CN112920844A - Device and method for improving quality of alkylated oil product - Google Patents

Device and method for improving quality of alkylated oil product Download PDF

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CN112920844A
CN112920844A CN202110072525.6A CN202110072525A CN112920844A CN 112920844 A CN112920844 A CN 112920844A CN 202110072525 A CN202110072525 A CN 202110072525A CN 112920844 A CN112920844 A CN 112920844A
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acid
separation
sulfuric acid
tower
alkylation
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CN112920844B (en
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白志山
鲁朝金
杨晓勇
王炳捷
吕福炜
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East China University of Science and Technology
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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
    • 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
    • C10G53/10—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one acid-treatment step
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

Fresh sulfuric acid and alkylation effluent are mixed by a mixer and then are subjected to acid washing separation in an acid washing tower, separated heavy-phase sulfuric acid is partially returned to a reactor or sent to a waste acid tank, the rest of the sulfuric acid is pumped back to the acid washing tower for cyclic acid washing extraction, separated light-phase effluent is introduced into a coalescer and a filter for coalescence separation and filtration separation, then is introduced into an deisobutanizer for fractionation to obtain alkylate, normal butane and isobutane, and finally the alkylate flows into an adsorption tank for deep adsorption. Also provides a device for improving the quality of the alkylated oil product. After the alkylation effluent is treated by the method, the sulfur content can be lower than 5 mg/kg per kg, and the traditional alkali washing and water washing process can be replaced; the whole separation system is operated in a dry mode, so that the energy consumption and the acid consumption can be greatly reduced, and the corrosion of equipment is avoided; solves the problems of poor pickling effect, low deacidification and desulfurization precision, short service life of the adsorbent and high sulfur content of the alkylate oil, and realizes the clean production of the alkylate oil.

Description

Device and method for improving quality of alkylated oil product
Technical Field
The invention belongs to the technical field of petrochemical oil refining treatment, and relates to a device and a method for improving the quality of an alkylated oil product, in particular to a method for removing organic sulfur compounds (such as mercaptan, thioether and thioester) and sulfuric acid in an alkylation reaction effluent by using acid washing separation, circulating liquid drop mass transfer, coalescence separation, ceramic ball filtration and deep adsorption.
Background
With the increasing strictness of the national environmental protection requirements, the upgrading pace of the quality of the national finished oil is accelerated, the comprehensive implementation of the national V gasoline standard and the coming promotion of the national VI gasoline standard promote the alkylate oil with high octane number and clean environmental protection to become the focus of attention of the petroleum refining industry. The alkylate oil has the advantages of no alkene, no aromatic hydrocarbon, low sulfur, high octane number, low vapor pressure and the like, and is an ideal component for preparing clean gasoline.
The alkylate oil is prepared by carrying out alkylation reaction on isobutane and butene under the action of an acid catalyst. Sulfuric acid and hydrofluoric acid are currently used as alkylation catalysts in industry, and due to the problems of toxicity, corrosivity, safety, environmental pollution and the like, a great deal of manpower, material resources and financial resources are invested at home and abroad to improve and enhance the liquid acid alkylation process, and important progress is made. Since sulfuric acid is better than hydrofluoric acid in safety, most of newly built alkylation devices in recent 20 years adopt a sulfuric acid process, and thus research on improvement of the sulfuric acid process is also active. The mainstream technologies of the existing sulfuric acid alkylation are mainly divided into two types: the first method is represented by a CDAlky process of Rumses and an SINOALKY process of a petrochemical engineering science research institute of China petrochemical industry, Inc., and the reaction temperature is-3 ℃; the other is represented by a STRATCO process of DuPont, and the reaction temperature is 3-8 ℃. However, sulfuric acid alkylation carries small amounts of sulfuric acid and sulfur-containing impurities in the reactor effluent, affects product quality, and causes severe corrosion to downstream equipment, and therefore, requires effective separation.
At present, the refining process of alkylated products mainly adopts an acid washing-alkali washing-water washing process to remove a small amount of sulfuric acid and sulfur-containing impurities contained in reaction effluents, and the acid-alkali neutralization process and the separation process of the process are easy to cause equipment corrosion, influence equipment stability and cause additional acid consumption and alkali consumption. Chinese patent CN102021016B discloses a deacidification method for alkylated effluent, which uses a hydrophobic modified ceramic membrane assembly for separation to reduce the amount of alkali and wastewater in the acid-base refining system of the alkylation process. Chinese patents CN1688524A and CN110305690A provide means for removing sulfuric acid from alkylate by means of mechanical coalescers and single and multi-stage coalescence-separation devices, respectively, instead of aqueous alkaline washing process. Chinese patent CN108070401B discloses a method for separating acid and hydrocarbon from alkylation effluent by sequentially passing through a membrane separation device, an acid injection mixing device, a cyclone and a coalescer, and omits the traditional complex treatment processes of alkali washing, water washing and the like. Although the above patents can remove the sulfuric acid from the alkylation effluent efficiently, the removal effect on the sulfur-containing compounds (such as sulfate) dissolved in the oil phase is very small, and the sulfur content in the product alkylate after deisobutanization fractionation is still very high, which is difficult to meet the production requirements. Chinese patent CN104927907B provides a method and apparatus for implementing desulfurization and deacidification of alkylation effluent by using "acid washing + coalescence + adsorption" technology. Although the alkaline washing process is omitted under the condition of ensuring the product to be qualified, the problems of poor acid washing effect and short service life of the adsorbent are solved, and the problem that the industrial application of the adsorbent is disturbed by high replacement frequency of the adsorbent.
