CN100348559C - Alkylation reaction technique catalyzed by ion liquid and reactor apparatus - Google Patents
Alkylation reaction technique catalyzed by ion liquid and reactor apparatus Download PDFInfo
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Abstract
This invention involves an ion liquid catalytic alkylation process and a responsing reactor. The process comprises carrying out a reaction of isobutene, C3-C5 olefins and ionic liquid catalyst in a rotating bed reactor with reaction temperature of 8~40DEG C, pressure of 0.3~1.0 MPa and rotor speed of 100~2500 rpm, wherein the volume ratio of ion liquid feed to alkanes-olefins is 0.1~1.5:1 and the molar ratio of alkanes to olefins is 10~300, and controlling the reaction time less than 1~10min. The invention improved alkylation reaction selectivity, and the octane value of alkylation product can reach to 94-100. The operation is simple and low-cost, and has no pollution to environment and beneficial to environment protection.
Description
Technical field
The present invention relates to alkylation reaction technique and reactor assembly, particularly carry out isoparaffin and olefin alkylation reaction technology, also relate to the application of high-gravity technology in chemical reaction engineering with ionic-liquid catalyst.
Background technology
In petroleum refining industry, the alkylation reaction technique of Trimethylmethane and C3～C5 alkene is a significant process of producing cleaning, stop bracket gasoline component, and the gasoline alkylate that obtains is a kind of refining of petroleum product of environmental protection.The catalyzer that present industrial alkylated reaction adopted is mainly liquid strong acid such as the vitriol oil or hydrofluoric acid.But these liquid strong acid have, and corrodibility is strong, production operation is difficult, product postprocessing trouble and have problem such as serious environmental pollution.Ionic liquid is a kind of a kind of salt that at room temperature exists with liquid form, compare with ionogen with traditional organic solvent, since ionic liquid have the temperature range that exists with liquid state wide, do not burn, a series of outstanding advantages such as not oxidation, chemical stability are good, the application in alkylated reaction obtains good effect as catalyzer or solvent with it in recent years.It is the method for catalyst in preparing alkylated oil with the compound ion liquid that CN 1500764A discloses a kind of, this method is a raw material with Trimethylmethane and C4 alkene, the compound ion liquid catalyst cation source is in the hydrohalogen of the amine that contains alkyl or the hydrohalogen of pyridine, and negatively charged ion is the composite anion that two or more metallic compound makes, alkylated reaction is at one 20～100 ℃, pressure 0.1～1.6MPa, raw material alkane alkene ratio is 1: 1-200: carry out under 1 condition, reactor is selected conventional autoclave for use.It is catalyzer with the ionic liquid at room temperature that CN1432627A discloses a kind of, with Trimethylmethane and alkene is the method for feedstock production alkylated oil, and wherein said room-temperature ion liquid body catalyst is with the hydrohalogen of the amine that contains alkyl or the hydrohalogen and the metal halide prepared in reaction of pyridine; Described alkylated reaction carries out in-20 ℃～+ 80 ℃ scopes, and reaction pressure is 0.1～1.6MPa, and raw material alkane alkene is than 1: 1-200: 1.The yield of prepared alkylated oil can reach 160～180% of alkene feed volume, the C8 proportion can reach 60～80% in the alkylated oil, used ionic-liquid catalyst is reused the productive rate of alkylated oil after 10 times and the selectivity of C8 isoparaffin does not descend the regenerability excellence.All be by ion liquid improvement is improved reaction yield in the above-mentioned patent, alkylation reaction technique still adopts traditional autoclave reaction process, and ionic liquid-catalyzed Trimethylmethane and butene alkylation are typical biliquid phase reactions, and interphase mass transfer speed has determined macroreaction speed.In this type of reaction system, under the situation of the abundant dispersing and mixing of two-phase, alkene can transform fully in very fast realization, if the reaction times is long, what begin to form has high-octane trimethylpentane (TMP) and will continue contact with highly acid ionic-liquid catalyst, can cause the isomerization of TMP to low-octane DMH.Therefore, adopt conventional autoclave to be difficult to be implemented in and obtain high-octane product when obtaining high conversion.And, the alkane during traditional still reaction process actually operating in the charging/alkene than and the material recycle ratio higher, cause difficulty to separation.
