的烷基化产物从酸洗分离罐顶部被送至酸烃分离段进行酸烃分离，其中，所述酸烃分离段为单级或多级酸烃分离装置；
(e)在酸烃分离装置中对所述硫酸含量约为0.01％～1.0％的烷基化产物中所夹带的硫酸进行粗分离和精细分离，得到硫酸含量低于10mg/kg的烷基化产物；分离出来硫酸富集后被送去酸洗沉降罐或者烷基化反应器或者外排；以及
(f)所得的硫酸含量低于10mg/kg的烷基化产物被送至吸附装置中，以吸附剩余的含量低于10mg/kg的硫酸，得到除去了硫酸酯和硫酸的烷基化产物。
在一个优选的实施方式中，所述步骤(a)还包括：在将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料以逆流或错流方式送入酸洗分离罐内之前，在混合器内使其充分混合。
在另一个优选的实施方式中，在步骤(d)中，所述酸烃分离段为两级酸烃分离装置梯度布置，一级酸烃分离装置粗分离得到的烷基化产物直接被送至二级酸 烃分离装置进行精细分离。
在另一个优选的实施方式中，在步骤(f)中，所得的硫酸含量低于10mg/kg的烷基化产物被送至装有交换吸附树脂床的吸附装置中，以吸附剩余的含量低于10mg/kg的硫酸，使其硫酸浓度降到低于1mg/kg。
另一方面，本发明提供了一种烷基化产物脱硫脱酸的装置，该装置包括：
酸洗分离罐，用于对送入其中的液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料进行酸洗、聚并分离；
在酸洗分离罐下部的酸洗丝网填料，用于使得硫酸酯和新鲜硫酸充分接触并相互溶解萃取、同时发生聚并分离；
在酸洗分离罐上部的分离丝网填料，用于使经过酸洗丝网填料(2)后的烷基化产物中超过95％的硫酸被聚并分离，得到硫酸含量约为0.01％～1.0％的烷基化产物；
与酸洗分离罐连接的酸烃分离段，其中，所述酸烃分离段为单级或多级酸烃分离装置，用于对所述硫酸含量约为0.01％～1.0％的的烷基化产物中所夹带的硫酸进行粗分离和精细分离，得到硫酸含量低于10mg/kg的烷基化产物；
与酸烃分离段连接的吸附装置，用于吸附剩余的含量低于10mg/kg的硫酸，得到除去了硫酸酯和硫酸的烷基化产物。
在一个优选的实施方式中，该装置还包括：与酸洗分离罐连接的混合器，用于在将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料送入酸洗分离罐内之前，使其充分混合。
在另一个优选的实施方式中，所述酸烃分离段为两级酸烃分离装置梯度布置，一级酸烃分离装置粗分离得到的烷基化产物直接被送至与其连接的二级酸烃分离装置进行精细分离。
在另一个优选的实施方式中，所述吸附装置装有交换吸附树脂床，用于吸附剩余的含量低于10mg/kg的硫酸，使其硫酸浓度降到低于1mg/kg。
在另一个优选的实施方式中，所述酸洗丝网填料的空隙率大于90％，丝网纤维直径为0.3～4mm，厚度为100～300mm，由聚四氟乙烯和金属纤维编织而成；所述分离丝网填料的空隙率为80％～90％，丝网纤维直径为0.1～3mm，厚度为大于200mm，其前半段由聚四氟乙烯和金属纤维编织而成，后半段由聚丙烯和金属纤维编织而成；并且，所述酸洗丝网填料和分离丝网填料之间的最短距离为0.3～4D， 且不少于500mm，其中D为酸洗分离器罐的内径；混合液进料口或新硫酸进料口位于酸洗丝网填料和分离丝网填料之间空隙中部偏上处；所述进料口处设置防冲整流器，所述的防冲整流器选自多孔管、分支管、防冲挡板、斜板和列式叶片中的一种。