Therefore, there is an urgent need in the art to develop a device and method that can replace the alkaline washing and water washing processes, efficiently remove or separate sulfuric acid and sulfur-containing impurities (such as mercaptans, thioethers, thioesters, etc.) in the alkylation effluent, and can reduce the consumption of the adsorbent, prolong the service life of the adsorbent, and improve the quality of the alkylated oil product.
Disclosure of Invention
The invention aims to solve the problems of poor acid pickling mixing effect, low deacidification and desulfurization precision, short service life of an adsorbent and high sulfur content of alkylate in the existing alkylate effluent treatment technology, and provides a novel device and a novel method for continuously carrying out acid pickling separation, fiber coalescence separation, ceramic ball filtration separation, product fractionation and deep adsorption treatment on alkylate effluent, so that sulfuric acid and sulfur-containing substances are efficiently separated and removed, the using amount of the adsorbent is reduced, the using time of the adsorbent is prolonged, the sulfur content of alkylate is reduced, and the quality of alkylate is improved.
In one aspect, the present invention provides an apparatus for improving the quality of an alkylate oil, comprising:
a mixer is connected with the pickling tower, the middle part of the small-diameter straight cylinder section at the lower part of the pickling tower is provided with a layer of fiber film forming internal part, and the middle part of the large-diameter straight cylinder section at the upper part of the pickling tower is provided with a layer of fiber separating internal part;
a coalescer is connected with a light phase outlet at the top of the pickling tower through an inlet of the coalescer, a combined fiber separation internal part is arranged at the front section of the coalescer, and a filter element separation internal part is arranged at the rear section of the coalescer;
a filter is connected with the upper light phase outlet of the coalescer through the inlet of the filter, and a micro-ceramic ball filter internal part is arranged in the filter;
the heavy phase outlets at the lower parts of the pickling tower, the coalescer and the filter are all connected with pipelines leading to the reactor or the discharge;
and the deisobutanizer is connected with a light phase outlet of the filter through an inlet of the deisobutanizer, the light phase outlet at the top of the tower is connected with the reactor, the upper part of the tower is provided with a normal butane discharge outlet, a heavy phase outlet at the bottom of the tower is connected with the adsorption tank, and the adsorption tank is filled with high-efficiency adsorption microspheres.
One end of a circulating pump is connected with a heavy phase outlet at the bottom of the pickling tower, and the other end of the circulating pump returns to the connecting pipe type distributor of the pickling tower.
The main body of the combined fiber separating internal member in the coalescer is formed by weaving acidophilic fibers with a contact angle less than 60 degrees, and the combined fiber separating internal member contains a plurality of layers of columnar film-forming fillers and a plurality of layers of inclined acid-discharging fillers; the columnar film-forming filler consists of acid-phobic fibers with contact angles of more than 120 degrees, the thickness T1 is 0.05-0.1L1, and the distance L2 is 0.1-0.3L 1; the inclined acid-removing filler consists of acid-repellent fibers with contact angles larger than 150 degrees, the inclination angle alpha is 130-150 degrees, the axial thickness T2 is 0.2-0.4L1, the radial thickness T3 is 0.05-0.1D, and the distance L3 is 0.1-0.3D; where L1 is the combined fiber separation internal length and D is the internal diameter of the barrel.
The exterior of the micro ceramic ball filtering internal part in the filter is wrapped by an acidophilic fiber filler, and the interior of the micro ceramic ball filtering internal part is a porous micro ceramic ball filling internal part; the porosity of the acidophilic fibrous filler is 50-70%, the thickness T4 is 0.05-0.2L3, and the acid contact angle of the acidophilic fibrous filler is less than 50 degrees; the porous micro-ceramic ball is super-hydrophilic and has the bulk density of 1200-1800kg/m3The particle size is 2-4mm, the average particle size is 3mm, and the pore volume is 0.6-0.8 wt%.
