CN108264929B - Sulfuric acid alkylation method - Google Patents
Sulfuric acid alkylation method Download PDFInfo
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- CN108264929B CN108264929B CN201611263054.2A CN201611263054A CN108264929B CN 108264929 B CN108264929 B CN 108264929B CN 201611263054 A CN201611263054 A CN 201611263054A CN 108264929 B CN108264929 B CN 108264929B
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/03—Acids of sulfur other than sulfhydric acid or sulfuric acid, e.g. halosulfonic acids
Abstract
A sulfuric acid alkylation process comprising: introducing an isobutane raw material, circulating isobutane from an isobutane separation tower and sulfuric acid from an acid-hydrocarbon separator into an external-kettle circulating emulsifying device consisting of a stirring kettle and a shear-type emulsifying device for premixing to form an acid-hydrocarbon emulsion containing isobutane and sulfuric acid; one part of the acid hydrocarbon emulsion enters a stirring kettle for circulation, and the other part of the acid hydrocarbon emulsion enters an alkylation reactor to be in contact reaction with the mixed olefin in the alkylation reactor; recycling a part of reaction effluent after the acid hydrocarbon emulsion and the mixed olefin react to the stirring kettle, and enabling a part of reaction effluent to enter an acid hydrocarbon separator, wherein the acid hydrocarbon separator separates the reaction effluent into sulfuric acid and hydrocarbon components; and the separated hydrocarbon component enters an isobutane separation tower, the isobutane separation tower separates the hydrocarbon component into isobutane and alkylate oil, wherein the separated isobutane is circulated to the stirring kettle. The method of the invention enhances the mixing degree of acid and hydrocarbon, is beneficial to the mass transfer of isobutane from a hydrocarbon phase to an acid phase, and improves the product quality of alkylate.
Description
Technical Field
The invention relates to a petroleum refining process, in particular to an alkylation reaction process for promoting mixing of isobutane and sulfuric acid.
Background
The alkylation refers to a chemical reaction process for introducing alkyl groups, and in various industrial applications of alkylation, isobutane is used as an alkylating agent to perform alkylation reaction on various low-carbon olefins such as C3-C5, and the alkylation of isobutane for producing high-octane gasoline blending components is one of the most important industrial applications of alkylation. In the development process of isobutane alkylation technology, two liquid acids, namely sulfuric acid and hydrofluoric acid, are mainly used as catalysts, and in recent years, ionic liquid, solid acid and the like are also used as alkylation catalysts, but the technology is not mature, and the large-scale application is not realized. Since hydrofluoric acid is volatile, and a small amount of hydrofluoric acid causes irreversible damage to human skeleton, the technology of alkylation with hydrofluoric acid is greatly restricted today with increasing environmental requirements, and is a better choice in spite of the problems of waste acid treatment and the like in sulfuric acid alkylation. In the sulfuric acid alkylation reaction, butylene is relatively easy to dissolve in a sulfuric acid catalyst to form an equilibrium composition of olefin and sulfuric acid monoester, isobutane has low solubility in sulfuric acid and forms a hydrocarbon phase together with product alkylate, and the mixing degree of the acid and the hydrocarbon phases determines the mass transfer rate of isobutane from the hydrocarbon phase to the acid phase, which is also the speed-determining step of the sulfuric acid alkylation reaction. If isobutane cannot enter the acid-hydrocarbon interface in time to react with olefins to produce the desired C8 component, the olefins will auto-polymerize to produce lower octane by-products, resulting in a reduction in the final alkylate octane. The common method is to adopt a very high isobutane/butene ratio, and the alkane-alkene ratio in an actual reaction zone can reach dozens or even hundreds, so that the dissolving limit of isobutane is made up, the side reaction of butene is inhibited, but the increase of the alkane-alkene ratio directly causes the increase of the energy consumption of the subsequent isobutane separation, and the economic benefit of the device is influenced.