在另一个优选的实施方式中，所述一级酸烃分离装置的内部装有两段纤维膜床，所述纤维膜床的孔隙率为80％～90％，纤维直径小于200μm，厚度大于200mm；其中，每段纤维膜床的前半段由聚四氟乙烯纤维编织而成，后半段由选自金属纤维、聚四氟乙烯纤维、聚丙烯纤维和聚酯纤维中的一种或多种编织而成；所述二级酸烃分离装置的内部装有两段经过超亲水或者超亲油改性处理的纳米纤维膜制成的纤维膜过滤滤芯，所述纤维膜的孔隙率小于80％，纤维直径小于100μm，厚度大于50mm；其中，所述纳米纤维膜是由选自金属纤维、聚四氟乙烯纤维、聚丙烯纤维和聚酯纤维中的一种或多种经改性后编织而成的；并且，所述一级酸烃分离装置内部的纤维膜床之间以及二级酸烃分离装置内部的纤维膜过滤滤芯之间的间隔最短距离为0.1～0.5D，且不少于500mm；一级酸烃分离装置和二级酸烃分离装置后面沉降段的最短距离为0.3～2D’，且不少于1000mm，其中D’为一级酸烃分离装置和二级酸烃分离装置的内径；所述一级酸烃分离装置和二级酸烃分离装置的内部进口处分别有流体均布整流板和，所述流体均布整流板和为多孔均布的开孔厚板。
附图说明
图1是根据本发明的一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。
图2是根据本发明的另一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。
图3是根据本发明的再一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。
具体实施方式
本申请的发明人经过广泛而深入的研究后发现，针对烷基化产物中携带的有机硫化合物和游离硫酸对后续设备的腐蚀问题，通过高效的机械性的酸洗分离罐除去了烷基化产物中的硫酸酯等含硫有机物和大部分硫酸；并利用纤维膜分离技术，通过高效的单级酸烃分离装置或者多级酸烃分离装置以除净烷基化产物中的酸，使得这一过程不需要水洗和碱洗也不需要加入任何催化剂，从而克服了水洗、碱 洗和加催化剂等对下级工艺装置的影响问题，缩短了流程，减少了投资，节省了能耗。基于上述发现，本发明得以完成。
本发明的技术构思如下：
纤维膜分离技术是近年发展起来的新型非均相分离技术，其工作原理主要包括了：(1)纤维改性技术：通过修改表面特性，建立材料超亲水/超亲油特性；(2)纤维捕捉聚并原理：纳米双亲纤维可以破坏烷基化产物中微细酸滴周围的乳化膜层，捕捉乳化油包裹中的细小酸滴，实现破乳作用；(3)纤维构型的诱导分离原理：诱导分离得益于特殊的纤维构型，纤维上的细小酸滴通过节点碰撞聚并形成较大酸滴；(4)纤维膜的非均相过滤特性：在宏观上，表现为两相的纤维膜透过阻力差异，对于油相来说，其透过性好，而酸相则难以快速通过纤维膜，因此，两相产生速度滑移特性，强化破乳。因此，纤维膜分离技术不仅基于液滴聚并原理，实现液-液两相快速分离，还具有强效的破乳作用。
通过高效的机械性的酸洗分离罐除去了烷基化产物中的硫酸酯等含硫有机物和大部分硫酸；并利用纤维膜分离技术，通过高效的单级酸烃分离装置或者多级酸烃分离装置以除净烷基化产物中的酸，使得这一过程不需要水洗和碱洗也不需要加入任何催化剂，从而克服了水洗、碱洗和加催化剂等对下级工艺装置的影响问题。
本发明通过将液态的烷基化产物及其夹带物和新硫酸通过逆流或错流方式在酸洗分离罐中进行混合酸洗，并对酸洗后的烷基化反应产物进行初次分离；酸洗分离后的烷基化产物经过一级酸烃分离装置进行粗分离，得到一级油相和一级酸相；一级油相进入二级酸烃分离装置进行精细分离，得到二级油相和二级酸相，得到的二级油相中含酸量极低；含有极微量硫酸的烷基化产物会被送至吸附设备做最后的处理，处理后的烷基化产物中的硫酸基本除尽，净化后的烷基化产物被送入脱异丁烷塔或下一级工艺；酸洗分离罐分离出来的硫酸和硫酸酯以及一级酸相和二级酸相富集后均重新回到烷基化反应器中或者酸洗沉降罐中继续参与反应，节省了硫酸使用量。本发明方法效果可靠，经吸附装置后的烷基化产物中游离硫酸含量不超过1mg/kg，硫酸酯脱除率高达99.9％，进而可省去后续碱洗、水洗等工艺，缩短了流程，减少了投资，节省了能耗。
在本发明的第一方面，提供了一种烷基化产物脱硫脱酸的方法，该方法包括以下步骤：
(a)液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料以逆流或错流方式进入酸洗分离罐内酸洗、聚并分离，或者在送入酸洗罐前在混合器内充分混合；