The high-efficiency adsorption microspheres in the adsorption tank are alkaline adsorbents, and the bulk density is 600-800kg/m3The particle size is 2-5mm, the average particle size is 3.2mm, the pore volume is 0.5-0.7 wt%, and the specific surface area is 300-400m2/g。
The acidphilic fiber is one or more selected from 904L metal fiber, glass fiber and polyamide fiber, or the acidphilic fiber is modified fiber which makes the contact angle of the fiber and acid less than 60 degrees by changing roughness or coating acidphilic coating on the surface.
The hydrophobic and acidic fiber is one or more selected from polytetrafluoroethylene fiber, polypropylene fiber and polyethylene fiber, or the hydrophobic and acidic fiber is modified fiber by changing roughness or coating hydrophobic and acidic coating on the surface so that the contact angle between the fiber and acid is more than 120 degrees.
In another preferred embodiment, on the basis that the adsorption tank is arranged after the deisobutanizer, the same adsorption tank is additionally arranged before the deisobutanizer, so that the sulfur content in the alkylation effluent is removed to the maximum extent, and the qualified sulfur content of the product alkylate is ensured.
In another aspect, the present invention provides a method for improving the quality of an alkylate oil, comprising the steps of:
(a) injecting fresh sulfuric acid into the alkylation effluent from the alkylation reactor, uniformly mixing by using a mixer, introducing into an acid washing tower for acid washing and separation, realizing enrichment of sulfur-containing impurities in the alkylation effluent into the fresh sulfuric acid in the processes of strong mixing and countercurrent acid washing, and settling the separated sulfuric acid as a heavy phase to the bottom of the acid washing tower and returning to the reactor or discharging to obtain the alkylation effluent after acid washing;
(b) introducing the alkylation effluent after acid washing in the step (a) into a multilayer internal member coalescer for fiber coalescence separation and filter element coalescence separation, and removing sulfur-containing impurities dissolved in sulfuric acid and more than 90% of sulfuric acid in the alkylation effluent to obtain alkylation effluent after fine coalescence separation;
(c) introducing the alkylation effluent subjected to fine coalescence separation in the step (b) into a filter for micro-ceramic ball filtration separation so as to remove sulfur-containing impurities and over 95% of sulfuric acid in the alkylation effluent, thereby obtaining the alkylation effluent subjected to filtration separation;
(d) introducing the alkylation effluent after filtration and separation in the step (c) into an isobutane removal tower for product fractionation, extracting isobutane from the tower top and returning the isobutane to an alkylation reactor, discharging n-butane from the upper part of the tower, and collecting alkylate oil from the tower bottom;
(e) directly sending the alkylate oil obtained in the step (d) to an adsorption tank for deep adsorption purification, and removing residual sulfur-containing impurities and sulfuric acid to obtain purified alkylate oil.
Wherein, the alkylation effluent after the reactor is a gas-liquid mixed phase from a STRATCO sulfuric acid alkylation reactor, a CDAlky sulfuric acid alkylation reactor or a SINOALKY sulfuric acid alkylation reactor, and sulfur-containing impurities contained in the effluent mainly comprise mercaptan, thioether and thioester.
In the step (a), the sulfuric acid part obtained from the bottom of the pickling tower after pickling returns to the pickling tower through a circulating pump, and the sulfuric acid is subjected to micro-acid drop dispersion through a tubular distributor, so that the sulfuric acid is used for circularly extracting sulfur-containing impurities in the pickling tower.
In step (a) of the process, the concentration of fresh sulfuric acid is not less than 96%, and the injection amount of fresh sulfuric acid is 2-15% of the volume flow of the alkylation effluent.
In steps (b) and (c) of the process, the coalescence-separation process of the coalescer and the filtration-separation process of the filter are carried out at a flow rate of the alkylation effluent of 0.005 to 0.1m/s and a pressure drop of 0.02 to 0.1 MPa.
After the alkylation effluent is subjected to acid washing separation in the step (a), the content of sulfuric acid in the alkylation effluent is reduced to 0.02-1.5 percent; after the fine coalescence-separation treatment in the step (b), the total sulfur content in the alkylation effluent is reduced to 50-200 mg/kg; after the filtration and separation treatment by the micro porcelain balls in the step (c), the total sulfur content in the alkylation effluent is reduced to 15-30 mg/kg per kg of water or lower; after deep adsorption in step (e), the total sulfur content of the alkylate is reduced to 1-5 mg/kg.