The reactor for sulfuric acid alkylation of the main stream is a horizontal stirred tank with a flow directing arrangement as disclosed in US3759318, the subsequent modification being to set the mechanical stirring to an eccentric configuration. Isobutane, butene and sulfuric acid catalyst flow towards the diffuser under the action of the stirring blades to achieve dispersion of the liquid phase. Chinese patent CN200880011181.0 discloses a high shear reactor which can shear hydrocarbon including isoparaffin and olefin and liquid acid catalyst into emulsion with average droplet of hydrocarbon less than 5 μm in acid continuous phase to promote mass transfer of reaction system. The mixing intensity of the mechanical stirring kettle is limited by the stirring power, the reaction temperature is generally about 10 ℃, the lower temperature is favorable for reaction selectivity, but the viscosity of the sulfuric acid is increased at the low temperature, and the power consumption of a motor is increased sharply to reach the same stirring degree.
DuPont reported a series of modifications to a horizontal eccentric stirred tank at the international petroleum refining annual meeting in 2007, including the addition of a pre-mix of isobutane and butene, followed by mixing with sulfuric acid to enhance the mass transfer process of isobutane to the reaction interface. Premixing of the reaction feed has become one of the concerns for the improvement of sulfuric acid alkylation technology, including premixing of isobutane and butenes, and premixing of isobutane and sulfuric acid catalyst.
U.S. Pat. No. 5,54, 799 discloses a vertical upflow type jet reactor, which adopts a premixing structure of isobutane and sulfuric acid with a distribution pipe, wherein isobutane is jetted from the distribution pipe and mixed with sulfuric acid entering from an annular space, and the premixed isobutane/sulfuric acid emulsion enters a reaction zone and is subjected to alkylation reaction with olefin entering from the reaction zone in an axial subsection manner. In addition to the premixing effect, the volumetric expansion of the stream may absorb a portion of the heat as the reaction zone increases in volume relative to the premixing zone.
US5785933 discloses an alkylation reaction apparatus in the form of a static mixer, where the raw material isobutane is combined with the acid hydrocarbon emulsion flowing out of the bottom of the reactor, mixed with sulfuric acid from a settling tank, further mixed by the static mixer, mixed with butene by the static mixer, and fed into the reaction zone. The main purpose of the technology is to reduce the use of mobile equipment, preferentially mix isobutane and sulfuric acid in terms of mixing selection, and add an acid hydrocarbon emulsion to improve the mixing efficiency.
Chinese patent 201510738217.7 discloses a sulfuric acid alkylation reaction method, wherein a double-feed nozzle with a special structure is designed to pre-mix sulfuric acid and isobutane, and the mixed acid-hydrocarbon mixture and mixed carbon four enter a reactor simultaneously to perform alkylation reaction. The inner section of the reactor is provided with a regular packing with mixing effect, and the acid-hydrocarbon mixture is further mixed and reacted in the packing layer. The method adopts a self-refrigeration heat-taking method, utilizes partial gasification of hydrocarbons to take away alkylation reaction heat, and keeps the reaction at a lower temperature.
Chinese patent 201310503473.9 discloses a sulfuric acid alkylation reaction process, wherein isobutane and sulfuric acid are premixed through a colloid mill, and then enter a rotating bed reactor to be mixed and reacted with another stream of isobutane and olefin raw materials, and the process realizes mixed mass transfer of reaction materials through sectional feeding of isobutane, the colloid mill and a jet mixer.
Analysis of the above technical solutions shows that, in order to solve the problem of mass transfer of isobutane into sulfuric acid in the sulfuric acid alkylation reaction, it has become one of the directions for technical improvement to enhance the premixing effect of isobutane and sulfuric acid. The scheme is different from the traditional alkane and alkene premixing, and the concentrated sulfuric acid can generate an extraction effect on an alkane and alkene mixed solution and dissolve most of alkene, so that the mass transfer effect of the alkane and alkene premixing on isobutane is not ideal. The technology of premixing isobutane and sulfuric acid and integrally mixing the reinforced alkylation raw materials is also obviously different from the technology of integrally mixing the isobutane and sulfuric acid, and the technology of the rotary packed bed disclosed by Chinese patent CN201310503460.1 and the like, the pulse flow and packing structure disclosed by U.S. patent US7319180, Chinese patent CN 03813341.5 and the like, and the technology of the shear type reactor and the like disclosed by the Chinese patent CN200880011181.0 and the like are mainly characterized in that the integral mixing action of reaction materials is inevitably provided with a local and transient non-uniform area in the process from macroscopic mixing to microscopic mixing, side reaction is possible to occur when the reaction materials are integrally mixed, the premixing of the isobutane and the sulfuric acid is only a physical process, no by-product is generated, and various technical schemes can be adopted to realize full mixing emulsification. However, the main scheme of the isobutane and sulfuric acid premixing technology disclosed at present is to adopt simple one-pass forms such as a static mixer and jet collision, which belong to the accessory structure of an alkylation reactor, and have certain limitation on strengthening the mass transfer from isobutane to sulfuric acid.