(b)在酸洗分离罐下部的酸洗丝网填料，使硫酸酯和新鲜硫酸充分接触并相互溶解萃取，同时发生聚并分离；溶于硫酸的硫酸酯和烷基化产物中50％以上的硫酸作为重相沉降下来至酸洗分离罐底部，富集后送至酸洗沉降罐或者烷基化反应器或者外排；
(c)作为轻相的烷基化产物进入酸洗分离罐上部的分离丝网填料；在分离丝网填料上，作为轻相的烷基化产物中95％以上的硫酸被聚并分离，得到硫酸含量约为0.01％～1.0％的烷基化产物；聚并分离后的硫酸沉降至酸洗分离罐底部；
(d)硫酸含量约为0.01％～1.0％的烷基化产物从酸洗分离罐顶部被送至酸烃分离段进行酸烃分离；
(e)酸烃分离段为单级或多级酸烃分离装置，优选两级酸烃分离装置；在酸烃分离装置中对烷基化产物所夹带的硫酸进行粗分离和精细分离，得到硫酸含量低于10mg/kg的烷基化产物；分离出来硫酸富集后被送去酸洗沉降罐或者烷基化反应器或者外排；以及
(f)硫酸含量低于10mg/kg的烷基化产物被送至吸附装置中，以吸附剩余的、极其微量的硫酸，得到除去硫酸酯和硫酸的烷基化产物；而后被送至脱异丁烷塔脱异丁烷或者送入下一级工艺进行处理。
在本发明中，新硫酸和液态的含有硫酸和硫酸酯的烷基化产物以逆流或错流的形式进入酸洗分离罐，由于丝网填料特殊的、狭小的、不规格的孔道结构，在酸洗丝网填料上被分散成液滴或细流，增大了新硫酸和硫酸酯的接触面积和接触几率，使其充分接触溶解、萃取，或者在送入酸洗罐前在混合器内充分混合，以除去烷基化产物中的硫酸酯等有机硫化合物。酸洗丝网填料可以把新硫酸和夹带硫酸酯的烷基化产物等两股物料分散成液滴或细流，并提供接触载体，大大增大了新硫酸和硫酸酯的接触面积和接触几率，使其充分接触溶解，进而极大地提高新硫酸对硫酸酯的萃取量；充分混合可以提高新硫酸对硫酸酯的萃取量；逆流或错流的方式也可以增加新硫酸与硫酸酯的接触机会，也能对硫酸酯的萃取产生有益效果。多次实验证明：相较于在混合器内混合酸洗，以丝网填料为载体，不仅可以增强酸洗效果，而且还可以在酸洗的同时有聚并分离作用，大大增加了烷基 化产物中夹带硫酸酯去除率。
在本发明中，酸洗后的烷基化产物进入酸洗分离罐上部的分离丝网填料；在分离丝网填料上，烷基化产物中95％以上的硫酸被聚并分离，得到硫酸含量约为0.01％～1.0％的烷基化产物；分离后的硫酸沉降至酸洗分离罐底部。分离丝网填料可以有效拦截、聚并分离95％以上的硫酸和硫酸溶解物。剩下未除尽的硫酸经管道被送进酸烃分离段进行纤维膜分离，从而达到除尽烷基化产物中硫酸的目的。
在本发明中，两级酸烃分离装置梯度布置，以实现对烷基化产物中夹带的硫酸进行粗分离和精细分离；其中，一级酸烃分离装置粗分离得到的烷基化产物直接被送至二级酸烃分离装置进行精细分离。由于从酸洗分离罐顶部出来的硫酸含量较高，其他杂质也较多，且用于精细分离的纳米纤维膜过滤滤芯分离能力有限，并且孔隙较小，若直接进行精细分离，很可能会堵塞酸烃分离装置或者分离效果不好，故在精细分离前必须加上粗分离，以除去大颗粒的硫酸和其他杂质，故优选两级酸烃分离装置。由酸洗分离罐顶部出来的烷基化产物经管道进入一级酸烃分离装置，经流体均布整流板重新分布后，进入一级酸烃分离装置内部的纤维膜床进行粗分离，得到粗分离后的烷基化产物；而后经管道直接被送至二级酸烃分离装置，经流体均布整流板再次重新分布后，进入二级酸烃分离装置内部的纳米纤维膜过滤滤芯进行精细分离，得到硫酸含量低于10mg/kg的烷基化产物。一级和二级酸烃分离装置分离出来的一级酸相和二级酸相，富集后经管道被送去酸洗沉降罐或者烷基化反应器循环使用或者外排。
在本发明中，分离后的硫酸含量低于10mg/kg的烷基化产物进入装有交换吸附树脂床的吸附装置，交换吸附树脂可以吸附烷基化产物中夹带的硫酸，使其硫酸浓度降到1mg/kg以下。
在本发明的第二方面，提供了一种烷基化产物脱硫脱酸的装置，该装置包括：
混合器，用于使得新硫酸与含有硫酸酯和硫酸的烷基化产物充分混合；
与混合器相连的酸洗分离罐，用于分离硫酸酯和绝大部分烷基化产物中夹带的硫酸；