The effective benefits are as follows:
the method and the device have the main advantages that:
(1) the acid washing process realizes the mixing mass transfer of the mixer, the film forming mass transfer of the internal parts at the bottom of the acid washing tower and the sulfuric acid circulating dispersion mass transfer in the acid washing tower, promotes the enrichment of organic acid and sulfur-containing impurities in the alkylation effluent into fresh sulfuric acid by the three times of mass transfer strengthening process, improves the washing effect of acid washing of the alkylation effluent, and reduces the consumption of the fresh sulfuric acid; meanwhile, the coalescence separation process of the fiber separation internals at the top of the pickling tower can carry out sulfuric acid pre-separation on the alkylation effluent after sulfuric acid is injected, and the special structure of the diameter expansion of the upper straight cylinder of the pickling tower can reduce the fluid flow rate and improve the sulfuric acid separation efficiency.
(2) The coalescer internal part adopts a novel isomeric combined fiber separating internal part, and the multilayer cylindrical acidity-phobic film-forming filler arranged at the front section of the combined fiber separating internal part is beneficial to forming an acid liquid film on the interface of the acidophilic fiber and the acidity-phobic fiber by sulfuric acid, strengthening sulfur-containing impurities in sulfuric acid extraction alkylation effluent, and improving the deacidification and desulfurization efficiency of the fiber internal part; the special directional liquid drainage channel is favorable for quickly discharging the sulfuric acid after coalescence in the internal member and realizing fine and quick separation of micro acid drops in alkylation effluent.
(3) In the filter, porous micro-ceramic balls are filled in the micro-ceramic ball filtering internal part, and the exterior is wrapped with an acidophilic fiber filler. The high pore volume of the porous micro-ceramic ball has strong adsorbability to acid drops, the hydrophilicity and the small particle size of the ceramic ball can adhere sulfuric acid, the coalescence among the acid drops is enhanced, meanwhile, the externally wrapped acid-philic fiber filler with low porosity has high deacidification efficiency, and the combination of the inside and the outside wrapping between the ceramic ball and the filler can greatly improve the separation precision of the acid drops.
(4) The new method of the invention creatively puts the adsorption tank behind the deisobutanizer, directly and specifically deeply adsorbs the liquid-phase alkylate, and overcomes the defects that the adsorption tank is put in front of the deisobutanizer, which causes extra consumption of sulfide in effluent gas phase to the adsorbent and short service life of the adsorbent; in addition, the alkaline adsorbent has large pore volume and specific surface area, provides more acid adsorption sites for sulfide, and improves the removal rate of sulfur-containing impurities.
(5) The device and the method are suitable for refining oil products, are also suitable for devices for extraction separation in oil refining chemical industry, removal of harmful substances in liquid and the like, and are suitable for great popularization in the petrochemical industry.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification to further illustrate the invention and not limit the invention.
FIG. 1 is a schematic diagram of the apparatus and process of the present invention.
Wherein: 1-mixer, 2-acid cleaning tower, 2-1-fiber film-forming internal part, 2-2-fiber separating internal part, 3-circulating pump, 4-coalescer, 4-1-combined fiber separating internal part, 4-2-filter element separating internal part, 5-filter, 5-1-micro ceramic ball filtering internal part, 6-deisobutanizer and 7-adsorption tank.
FIG. 2 is a schematic cross-sectional view of a composite fiber separating internal in a coalescer according to the invention.
Wherein: 411-column film forming filler, 412-oblique acid discharging filler.
FIG. 3 is an axial schematic view of a composite defibrator internals in a coalescer.
Among them, 412-oblique acid discharge filler.
FIG. 4 is a schematic cross-sectional view of a micro-ceramic ball filter insert in a filter.
Wherein: 511-acid-philic fiber filler, 512-micro ceramic ball filling internal member.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention can effectively overcome the defects of poor washing effect and poor deacidification and desulfurization effect of fresh sulfuric acid in the existing pickling process by combining the high-efficiency mixing of the mixer, the film-forming strengthening mass transfer of internal parts at the bottom of the pickling tower and the circulating dispersion mass transfer of sulfuric acid in the pickling tower; meanwhile, the top of the pickling tower is provided with a separation internal part and an upper straight cylinder expanding special structure of the pickling tower, so that the pre-separation effect on sulfuric acid can be effectively strengthened, and the separation efficiency of the sulfuric acid is improved. The micro acid drops in the alkylation effluent can be rapidly separated in multiple levels and multiple levels by the coalescence separation of the novel acidophilic combined fiber separation internal member and the filter element separation internal member in the coalescer and the filtration separation of the micro ceramic ball filtration internal member in the filter, the separation precision of the acid is obviously improved, and the removal of the sulfuric acid and the sulfur-containing substances in the alkylation effluent is realized. The adsorption tank is placed behind the deisobutanizer to deeply adsorb the liquid-phase alkylate oil, so that the defect of extra consumption of the sulfide in the effluent gas phase to the adsorbent can be overcome, the service life of the adsorbent is prolonged, and better economic benefit is achieved.