Disclosure of Invention
The invention aims to provide a sulfuric acid alkylation method.
To achieve the above object, the present invention provides a sulfuric acid alkylation process comprising the steps of:
step one, introducing an isobutane raw material, circulating isobutane from an isobutane separation tower and sulfuric acid from an acid-hydrocarbon separator into an external-kettle circulating emulsifying device consisting of a stirring kettle and a shear-type emulsifying device for premixing to form an acid-hydrocarbon emulsion containing isobutane and sulfuric acid;
secondly, enabling a part of the acid hydrocarbon emulsion to enter a stirring kettle for circulation, and enabling a part of the acid hydrocarbon emulsion to enter an alkylation reactor for contact reaction with the mixed olefin in the alkylation reactor;
step three, recycling a part of reaction effluent after the acid hydrocarbon emulsion and the mixed olefin are reacted to the stirring kettle, enabling a part of reaction effluent to enter an acid hydrocarbon separator, and separating the reaction effluent into sulfuric acid and hydrocarbon components by the acid hydrocarbon separator; and
and step four, the hydrocarbon component separated in the step three enters an isobutane separation tower, the hydrocarbon component is separated into isobutane and alkylate oil by the isobutane separation tower, and the separated isobutane is circulated to the stirring kettle.
Further, sulfuric acid in the acid hydrocarbon emulsion is a continuous phase, hydrocarbons containing isobutane are dispersed droplets, and the average diameter of the dispersed droplets is less than 50 μm.
Further, the shear type emulsifying device comprises a stator and a rotor, the mixing of the material flow is realized through the rotation of the rotor, and the rotating speed range of the rotor is 300-5000 rpm.
Further, the outlet temperature of the acid hydrocarbon emulsion formed by the shear type emulsifying device is-5-10 ℃.
Further, the alkylation reactor is provided with a rotating structure.
Further, the shear type emulsifying device is coaxially connected with the alkylation reactor.
Further, the alkylation reactor with a rotating structure is one of a rotating packed bed or a stator-rotor supergravity reactor.
Further, the mixed olefin is C3-C5 olefin.
Further, the mixed olefins are C4 olefins.
The invention has the beneficial effects that:
(1) the dispersion degree of acid hydrocarbon in the alkylation reaction is enhanced, the mass transfer of isobutane to an acid phase is promoted, the side reaction of olefin in the acid phase is reduced, and the selectivity of high-octane number components in the alkylate oil is improved.
(2) The isobutane/sulfuric acid emulsion formed by premixing can reduce the mixing intensity in the reactor, and is beneficial to the design of mass transfer and heat transfer in an alkylation reaction zone.
Drawings
FIG. 1 is a schematic diagram of a process for the pre-mixing alkylation in an in-line shear emulsification apparatus.
FIG. 2 is a schematic view of the process flow of the alkylation process with premixing by the external circulation type shear emulsifying device.
FIG. 3 is a schematic view of a self-refrigeration alkylation process with shear premixing.
Wherein, the reference numbers:
1 Isobutane feedstock
2 shear type emulsification device
3 mixed butene
4 reactor
5 reaction effluent
6 acid hydrocarbon separator
7 sulfuric acid
8 acid hydrocarbon mixture stream
9 hydrocarbons
10 isobutane separation tower
11 alkylated oil
12 cycle isobutane
13 Isobutane/sulfuric acid emulsion
14 isobutane/sulfuric acid mixing stirring kettle
15 cauldron extrinsic cycle shearing emulsion commodity circulation
16 propane
17 compression condensing tank
18 cooler
19 gas compressor
20 compression of condensate
21 reactor outlet gas hydrocarbons
22 acid hydrocarbon separator gas hydrocarbons
Detailed Description
The invention is further illustrated below with reference to the figures.