实现梯度分离的单级或多级酸烃分离装置，优选两级酸烃分离装置，即，与酸洗分离罐顶部相连的一级酸烃分离装置和与一级酸烃分离装置的油相出口相连的二级酸烃分离装置，其中，一级酸烃分离装置用于对烷基化产物中夹带的硫酸进行粗分离，以除去大颗粒粒径的硫酸；二级酸烃分离装置用于对烷基化产物中 夹带少量的硫酸进行精细分离，除去较小颗粒粒径的硫酸；
与酸烃分离段串联的吸附装置，其内部装有交换吸附树脂床，用于吸附烷基化产物中极微量的硫酸，以把烷基化产物中的硫酸浓度降到1mg/kg以下。
在本发明中，所述酸洗分离罐下部的酸洗丝网填料的空隙率大于90％，丝网纤维直径为0.3～4mm，厚度为100～300mm，由聚四氟乙烯纤维和金属纤维按照一定的编制方式编织而成；所述酸洗分离罐上部的分离丝网填料的空隙率为80％～90％，丝网纤维直径为0.1～3mm，厚度为200mm以上，其前半段由聚四氟乙烯纤维和金属纤维按照一定的编制方式编织而成，后半段由聚丙烯纤维和金属纤维按照一定的编制方式编织而成，其可以有效拦截、聚并分离95％以上的硫酸及其溶解物，剩下未除尽的硫酸将被送进酸烃分离段进行多级纤维膜分离，从而达到除尽烷基化产物中硫酸的目的。
在本发明中，所述酸洗分离罐内的酸洗丝网填料和分离丝网填料之间的最短距离为0.3～4D，且不少于500mm(D为酸洗分离器罐的内径)；混合液进料口或新硫酸进料口位于酸洗丝网填料和分离丝网填料之间空隙中部偏上处；所述进料口处设置防冲整流器，所述防冲整流器为选自多孔管、分支管、防冲挡板、斜板和列式叶片中的一种。
较佳地，设置实现梯度分离的两级或多级酸烃分离装置，优选两级酸烃分离装置。所述一级酸烃分离装置的内部装有两段具有特殊结构构造的纤维膜床，可分离大粒径的硫酸颗粒。所述二级酸烃分离装置的内部装有两段经过超亲水或超亲油改性处理的纳米纤维膜制成的过滤滤芯，能够有效分离粒径较小的硫酸颗粒。其有益效果是实现了对流出物中所夹带的酸进行梯度分离，特别是经过改性的纳米纤维材料对酸的分离能力更好。
在本发明中，所述一级酸烃分离装置的内部装有两段具有特殊结构构造的纤维膜床；所述纤维膜床的孔隙率为80％～90％，所述纤维膜床的纤维直径小于200μm；每段纤维膜床厚度为200mm以上；其中每段纤维膜床的前半段由聚四氟乙烯纤维编织而成；每段纤维膜床的后半段由选自金属纤维、聚四氟乙烯纤维、聚丙烯纤维和聚酯纤维等中的一种或多种编织而成。
在本发明中，所述二级酸烃分离装置的内部装有两段经过超亲水或者超亲油改性处理的纳米纤维膜制成的过滤滤芯；所述纤维膜的孔隙率小于80％，纤维直径小于100μm；所述每段滤芯的纳米纤维膜厚度为50mm以上；所述纳米纤维膜 是由选自金属纤维、聚四氟乙烯纤维、聚丙烯纤维和聚酯纤维等中的一种或多种经改性后编织而成的。
在本发明中，所述一级和二级酸烃分离装置内部的每两段纤维膜床之间的间隔最短距离为0.1～0.5D’，且不少于500mm；酸烃分离装置后面沉降段最短距离为0.3～2D’，且不少于1000mm(D’为酸烃分离装置的内径)。
在本发明中，所述一级和二级酸烃分离装置的内部进口处均有流体均布整流板，所述流体均布整流板为多孔均布的开孔厚板。
以下参看附图。
图1是根据本发明的一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。如图1所示，酸洗分离罐1下部装有一段酸洗丝网填料2，上部装有一段分离丝网填料3，两段丝网填料之间相隔至少500mm；新硫酸从两层丝网填料之间且靠近分离丝网填料3一侧进入，烷基化产物从底部进入，经防冲整流器4整流后，两股物流以逆流的形式进入酸洗分离罐1；下部的酸洗丝网填料2可以把新硫酸和夹带硫酸酯的烷基化产物等两股物料分散成液滴或细流，并提供接触载体，大大增大了新硫酸和硫酸酯的接触面积和接触几率，使其充分接触溶解，从而有利于硫酸酯溶于硫酸中，聚集并沉降下来；上部的分离丝网填料3可以有效的拦截聚并分离95％以上的硫酸，得到含有少量硫酸的烷基化产物；酸洗分离后的烷基化产物(烷类与少量硫酸)从酸洗分离罐1顶部引出；沉降下来的硫酸与硫酸酯和在酸洗分离罐1底部富集后，被送回酸洗沉降罐或者烷基化反应器或者外排；含有少量硫酸的烷基化产物会被送到一级酸烃分离装置7进行粗分离；进入一级