FIG. 1 is a schematic diagram of the apparatus and process of the present invention. As shown in fig. 1, fresh sulfuric acid with a concentration of 97% or more is injected into the alkylation effluent from the STRATCO alkylation reactor, the CDAlky alkylation reactor or the SINOALKY alkylation reactor according to 5% -15% of the volume flow, and is uniformly mixed by a high-efficiency mixer, and then is introduced into an acid washing tower for acid washing and separation, so that sulfur-containing impurities such as mercaptan, thioether, thioester and the like in the alkylation effluent are enriched in the fresh sulfuric acid in the processes of intensive mixing and countercurrent acid washing. The sulfuric acid is used as a heavy phase to settle to the bottom of the pickling tower, part of the sulfuric acid returns to the reactor or is discharged outside, the other part returns to the pickling tower through a circulating pump, and the circulating sulfuric acid is subjected to micro-acid drop dispersion through a tubular distributor, so that the circulating sulfuric acid is used for circularly extracting sulfur-containing impurities in the pickling tower, and an alkylation effluent with the sulfuric acid content of 0.02-1.5% after pickling is obtained. And (3) feeding the alkylated effluent after acid washing into a multilayer internal member coalescer to carry out fiber coalescence separation and filter element coalescence separation under the conditions that the flow rate is 0.005-0.1m/s and the pressure drop is 0.02-0.1MPa so as to remove sulfur-containing impurities such as thioesters dissolved in sulfuric acid and more than 90% of sulfuric acid in the alkylated effluent, and obtaining the alkylated effluent with the total sulfur content of less than 200 mg/kg. Passing the finely coalesced and separated alkylation effluent to a filter for micro-ball filtration separation at a flow rate of 0.005 to 0.1m/s and a pressure drop of 0.02 to 0.1MPa to remove sulphur-containing impurities dissolved in the sulphuric acid and more than 95% of the sulphuric acid in the alkylation effluent to obtain an alkylation effluent having a total sulphur content of less than 30 mg/kg or less. And (3) introducing the filtered and separated alkylation effluent into an isobutane removal tower for product fractionation, pumping isobutane out from the tower top and returning to an alkylation reactor, discharging n-butane out of the upper part of the tower, and collecting alkylate oil at the tower bottom. And directly sending the obtained alkylate to an adsorption tank for deep adsorption to adsorb residual sulfur-containing impurities, wherein the total sulfur content of the alkylate is reduced to below 2 mg/kg to obtain the purified alkylate.
Wherein, the mixer is provided with a mixing element for strengthening the mixing between the alkylation effluent containing sulfuric acid, mercaptan, thioether and thioester mixed with gas and liquid and fresh sulfuric acid and promoting the extraction of sulfur-containing impurities by the fresh sulfuric acid. The middle part of the small-diameter straight cylinder section of the pickling tower is provided with a layer of fiber film forming internals with the thickness of 100-350 mm, and the middle part of the large-diameter straight cylinder section is provided with a layer of fiber separation internals with the thickness of 150-350mm, and the fiber film forming internals are used for carrying out countercurrent circulation pickling and separation on the alkylation effluent mixed with gas and liquid so as to remove sulfuric acid and sulfur-containing impurities in the alkylation effluent. And the circulating pump is connected with the bottom of the pickling tower and is used for pumping the sulfuric acid part separated from the bottom of the pickling tower into the pickling tower again for redispersion so as to realize the sulfuric acid cyclic extraction of sulfur-containing impurities. The coalescer is connected with the acid cleaning tower, the front section of the coalescer is provided with a combined fiber separation internal part with the thickness of 200-300mm, and the rear section is provided with a filter element separation internal part for carrying out multistage fine coalescence separation on the alkylation effluent obtained after acid cleaning so as to realize emulsion breaking of emulsified acid, coalescence of micro acid drops and collection of sulfuric acid and remove sulfuric acid and sulfur-containing impurities in the alkylation effluent. The filter being connected to the coalescerThe filter is internally provided with a micro-ceramic ball filtering internal member with the thickness of 200-300mm, and is used for carrying out micro-ceramic ball filtering separation on the alkylation effluent obtained after fine coalescence separation, and removing sulfur-containing impurities dissolved in sulfuric acid and over 95 percent of sulfuric acid in the alkylation effluent through the adsorption and wetting and wrapping of porous micro-ceramic balls. And the deisobutanizer is connected with the filter and is used for carrying out product fractionation on the alkylation effluent obtained after filtration and separation, the light component isobutane obtained at the tower top returns to the reaction system, n-butane is discharged from the upper part of the tower, and the heavy component obtained at the tower bottom is the required product alkylate oil. The adsorbent is connected with the deisobutanizer, and the inside of the adsorption tank is filled with high-efficiency adsorption microspheres for high-efficiency deep adsorption to remove sulfur-containing impurities in the fractionated alkylate oil so as to reduce the sulfur content in the alkylate oil and meet the production requirements. The high-efficiency adsorption microspheres in the adsorption tank are alkaline adsorbents, and the bulk density is 600-800kg/m3The particle size is 2-5mm, the average particle size is 3.2mm, the pore volume is 0.5-0.7 wt%, and the specific surface area is 300-400m2/g。
FIGS. 2 and 3 are schematic cross-sectional views of internals for combined fiber separation in an inventive coalescer. The main body of the combined fiber separating internal member is formed by weaving acidophilic fibers with a contact angle less than 60 degrees, and contains a plurality of layers of columnar film-forming fillers and a plurality of layers of inclined acid-discharging fillers. The columnar film-forming filler consists of acid-phobic fibers with a contact angle of 120 degrees, the thickness T1 is 0.05-0.1L1, and the distance L2 is 0.1-0.3L 1. The inclined acid-removing filler is composed of acid-repellent fibers with contact angles larger than 150 degrees, the inclination angle alpha is 130-150 degrees, the axial thickness T2 is 0.2-0.4L1, the radial thickness T3 is 0.05-0.1D, the distance L3 is 0.1-0.3D, wherein L1 is the length of the combined fiber separating internal member, and D is the inner diameter of the cylinder body.