A sulfuric acid alkylation process comprising the steps of:
step one, introducing an isobutane raw material, circulating isobutane from an isobutane separation tower and sulfuric acid from an acid-hydrocarbon separator into an external-kettle circulating emulsifying device consisting of a stirring kettle and a shear-type emulsifying device for premixing to form an acid-hydrocarbon emulsion containing isobutane and sulfuric acid;
secondly, enabling a part of the acid hydrocarbon emulsion to enter a stirring kettle for circulation, and enabling a part of the acid hydrocarbon emulsion to enter an alkylation reactor for contact reaction with the mixed olefin in the alkylation reactor;
step three, recycling a part of reaction effluent after the acid hydrocarbon emulsion and the mixed olefin are reacted to the stirring kettle, enabling a part of reaction effluent to enter an acid hydrocarbon separator, and separating the reaction effluent into sulfuric acid and hydrocarbon components by the acid hydrocarbon separator; and
and step four, the hydrocarbon component separated in the step three enters an isobutane separation tower, the hydrocarbon component is separated into isobutane and alkylate oil by the isobutane separation tower, and the separated isobutane is circulated to the stirring kettle.
Further, sulfuric acid in the acid hydrocarbon emulsion is a continuous phase, hydrocarbons containing isobutane are dispersed droplets, and the average diameter of the dispersed droplets is less than 50 μm.
Further, the shear type emulsifying device comprises a stator and a rotor, the mixing of the material flow is realized through the rotation of the rotor, and the rotating speed range of the rotor is 300-5000 rpm.
Further, the outlet temperature of the acid hydrocarbon emulsion formed by the shear type emulsifying device is-5-10 ℃.
Further, the alkylation reactor is provided with a rotating structure.
Further, the shear type emulsifying device is coaxially connected with the alkylation reactor.
Further, the alkylation reactor with a rotating structure is one of a rotating packed bed or a stator-rotor supergravity reactor.
Further, the mixed olefin is C3-C5 olefin.
Further, the mixed olefins are C4 olefins.
The isobutane raw material is a hydrocarbon material rich in isobutane, and the mixed olefin is a hydrocarbon material rich in C3-C5 olefins, and particularly, a mixed butene material rich in 1-butene, cis/trans 2-butene and isobutene is preferred. The technical scheme has been reported in the published technical documents, and all the technical schemes have certain effects, but the adopted premixing mode is limited to a static mixer, a nozzle, a distributor and the like, the mixing time is very short, only part of isobutane participates in premixing, and the mixing intensity is also low. The method provided by the invention selects a shearing type emulsifying device with external power, and mixes all isobutane-containing materials entering a reactor, including fresh raw material isobutane and circulating isobutane, with a catalyst containing sulfuric acid in a premixing process, so that isobutane and sulfuric acid are fully mixed into an emulsion, and the emulsion is suitable for a wide range of acid-hydrocarbon two-phase proportion.
The shear type emulsifying device is adopted to premix isobutane and sulfuric acid, and the premixing can be carried out in a one-time passing mode, namely isobutane and sulfuric acid directly enter a subsequent reactor after passing through the shear type emulsifying device, and the technical field is generally called pipeline type emulsification. If the pipeline type emulsification needs to reach a higher emulsification degree, the consumed power is very large, and the pipeline type emulsification is difficult to be applied to large-scale devices. The method preferably adopts external circulation type emulsification, namely mixing of material flows of isobutane and sulfuric acid through the combination of the shear type emulsification device and the stirring kettle, forming external circulation of the material flows in the stirring kettle through the shear type emulsification device, enabling part of the material flows at the outlet of the shear type emulsification device to enter the stirring kettle for circulation, and enabling part of the material flows to enter the alkylation reactor for reaction with the mixed butylene. The external circulation type emulsification method can adopt a shear type emulsification device with lower power, and a certain residence time is controlled to achieve a mixing effect, because the mixture does not contain olefin and does not generate side reaction after long-time mixing, the circulation type emulsification can adopt a longer residence time, and the preferred residence time of the method is 0.1-1 h.
For sulfuric acid alkylation, the preferred suitable acid to hydrocarbon ratio of the present invention is such that sulfuric acid is the continuous phase and isobutane is the dispersed phase. The average diameter of the dispersed phase droplets formed by the external circulation type emulsifying device is less than 50 mu m. As a preferable scheme, the invention selects a high-speed shear type emulsifying device comprising a stator and a rotor structure, realizes the mixing of material flows through the high-speed rotation of the rotor, the rotating speed range of the rotor is 300-5000 r/min, more preferably 600-2000 r/min, and the average diameter of the formed dispersed phase droplets is less than 30 μm. Conventional equipment can be selected for use to shear type emulsification device, including shearing emulsion machine, rubber grinder pump etc. does not need special design, is favorable to the use and the maintenance of equipment, and some shear type emulsification devices have the effect of lifting pressure simultaneously moreover, can regard as the delivery pump to use.