酸烃分离装置7后会经流体均布整流板8，随后经过两段纤维膜床8和9进行粗分离，烷基化产物中的酸浓度进一步降低，主要去除了夹带的大粒径硫酸；随后再进入二级酸烃分离装置10继续聚并分离，经流体均布整流板11，随后经过两段纤维膜过滤滤芯料11和12进行精细分离，烷基化产物中的酸含量降至10mg/kg以下，主要去除了夹带的小粒径硫酸；酸烃分离装置分离出来的硫酸富集后会被送回酸洗沉降罐或者烷基化反应器或者外排；对于剩余的、极其微量的、粒径更小的硫酸将被送去吸附装置13除去，吸附装置13内装有交换吸附树脂床14，可以将硫酸浓度降到1mg/kg，甚至更低；从吸附装置13出来的烷基化产物中的硫酸几乎全部除净，满足下一级工艺要求，会被送去脱异丁烷塔或者下一级工艺。
图2是根据本发明的另一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。如图2所示，在循环泵5的推动下新硫酸和液态的含有硫酸和硫酸酯等的烷基化产物等两股物流以错流的形式进入混合器6充分混合后，经防冲整流器4整流后进入酸洗分离罐1；酸洗分离罐1下部的酸洗丝网填料2可以把新硫酸和夹带硫酸酯的烷基化产物等两股物料分散成液滴或细流，并提供接触载体，大大增大了新硫酸和硫酸酯的接触面积和接触几率，使其充分接触溶解，从而有利于硫酸酯溶于硫酸中，聚集并沉降下来；酸洗分离罐1上部的分离丝网填料3可以有效的拦截聚并分离大部分的硫酸，得到含有少量硫酸的烷基化产物；酸洗分离后烷基化产物(烷类与少量硫酸)从酸洗分离罐1顶部引出；沉降下来的硫酸与硫酸酯在酸洗分离罐1底部富集后，被送回酸洗沉降罐或者烷基化反应器或者外排；含有少量硫酸的烷基化产物会被送到一级酸烃分离装置7进行粗分离；进入一级酸烃分离装置7后会经流体均布整流板8，随后经过两段纤维膜床9进行粗分离，烷基化产物中的酸浓度进一步降低，主要去除了夹带的大粒径硫酸；随后再进入二级酸烃分离装置10继续聚并分离，经流体均布整流板11，随后经过两段纤维膜过滤滤芯12进行精细分离，烷基化产物中的酸含量降至10mg/kg以下，主要去除了夹带的小粒径硫酸；酸烃分离装置分离出来的硫酸富集后会被送回酸洗沉降罐或者烷基化反应器或者外排；对于粒径更小的硫酸将被送去吸附装置13除去，吸附装置13内装有交换吸附树脂床14，可以将硫酸浓度降到1mg/kg，甚至更低；从吸附装置13出来的烷基化产物中的硫酸几乎全部除净，满足下一级工艺要求会被送去脱异丁烷塔或者下一级工艺。
图3是根据本发明的再一个实施方式的烷基化产物脱硫脱酸工艺流程示意图。如图3所示，在循环泵5的推动下新硫酸和液态的含有硫酸和硫酸酯等的烷基化产物等两股物流以错流的形式进入混合器6充分混合后，经防冲整流器4整流后进入酸洗分离罐1；酸洗分离罐1下部的酸洗丝网填料2和上部的分离丝网填料3可以提供接触载体，增大了新硫酸和硫酸酯的接触面积和接触几率，使其充分接触溶解，从而有利于硫酸酯溶于硫酸中，并通过聚并作用除去硫酸酯和绝大部分的硫酸，得到含有少量硫酸的烷基化产物；酸洗分离后烷基化产物(烷类与少量硫酸)从酸洗分离罐1顶部引出；沉降下来的硫酸与硫酸酯在酸洗分离罐1底部富集后，被送回酸洗沉降罐或者烷基化反应器或者外排；含有少量硫酸的烷基化产物会被送到一级酸烃分离装置7进行粗分离；进入一级酸烃分离装置7后会经 流体均布整流板8，随后经过两段纤维膜床9进行粗分离，烷基化产物中的酸浓度进一步降低，主要去除了夹带的大粒径硫酸；随后再进入二级酸烃分离装置10继续聚并分离，经流体均布整流板11，随后经过两段纤维膜过滤滤芯12进行精细分离，烷基化产物中的酸含量降至10mg/kg以下，主要去除了夹带的小粒径硫酸；酸烃分离装置分离出来的硫酸富集后会被送回酸洗沉降罐或者烷基化反应器或者外排；对于粒径更小的硫酸将被送去吸附装置13除去，吸附装置13内装有交换吸附树脂床14，可以将硫酸浓度降到1mg/kg，甚至更低；从吸附装置13出来的烷基化产物中的硫酸几乎全部除净，满足下一级工艺要求会被送去脱异丁烷塔或者下一级工艺。
本发明的方法和装置的主要优点在于：