FIG. 4 is a schematic view of the internal components of the micro-ceramic ball filter of the present invention. The exterior of the micro ceramic ball filtering internal part is wrapped by acidophilic fiber filler, and the interior is a porous micro ceramic ball filling internal part. The porosity of the acidophilic fibrous filler is 50-70%, the thickness T4 is 0.05-0.2L3, and the acid contact angle of the acidophilic fibrous filler is less than 50 degrees. The porous micro-ceramic ball is super-hydrophilic and has the bulk density of 1200-1800kg/m3The particle size is 2-4mm, the average particle size is 3mm, and the pore volume is 0.6-0.8 wt%.
Examples
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
Example 1:
the sulfuric acid alkylation device of Shanghai chemical plant adopts the STRATCO process of DuPont company, and sequentially carries out alkali washing separation, coalescence separation, filtration separation, product fractionation and adsorption separation on alkylation reaction effluent according to the device and method process flow for improving the quality of the alkylated oil product shown in figure 1 to remove sulfuric acid and sulfur-containing impurities contained in the alkylation reaction effluent, wherein
(1) Process conditions
The method is characterized in that ether carbon four, hydrocracking liquefied gas, gas carbon four and isooctane are used as raw materials, concentrated sulfuric acid with the concentration of 95% is used as a catalyst, the volume ratio of acid to hydrocarbon fed into a reactor is 1.2, the quantity ratio of alkane and alkene substances is 8.13, the reaction temperature of the reactor is 3-8 ℃, and the reaction pressure is 0.48 MPa. The concentration of the fresh sulfuric acid for pickling is 98%, and the injection amount is 8% of the volume flow of the alkylation effluent. The coalescence separation process and the filtration separation process both have a flow rate of 0.015m/s of the alkylation effluent and a pressure drop of 0.02 MPa.
(2) Process flow and apparatus
As shown in fig. 1, 2, 3 and 4.
(3) Application effects
By using the device disclosed by the invention, the sulfuric acid content in the alkylation effluent at the top of the pickling tower is about 0.8%, the total sulfur content in the alkylation effluent at the oil phase outlet of the coalescer device is about 60 mg/kg, the total sulfur content in the alkylation effluent at the oil phase outlet of the filter device is about 15 mg/kg, and the sulfur content in the alkylation effluent from the adsorption device can hardly be detected, so that the production requirement of the product alkylate oil is completely met.
Example 2:
the sulfuric acid alkylation device of Shijiazhan chemical plant adopts SINOALKY process of petrochemical engineering scientific research institute of China petrochemical Co., Ltd, and sequentially performs alkali washing separation, coalescence separation, filtration separation, product fractionation and adsorption separation on alkylation reaction effluent according to the device and method process flow for improving the quality of the alkylated oil product shown in figure 1 to remove sulfuric acid and sulfur-containing impurities contained in the alkylation reaction effluent, wherein
(1) Process conditions
The method is characterized in that etherified tetracarbon and isooctane are used as raw materials, concentrated sulfuric acid with the concentration of 98% is used as a catalyst, the volume ratio of acid and hydrocarbon fed into a reactor is 1.12, the quantity ratio of alkane and alkene substances is 10.2, the reaction temperature of the reactor is 0-4 ℃, and the reaction pressure is 0.42 MPa. The concentration of the fresh sulfuric acid for pickling is 98%, and the injection amount is 10% of the volume flow of the alkylation effluent. The coalescence separation process and the filtration separation process both have a flow rate of 0.02m/s of the alkylation effluent and a pressure drop of 0.04 MPa.