The method provided by the invention is suitable for low-temperature alkylation reaction, the stirring is difficult and the mixing dispersion efficiency is reduced due to the fact that the viscosity of sulfuric acid is increased at a low temperature, the premixing of isobutane and sulfuric acid is realized by adopting the shear type emulsifying device, the method can be carried out at a high viscosity, the temperature of the outlet of the shear type emulsifying device is preferably-5-10 ℃, the temperature is the same as the temperature of the alkylation reaction, and the temperature of the outlet of the shear type emulsifying device and the temperature of a reactor can be controlled by adopting the known schemes in the technical field, such as a cooling jacket, a coil pipe, gasification and the like.
After isobutane and sulfuric acid are mixed to achieve a good emulsified state, the separation of acid hydrocarbon needs a long time, so that under the condition that the premixing effect of isobutane and sulfuric acid is good, the mixing intensity in the reactor can be reduced, such as the power of a stirring motor, or the design height and flow rate of a filler. The stability of the acid hydrocarbon emulsion is related to the composition of the hydrocarbon, and the stability of the emulsion is improved when the hydrocarbon contains heavier alkylate oil. Therefore, as a preferred method of the present invention, the pre-mixed stream introduced into the external circulation type shear emulsifying device comprises isobutane raw material, circulating isobutane, circulating sulfuric acid, and stream containing sulfuric acid and alkylate at the outlet of the reactor, and the streams are pre-mixed by the shear emulsifying device and then enter the reactor to react with the carbon tetraolefin. The material flow containing sulfuric acid and alkylate at the outlet of the reactor is introduced into a shear type emulsifying device to be mixed with isobutane, so that alkylate and sulfate in the material flow are further in full contact with isobutane, the generation of side reaction can be reduced, the product quality of alkylate is improved, and the degree of freedom of reactor operation is increased.
The method of the invention realizes the full premixing of the isobutane and the sulfuric acid, reduces the requirement of the mixing strength in the subsequent reaction process, and the reactor of the method of the invention can select a conventional stirred tank and a filler bed layer, and can also be the existing internal circulation horizontal eccentric stirred tank. The invention preferably uses a reactor with a rotary structure, a shear type emulsifying device and the reactor with the rotary structure are coaxially connected, power is provided by the same motor, and the rotating speeds of the shear type emulsifying device and the reactor are respectively controlled by adopting a transmission structure known by the technical personnel in the field. The equipment structure of the scheme is compact, and the equipment investment can be saved. As a more preferable scheme, the reactor with the rotating structure is one of a rotating packed bed or a stator-rotor hypergravity reactor.
The alkylation process flow of the present invention is shown in fig. 2, which shows only the main equipment and flow paths for illustrating the technical solution of the present invention, and the contents known in the art are omitted. Isobutane raw material 1, circulating isobutane 12 from the top outlet of an isobutane separation tower 10, sulfuric acid 7 from the bottom of an acid hydrocarbon separator 6 and an acid hydrocarbon mixture flow 8 formed by combining alkylate, isobutane and sulfuric acid-containing reaction effluent 5 flowing out from the bottom of a reactor 4 enter an isobutane/sulfuric acid stirring kettle 14 for mixing, stirring is used for maintaining disturbance of the stream in the kettle, an extrakettle circulating shear emulsion stream 15 at the bottom outlet of the isobutane/sulfuric acid stirring kettle 14 enters a shear type emulsifying device 2 for shear emulsification, a part of the stream at the outlet of the shear type emulsifying device 2 enters the isobutane/sulfuric acid stirring kettle 14 for circulating emulsification, and a part (isobutane/sulfuric acid emulsion 13) is used as an inlet stream of the reactor 4 and reacts with mixed butene 3. The effluent of the reactor 4 enters an acid hydrocarbon separator 6 for separation, and the overhead hydrocarbon enters an isobutane separation tower 10 for further separation into isobutane 12 and alkylate oil 11.