本发明将重力沉降、聚并分离、纤维膜分离、吸附分离等四种分离方法和表面改性技术有效结合起来，并通过多级分离针对性的来实现对烷基化产物中所夹带的酸的分离，可以适应不同的酸浓度，具有很高的分离效率和处理能力，能有效去除烷基化产物中夹带的硫酸和硫酸酯，使其含量满足下一级生产工艺的要求；其过程不需要水洗和碱洗也不需要加入任何催化剂，简化了烷基化生产工艺过程，从而克服了水洗、碱洗和加入任何催化剂对下级工艺装置的影响问题，缩短了流程，减少了投资，节省了能耗。
实施例
下面结合具体的实施例进一步阐述本发明。但是，应该明白，这些实施例仅用于说明本发明而不构成对本发明范围的限制。下列实施例中未注明具体条件的试验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另有说明，所有的百分比和份数按重量计。
实施例1：
山东某石化公司试用了本发明的烷基化产物脱硫脱酸装置，对其烷基化反应产物中所含有的硫酸和硫酸酯等杂质进行分离，以保证下游生产装置的安全和优化生产工艺，减少成本。
其具体运作和效果描述如下：
烷基化产物脱硫脱酸过程主要参数：酸洗分离罐工作压力为0.5MPa，补充的新硫酸＝98重量％，烷基化产物处理量为13t/h，其中硫酸含量为15重量％，硫酸酯＝2～3重量％。
下表1中示出了酸洗分离罐设计物性参数：
表1
Figure PCTCN2015098011-appb-000001
下表2中示出了第一级酸烃分离装置设计参数：
表2
Figure PCTCN2015098011-appb-000002
实施过程：
工艺流程如图1所示。
新硫酸从两层丝网填料之间且靠近分离丝网填料一侧进入，液态的烷基化产物从底部进入，两股物流以逆流的形式进入酸洗分离罐。在酸洗丝网填料上，大部分硫酸酯和新硫酸充分接触溶解，并和硫酸一起作为重相沉降下来至酸洗罐底部。作为轻相的烷基化产物向上运动至上部的分离丝网填料，大部分夹带在烷基化产物里的硫酸被聚并分离。夹带少量硫酸的基化产物从酸洗分离罐顶部被送至一级酸烃分离装置，先经均布整流板进行整流后穿过两段纤维膜床，分离出大颗粒粒径的硫酸；净化后的烷基化产物由一级酸烃分离装置油相出口进入二级酸烃分离装置，经均布整流板重新整流后穿过两段纤维膜过滤滤芯，分离出小颗粒粒径的硫酸；二级酸烃分离装置油相出口出来的烷基化产物进入吸附装置，吸附剩余的及其微量的硫酸，随后进入下一级工艺。
平稳流动的液态酸烃混合物经防冲整流器整流后进入酸洗分离罐，进而进入一级酸烃分离装置和二级酸烃分离装置。其中酸洗分离罐下部酸洗丝网填料和上部分离丝网填料均由316L金属纤维(购自宝山钢铁集团公司)按照一定方式编制而成，只是二者的纤维直径和填料厚度不同。一级酸烃分离装置内部的纤维膜床和二级酸烃分离装置内部的纤维膜过滤滤芯均由316L金属纤维和聚四氟乙烯纤维按照一定比例、一定方式编制而成。
结果分析：
经过使用本发明的装置，酸洗分离灌顶部硫酸含量约0.1％～0.4％，硫酸酯已基本除尽，一级酸烃分离装置油相出口的烷基化产物中硫酸浓度约为100mg/kg，二级酸烃分离装置油相出口的烷基化产物中硫酸浓度小于10mg/kg，由吸附装置出来的烷基化产物中几乎检测不出硫酸含量，完全达到了下游生产工艺的要求。
实施例2：
河北省某石化公司烷基化中试装置试用了本发明的烷基化产物脱硫脱酸装置，对其烷基化反应产物中所含有的硫酸和硫酸酯等杂质进行分离，以保证下游生产装置的安全和优化生产工艺，减少成本。
其具体运作和效果描述如下：
烷基化产物脱硫脱酸过程主要参数：酸洗分离罐工作压力为0.6MPa，补充的新硫酸＝98重量％，烷基化产物处理量为500L/h，其中硫酸含量＝18重量％，硫酸酯＝1～2.5重量％。
实施过程：
工艺流程如图2所示。