(2) Process flow and apparatus
As shown in fig. 1, 2, 3 and 4.
(3) Application effects
By using the device disclosed by the invention, the sulfuric acid content in the alkylated effluent at the top of the pickling tower is about 0.6%, the total sulfur content in the alkylated effluent at the oil phase outlet of the coalescer device is about 100 mg/kg, the total sulfur content in the alkylated effluent at the oil phase outlet of the filter device is about 25 mg/kg, and the sulfur content in the alkylated oil from the adsorption device is about 3 mg/kg, which completely meets the production requirement of the product alkylated oil.
Example 3:
a chemical plant in Jinzhou adopts a CDAlky process of Lummus company, and according to a device and a method process flow for improving the quality of an alkylated oil product shown in figure 1, the alkylated effluent is sequentially subjected to alkali washing separation, coalescence separation, filtration separation, product fractionation and adsorption separation to remove sulfuric acid and sulfur-containing impurities contained in the alkylated effluent, wherein the process flow comprises the steps of alkali washing separation, coalescence separation, filtration separation, product fractionation and adsorption separation, and the sulfuric acid and the sulfur-containing impurities are removed from the alkylated effluent, and the process flow comprises the steps
(1) Process conditions
The method is characterized in that ether C4, hydrocracking liquefied gas, aromatic hydrocarbon combined liquefied gas and isooctane are used as raw materials, sulfuric acid with the concentration of 97% is used as a catalyst, the volume ratio of acid to hydrocarbon fed into a reactor is 1.1, the quantity ratio of alkane and alkene substances is 10, the reaction temperature of the reactor is-3 ℃, and the reaction pressure is 0.46 MPa. The concentration of fresh sulfuric acid was 98% and the injection amount was 12% of the volume flow of the alkylation effluent. The coalescence separation process and the filtration separation process both performed at an alkylation effluent flow rate of 0.015m/s and a pressure drop of 0.05 MPa.
(2) Process flow and apparatus
As shown in fig. 1, 2, 3 and 4.
(3) Application effects
By using the device disclosed by the invention, the sulfuric acid content in the alkylated effluent at the top of the pickling tower is about 0.7%, the total sulfur content in the alkylated effluent at the outlet of the oil phase of the coalescer device is about 50 mg/kg, the total sulfur content in the alkylated effluent at the outlet of the oil phase of the filter device is about 18 mg/kg, and the sulfur content in the alkylated oil from the adsorption device is about 2 mg/kg, which completely meets the production requirement of the product alkylated oil.

Claims (12)

1. An apparatus for upgrading an alkylate oil, comprising:
a mixer is connected with the pickling tower, the middle part of the small-diameter straight cylinder section at the lower part of the pickling tower is provided with a layer of fiber film forming internal part, and the middle part of the large-diameter straight cylinder section at the upper part of the pickling tower is provided with a layer of fiber separating internal part;
a coalescer is connected with a light phase outlet at the top of the pickling tower through an inlet of the coalescer, a combined fiber separation internal part is arranged at the front section of the coalescer, and a filter element separation internal part is arranged at the rear section of the coalescer;
a filter is connected with the upper light phase outlet of the coalescer through the inlet of the filter, and a micro-ceramic ball filter internal part is arranged in the filter;
the heavy phase outlets at the lower parts of the pickling tower, the coalescer and the filter are all connected with pipelines leading to the reactor or the discharge;
and the deisobutanizer is connected with a light phase outlet of the filter through an inlet of the deisobutanizer, the light phase outlet at the top of the tower is connected with the reactor, the upper part of the tower is provided with a normal butane discharge outlet, a heavy phase outlet at the bottom of the tower is connected with the adsorption tank, and the adsorption tank is filled with high-efficiency adsorption microspheres.
2. The apparatus for upgrading an alkylate oil of claim 1, wherein the apparatus comprises a circulating pump, wherein the circulating pump is connected at one end to the outlet of the heavy phase at the bottom of the acid tower and at the other end to the connecting-pipe distributor of the acid tower.
3. The apparatus for upgrading an alkylate oil of claim 1, wherein the combined internal fiber-separating member of the coalescer comprises a plurality of layers of columnar film-forming fillers and a plurality of layers of inclined acid-removing fillers, and the main body of the internal fiber-separating member is woven from acid-philic fibers having a contact angle of less than 60 °; the columnar film-forming filler consists of acid-phobic fibers with contact angles of more than 120 degrees, the thickness T1 is 0.05-0.1L1, and the distance L2 is 0.1-0.3L 1; the inclined acid-removing filler consists of acid-repellent fibers with contact angles larger than 150 degrees, the inclination angle alpha is 130-150 degrees, the axial thickness T2 is 0.2-0.4L1, the radial thickness T3 is 0.05-0.1D, and the distance L3 is 0.1-0.3D; where L1 is the combined fiber separation internal length and D is the internal diameter of the barrel.