An example of the process of the present invention in combination with a rotating packed bed reactor and a gasification refrigeration scheme is shown in figure 3. The shear type emulsification device 2 and the rotating packed bed reactor 4 can be coaxially connected, and can use the same power source or can be independent of the power source. The isobutane raw material 1, the compressed condensate 20, the circulating isobutane 12 and the acid hydrocarbon mixture flow 8 are sheared and emulsified in the shearing type emulsifying device 2, enter the reactor 4 to react with the mixed butene 3, and the pressure of the reactor 4 is controlled to enable hydrocarbons in the reactor 4 to be partially gasified, so that the reaction temperature in the reactor 4 is controlled. The gas hydrocarbon 21 at the outlet of the reactor enters a gas compressor 19, is compressed together with a small amount of gas from the top of the acid hydrocarbon separator 6 and is condensed by a cooler 18, a compressed condensate 20 at the bottom of a compressed condensate tank 17 is circulated back to the shear-type emulsification device 2, and a small amount of gas at the top of the compressed condensate tank 17 is propane 16 and is discharged as an effluent stream. The example shown in fig. 3 is intended to illustrate the use of a shear emulsification device for pre-mixing isobutane and sulfuric acid, which is easily integrated with the self-refrigeration process, as one skilled in the art would appreciate, the process of the present invention is also easily integrated with the effluent refrigeration process.
Example 1
The process adopts the flow shown in figure 1, belongs to an in-line emulsification mode, and comprises the steps of combining an isobutane raw material 1 with circulating isobutane 12 from an outlet at the top of an isobutane separation tower 10, combining sulfuric acid 7 from the bottom of an acid hydrocarbon separator 6 and an acid hydrocarbon mixed effluent 5 containing alkylate, isobutane and sulfuric acid flowing out from the bottom of a reactor 4, respectively entering two inlets of a shear type emulsification device 2, emulsifying, and then entering the reactor 4 to be in contact reaction with an olefin-containing raw material 3 entering the reactor. The device is a pilot test device with the scale of 2kg of butylene/h, the raw material is refinery isobutane with the purity of 96 v%, and refinery etherified C4, wherein the content of mixed butylene is 48 v%, and the mixed butylene content is 92 wt% concentrated sulfuric acid. The rotation speed of the shear type emulsifying device is 1200 r/min, the temperature rises by 2 ℃, the outlet temperature is controlled to be 8 ℃, the pressure is 0.5MPa, the reactor is a stirring kettle, the stirring rotation speed is 200 r/min, the average residence time of material flow is 15min, and the reaction temperature is controlled to be 8 ℃ through a cooling jacket. The mole ratio of the premixed isobutane to the sulfuric acid is 0.9:1, the mole ratio of the alkane to the olefin entering the reactor is 12:1, and all the material flow 5 at the outlet of the reactor enters the acid hydrocarbon separation tank and does not participate in the premixing of the acid hydrocarbon. The average particle size of the material at the outlet of the shear type emulsification device was analyzed by an in situ laser granulometer to be 35 μm. The alkylate was analyzed by chromatography for composition and calculated research octane number was 95.6. The target product of the alkylation reaction is C8 alkane, the selectivity of which can reflect the efficiency of the mixing and reaction process, and the selectivity and octane number of C8 alkane have a corresponding relation, so that the effect of the mixing and reaction can be judged through the octane number.
Reference ratio
The process conditions were the same as in example 1, isobutane and circulating sulfuric acid were fed directly into the stirred tank reactor together with the mixed butenes without passing through a shear type emulsification device for reaction. The alkylate has a research octane number of 94.
Example 2
By adopting the same process parameters as in example 1, a part of the reaction effluent 5 is introduced into a shear type emulsifying device to be sheared and emulsified together with isobutane and sulfuric acid, the mass ratio of the introduced material flow to the material flow entering the acid-hydrocarbon separator is 1:6, and the research octane number of the obtained alkylate is 96.1.