在循环泵的推动下新鲜硫酸和含有硫酸和硫酸酯等的烷基化产物在混合器充分混合后进入酸洗分离罐。在酸洗丝网填料上，大部分硫酸酯和新硫酸充分接触溶解，并和硫酸一起作为重相沉降下来至酸洗分离罐底部。作为轻相的烷基化产物向上运动至上部的分离丝网填料，绝大部分夹带在烷基化产物里的硫酸被聚并分离。夹带少量硫酸的基化产物从酸洗罐顶部被送至一级酸烃分离装置，先经均布整流板进行整流后穿过两段纤维膜床，分离出大颗粒粒径的硫酸；净化后的烷基化产物由一级酸烃分离装置油相出口进入二级酸烃分离装置，经均布整流板重新整流后穿过两段纤维膜过滤滤芯，分离出小颗粒粒径的硫酸；二级酸烃分离装置油相出口出来的烷基化产物完全满足工艺要求，随后直接进入下一级工艺。
平稳流动的液态酸烃混合物经防冲整流器整流后进入酸洗分离罐，进而进入一级酸烃分离装置和二级酸烃分离装置。其中酸洗分离罐下部酸洗丝网填料由直径为2mm的316L金属丝(购自宝山钢铁集团公司)按照一定方式编制而成，厚度为200mm；酸洗分离罐上部分离丝网填料由直径为1mm的316L金属丝和聚四氟乙烯按照一定比例、一定方式编制而成，厚度为300mm；一级酸烃分离装置内部的纤维膜床均由金属纤维、聚四氟乙烯纤维和聚丙烯纤维按照一定比例、一定方式编制而成，二级酸烃分离装置内部的纤维膜过滤滤芯由聚丙烯和聚四氟乙烯纤维按照一定比例、一定的方式编制而成。
结果分析：
经过使用本发明的装置，酸洗分离灌顶部硫酸含量约0.5％，硫酸酯已基本除尽，一级酸烃分离装置油相出口的烷基化产物中硫酸浓度约为30～150mg/kg，二级酸烃分离装置油相出口的烷基化产物中硫酸浓度均小于6mg/kg；完全达到了下游生产工艺的要求。
下表3中示出了工业现场中试试验中第一级酸烃分离装置进出口硫酸含量的 部分实验数据。
表3
Figure PCTCN2015098011-appb-000003
上述所列的实施例仅仅是本发明的较佳实施例，并非用来限定本发明的实施范围。即凡依据本发明申请专利范围的内容所作的等效变化和修饰，都应为本发明的技术范畴。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种烷基化产物脱硫脱酸的方法，该方法包括以下步骤：
    (a)将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料以逆流或错流方式送入酸洗分离罐(1)内酸洗、聚并分离；
    (b)在酸洗分离罐(1)下部的酸洗丝网填料(2)中，硫酸酯和新硫酸充分接触并相互溶解萃取，同时发生聚并分离；溶于硫酸的硫酸酯和烷基化产物中超过50％的硫酸作为重相沉降下来至酸洗分离罐(1)底部，富集后送至酸洗沉降罐或者烷基化反应器或者外排；
    (c)作为轻相的烷基化产物进入酸洗分离罐(1)上部的分离丝网填料(3)，其中，在分离丝网填料(3)上，作为轻相的烷基化产物中超过95％的硫酸被聚并分离，得到硫酸含量为0.01％～1.0％的烷基化产物；聚并分离后的硫酸沉降至酸洗分离罐(1)底部；
    (d)所得的硫酸含量为0.01％～1.0％的烷基化产物从酸洗分离罐(1)顶部被送至酸烃分离段进行酸烃分离，其中，所述酸烃分离段为单级或多级酸烃分离装置；
    (e)在酸烃分离装置中对所述硫酸含量为0.01％～1.0％的烷基化产物中所夹带的硫酸进行粗分离和精细分离，得到硫酸含量低于10㎎/㎏的烷基化产物；分离出来硫酸富集后被送去酸洗沉降罐或者烷基化反应器或者外排；以及
    (f)所得的硫酸含量低于10㎎/㎏的烷基化产物被送至吸附装置(13)中，以吸附剩余的含量低于10㎎/㎏的硫酸，得到除去了硫酸酯和硫酸的烷基化产物。
  2. 如权利要求1所述的方法，其特征在于，所述步骤(a)还包括：在将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料以逆流或错流方式送入酸洗分离罐内(1)之前，在混合器(6)内使其充分混合。
  3. 如权利要求1或2所述的方法，其特征在于，在步骤(d)中，所述酸烃分离段为两级酸烃分离装置梯度布置，一级酸烃分离装置(7)粗分离得到的烷基化产物直接被送至二级酸烃分离装置(10)进行精细分离。
  4. 如权利要求1或2所述的方法，其特征在于，在步骤(f)中，所得的硫酸含量低于10㎎/㎏的烷基化产物被送至装有交换吸附树脂床(14)的吸附装置(13)中，以吸附剩余的含量低于10㎎/㎏的硫酸，使其硫酸浓度降到低于1㎎/㎏。