4. The apparatus for improving the quality of the alkylated oil product according to claim 1, wherein the micro-ceramic ball filter internals in the filter are externally wrapped by the acidophilic fiber filler, and internally wrapped by the porous micro-ceramic ball filler internals; the porosity of the acidophilic fibrous filler is 50-70%, the thickness T4 is 0.05-0.2L3, and the acid contact angle of the acidophilic fibrous filler is less than 50 degrees; the porous micro-ceramic ball is super-hydrophilic and has the bulk density of 1200-1800kg/m3The particle size is 2-4mm, the average particle size is 3mm, and the pore volume is 0.6-0.8 wt%.
5. The apparatus for improving the quality of an alkylated oil product as claimed in claim 1, wherein the high efficiency adsorption microspheres in the adsorption tank are alkaline adsorbents with a bulk density of 600-3The particle diameter is 2-5mm, the average particle diameter is 3.2mm, and the pore volume0.5-0.7 wt%, and a specific surface area of 300-2/g。
6. The apparatus for upgrading alkylated oil product of claim 3 or 4, wherein the acid-philic fibers are one or more selected from 904L metal fibers, glass fibers, polyamide fibers, or modified fibers with a modified roughness or surface coating such that the contact angle of the fibers with acid is less than 60 °.
7. The apparatus for upgrading alkylated oil product of claim 3, wherein the acid-phobic fibers are one or more fibers selected from the group consisting of polytetrafluoroethylene fibers, polypropylene fibers, polyethylene fibers, or modified fibers with a roughness-changing or acid-phobic coating applied on the surface such that the contact angle of the fibers with acid is >120 °.
8. The apparatus for upgrading the quality of alkylate oil of claim 1, wherein an identical adsorption tank is added before the deisobutanizer.
9. A method for improving the quality of an alkylated oil product is characterized by comprising the following steps:
(a) injecting fresh sulfuric acid into the alkylation effluent from the alkylation reactor, uniformly mixing by using a mixer, introducing into an acid washing tower for acid washing and separation, realizing enrichment of sulfur-containing impurities in the alkylation effluent into the fresh sulfuric acid in the processes of strong mixing and countercurrent acid washing, and settling the separated sulfuric acid as a heavy phase to the bottom of the acid washing tower and returning to the reactor or discharging to obtain the alkylation effluent after acid washing;
(b) introducing the alkylation effluent after acid washing in the step (a) into a multilayer internal member coalescer for fiber coalescence separation and filter element coalescence separation, and removing sulfur-containing impurities dissolved in sulfuric acid and more than 90% of sulfuric acid in the alkylation effluent to obtain alkylation effluent after fine coalescence separation;
(c) introducing the alkylation effluent subjected to fine coalescence separation in the step (b) into a filter for micro-ceramic ball filtration separation so as to remove sulfur-containing impurities and over 95% of sulfuric acid in the alkylation effluent, thereby obtaining the alkylation effluent subjected to filtration separation;
(d) introducing the alkylation effluent after filtration and separation in the step (c) into an isobutane removal tower for product fractionation, extracting isobutane from the tower top and returning the isobutane to an alkylation reactor, discharging n-butane from the upper part of the tower, and collecting alkylate oil from the tower bottom;
(e) directly sending the alkylate oil obtained in the step (d) to an adsorption tank for deep adsorption purification, and removing residual sulfur-containing impurities and sulfuric acid to obtain purified alkylate oil.
10. The method of claim 8, wherein the post-reactor alkylation effluent is a mixed gas-liquid phase from a STRATCO sulfuric acid alkylation reactor, a CDAlky sulfuric acid alkylation reactor, or a SINOALKY sulfuric acid alkylation reactor, and the effluent contains sulfur-containing impurities mainly including mercaptans, thioethers, and thioesters.
11. The method of upgrading an alkylate oil of claim 8, wherein in step (a) the sulfuric acid fraction obtained from the bottom of the pickling section after pickling is recycled back to the pickling section by means of a circulation pump and is dispersed in micro-droplets by means of a tubular distributor.
12. The method for upgrading an alkylated oil product of claim 8, wherein in step (a) of the method, the concentration of fresh sulfuric acid is not less than 96%, and the injection amount of fresh sulfuric acid is 2-15% of the volume flow of the alkylation effluent;
in steps (b) and (c) of the process, the coalescence-separation process of the coalescer and the filtration-separation process of the filter are carried out at a flow rate of the alkylation effluent of 0.005 to 0.1m/s and a pressure drop of 0.02 to 0.1 MPa.
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