Example 3
The procedure of FIG. 2 was followed, and the raw materials were the same as in example 1, and the inline shear emulsification protocol in the pilot plant was changed to the preferred extracorporeal circulation emulsification protocol in the present invention, which consisted of a stirred tank and a shear emulsification apparatus. The temperature in the stirring kettle is controlled to be-3 ℃, the pressure is 0.5MPa, the circulation ratio is 8:1, the rotating speed of the shear type emulsifying device is 850 r/m, and the average residence time is calculated to be 18 min. The molar ratio of isobutane to sulfuric acid was 0.85:1, the reactor was a wire mesh packed bed, the coils were heated, the reaction temperature was-3 ℃, the average residence time was 7min, the alkane/olefin ratio in the reaction zone was 15:1, the reactor outlet stream was partially recycled to the premixing, and the flow ratio was the same as in example 2. On-line particle size analysis showed that the pre-mixed emulsion had an average particle size of 25 μm and the alkylate had a research octane number of 97.2.
Example 4
The process conditions were the same as in example 3, the reactor was changed to a rotating packed bed, the speed was 600 rpm, the residence time was about 5s, and the mass ratio of reactor outlet stream recycle to premix flow to entering the acid hydrocarbon separator was 3: 1, adjusting the outlet pressure of the shear type emulsifying device to 0.3MPa, and heating by rotating an outer jacket of a packed bed at the temperature of 5 ℃. The alkylate has a research octane number of 96.2.
Example 5
The flow shown in figure 3 is adopted, the rotating speed is 1600 rpm, the temperature rise is 4 ℃, the outlet temperature is controlled to be 6 ℃, the pressure is 0.5MPa, the reactor is the same as the embodiment 4, the molar ratio of the isobutane to the sulfuric acid is 0.85:1, the alkane-alkene ratio of the reaction zone is 15:1, the mass ratio of the outlet material flow of the reactor to the premixing flow to the acid-hydrocarbon separator is 5:1, the reactor does not adopt a jacket for heat extraction, the reaction temperature is controlled to be 8 ℃ by adjusting the reaction pressure, and the gasification of hydrocarbons occurs in a reaction zone to absorb part of the reaction heat. The alkylate has a research octane number of 96.4.
Example 6
The process conditions were the same as in example 5, the outlet temperature and the reaction temperature of the shear emulsification apparatus were adjusted to-5 ℃ and the research octane number of the alkylate was 97.3.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A sulfuric acid alkylation process, comprising the steps of:
step one, introducing an isobutane raw material, circulating isobutane from an isobutane separation tower and sulfuric acid from an acid-hydrocarbon separator into an external-kettle circulating emulsifying device consisting of a stirring kettle and a shear-type emulsifying device for premixing to form an acid-hydrocarbon emulsion containing isobutane and sulfuric acid;
secondly, enabling a part of the acid hydrocarbon emulsion to enter a stirring kettle for circulation, and enabling a part of the acid hydrocarbon emulsion to enter an alkylation reactor for contact reaction with the mixed olefin in the alkylation reactor;
step three, recycling a part of reaction effluent after the acid hydrocarbon emulsion and the mixed olefin are reacted to the stirring kettle, enabling a part of reaction effluent to enter an acid hydrocarbon separator, and separating the reaction effluent into sulfuric acid and hydrocarbon components by the acid hydrocarbon separator; and
and step four, the hydrocarbon component separated in the step three enters an isobutane separation tower, the hydrocarbon component is separated into isobutane and alkylate oil by the isobutane separation tower, and the separated isobutane is circulated to the stirring kettle.
2. The sulfuric acid alkylation process of claim 1, wherein the sulfuric acid in the acid hydrocarbon emulsion is a continuous phase and the hydrocarbon comprising isobutane is dispersed droplets having an average diameter of less than 50 μm.
3. The sulfuric acid alkylation process of claim 1, wherein the shear emulsification device comprises a stator and a rotor, and the mixing of the streams is achieved by rotation of the rotor in the range of 300-.
4. The sulfuric acid alkylation process of claim 1, wherein the shear emulsification device forms an acid-hydrocarbon emulsion having an exit temperature of-5 to 10 ℃.
5. The sulfuric acid alkylation process of claim 1, wherein the alkylation reactor has a rotating structure.
6. The sulfuric acid alkylation process of claim 1, wherein the shear emulsification device and the alkylation reactor are coaxially connected.
7. The sulfuric acid alkylation process of claim 1, wherein the alkylation reactor with a rotating structure is one of a rotating packed bed or a stator-rotor hypergravity reactor.
8. The sulfuric acid alkylation process of claim 1, wherein the mixed olefins are C3-C5 olefins.
9. The sulfuric acid alkylation process of claim 1, wherein the mixed olefins are C4 olefins.
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