  5. 一种烷基化产物脱硫脱酸的装置，该装置包括：
    酸洗分离罐(1)，用于对送入其中的液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料进行酸洗、聚并分离；
    在酸洗分离罐(1)下部的酸洗丝网填料(2)，用于使得硫酸酯和新鲜硫酸充分接触并相互溶解萃取，同时发生聚并分离；
    在酸洗分离罐(1)上部的分离丝网填料(3)，用于使经过酸洗丝网填料(2)后的烷基化产物中超过95％的硫酸被聚并分离，得到硫酸含量为0.01％～1.0％的烷基化产物；
    与酸洗分离罐(1)连接的酸烃分离段，其中，所述酸烃分离段为单级或多级酸烃分离装置，用于对所述硫酸含量为0.01％～1.0％的烷基化产物中所夹带的硫酸进行粗分离和精细分离，得到硫酸含量低于10㎎/㎏的烷基化产物；
    与酸烃分离段连接的吸附装置(13)，用于吸附剩余的含量低于10㎎/㎏的硫酸，得到除去了硫酸酯和硫酸的烷基化产物。
  6. 如权利要求5所述的装置，其特征在于，该装置还包括：与酸洗分离罐(1)连接的混合器(6)，用于在将液态的含有硫酸和硫酸酯的烷基化产物和新硫酸两股物料送入酸洗分离罐内(1)之前，使其充分混合。
  7. 如权利要求5或6所述的装置，其特征在于，所述酸烃分离段为两级酸烃分离装置梯度布置，一级酸烃分离装置(7)粗分离得到的烷基化产物直接被送至与其连接的二级酸烃分离装置(10)进行精细分离。
  8. 如权利要求5或6所述的装置，其特征在于，所述吸附装置(13)装有交换吸附树脂床(14)，用于吸附剩余的含量低于10㎎/㎏的硫酸，使其硫酸浓度降到低于1㎎/㎏。
  9. 如权利要求5或6所述的装置，其特征在于，所述酸洗丝网填料(2)的空隙率大于90％，丝网纤维直径为0.3～4mm，厚度为100～300mm，由聚四氟乙烯纤维和金属纤维编织而成；所述分离丝网填料(3)的空隙率为80％～90％，丝网纤维直径为0.1～3mm，厚度大于200mm，其前半段由聚四氟乙烯和金属纤维编织而成，后半段由聚丙烯和金属纤维编织而成；并且，所述酸洗丝网填料(2)和分离丝网填料(3)之间的最短距离为0.3～4D，且不少于500mm，其中D为酸洗分离器罐(1)的内径；混合液进料口或新硫酸进料口位于酸洗丝网填料(2)和分离丝网填料(3)之间空隙中部偏上处；所述进料口处设置防冲整流器(4)， 所述的防冲整流器(4)选自多孔管、分支管、防冲挡板、斜板和列式叶片中的一种。
  10. 如权利要求5或6所述的装置，其特征在于，所述一级酸烃分离装置(7)的内部装有两段纤维膜床(9)，所述纤维膜床(9)的孔隙率为80％～90％，纤维直径小于200μm，厚度大于200mm；其中，每段纤维膜床(9)的前半段由聚四氟乙烯纤维编织而成，后半段由选自金属纤维、聚丙烯纤维、聚四氟乙烯纤维和聚酯纤维中的一种或多种编织而成；所述二级酸烃分离装置(10)的内部装有两段经过超亲水或者超亲油改性处理的纳米纤维膜制成的纤维膜过滤滤芯(12)，所述纤维膜的孔隙率小于80％，纤维直径小于100μm，厚度大于50mm；其中，所述纳米纤维膜是由选自金属纤维、聚四氟乙烯纤维、聚丙烯纤维和聚酯纤维中的一种或多种经改性后编织而成的；并且，所述一级酸烃分离装置(7)内部的纤维膜床(9)之间以及二级酸烃分离装置(10)内部的纤维膜过滤滤芯(12)之间的间隔最短距离为0.1～0.5D，且不少于500mm；一级酸烃分离装置(7)和二级酸烃分离装置(10)后面沉降段的最短距离为0.3～2D’，且不少于1000mm，其中D’为一级酸烃分离装置(7)和二级酸烃分离装置(10)的内径；所述一级酸烃分离装置(7)和二级酸烃分离装置(10)的内部进口处分别有流体均布整流板(8)和(11)，所述流体均布整流板(8)和(11)为多孔均布的开孔厚板。
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