High-gravity technology is the reinforcing mass transfer process greatly, can be used for liquid-liquid phase, liquid-solid phase, the mass transfer process of gas-liquid phase, applied research in field of chemical engineering in recent years makes important progress, particularly the Chinese patent " preparation method of ultrafine particle " (application number 95105344.2) that proposes of the applicant (Beijing University of Chemical Technology) and " preparation method of calcium carbonate superfine powder " (95105343.4) etc. the patent No.: series of patents proposes to carry out the chemosynthesis of nano particle with the hypergravity device, the application of high-gravity technology from separating, resolving is exploited to chemical reaction process.In " preparation method of calcium sulfonate with high base number purification agent " (application number 2004100378859) patent application, the applicant is applied to the calcium sulfonate with high base number purification agent preparation process than the complex reaction process such as neutralization reaction, carbonating, phase inversion to high-gravity technology again, obtains high-quality calcium sulfonate detergents.Above-mentioned patent certificate high-gravity technology has changed traditional chemical reaction process, has the wide development application prospect in many chemical reaction processes.Therefore, adopt high-gravity technology to be implemented in and obtain high-octane product when obtaining high conversion.
Summary of the invention
The present invention proposes a kind of processing method of finishing ionic liquid-catalyzed isoparaffin and alkene liquid-liquid phase alkylated reaction in hypergravity swinging bed device, can greatly improve alkylated reaction speed, reduce alkane/alkene ratio and the material recycle ratio in the charging, when obtaining high conversion, obtain high-octane product; The present invention also provides the rotating packed bed reactor device of suitable alkylation reaction technique.
The alkylation reaction technique method that the present invention proposes: liquid alkylated reaction raw material and ionic-liquid catalyst proportionally enter high-gravity rotating bed, in the packing layer of rotation, carry out alkylated reaction, the volume ratio of charging intermediate ion liquid and alkane alkene is controlled at 0.1～1.5: 1, keep total alkane/alkene mol ratio β=10～300 in the reaction mass in the reaction process, temperature of reaction is 8～40 ℃, reaction pressure is 0.3～1.0MPa, the rotating speed of rotating bed rotor is 100～2500rpm, the mean residence time of material in reactor is controlled at≤1～10min, and reacted product separates with raw material and ionic liquid.
Above-mentioned reaction mass can adopt the circulating reaction mode according to the needs of alkylated reaction, the alkane of initial feed/alkene mol ratio is 1: 1～8: 1, reacted partial material, by mixing tank with after fresh ionic liquid mixes, return rotary filler layer and continue to mix with fresh reaction mass, during circulating reaction in maintenance circulating reaction material and the fresh feed mixed solution total alkane/alkene than β=10～300.
Above-mentioned reaction mass and catalyzer are conventional alkylation reaction system, that is: be reaction mass with Trimethylmethane and C3～C5 alkene, and reaction generates gasoline alkylate in acidic ion liquid.Main component in the product is the high C8 isoparaffin of octane value.
Above-mentioned material circulating reaction mode adopts internal recycle, that is: reacted partial material, by mixing tank with after fresh ionic liquid mixes, directly return the rotary filler layer continuation in the reactor and mix with fresh reaction mass.
Above-mentioned material circulating reaction mode, adopt outer circulation, that is: reacted partial material, by mixing tank with leave reactor after fresh ionic liquid mixes, after outside reactor, carrying out heat exchange, return rotary drill reactor, in the packing layer of rotation, continue to mix with fresh reaction mass.
The present invention also provides the rotating bed reaction that is suitable for above-mentioned reaction process apparatus, this device comprises reactor shell, charging opening and discharge port are arranged on the housing, be equipped with in the reactor shell by rotor, the rotating packed bed that packing layer is formed, feed-pipe is wherein arranged, the feed liquid shower nozzle, rotating packed bed is positioned at housing top, lower housing portion is a container for storing liquid, in reactor center whipping appts is housed, can the reaction mass of container for storing liquid be stirred, container for storing liquid and feed liquid recycle pump connect and compose the rotating bed recirculation reactor, the tail pipe ingress of recycle pump is connected with mixing tank, have alkane alkene feed liquid suction port and ionic liquid import on the mixing tank, reacted part feed liquid and ionic liquid mix at mixing tank, and the discharge port of recycle pump connects the feed-pipe of rotating packed bed, and recycle pump is delivered to rotating packed bed to mixed feed liquid and carried out circulating reaction, liquid level control meter is housed, the residence time of control feed liquid on container for storing liquid.
Above-mentioned recycle pump discharge port directly connects the rotating packed bed feed-pipe at inside reactor, forms inner circulation structure, is suitable for the less relatively response situation of reaction heat.
Be serially connected with the outer interchanger portion of reactor that is positioned between above-mentioned recycle pump discharge port and the rotating packed bed feed-pipe, formation outer circulation structure, it is relatively large to be suitable for reaction heat, needs the response situation of heat exchange.
The present invention proposes the reaction process and the reaction unit of ionic liquid-catalyzed isoparaffin and olefin alkylation under the hypergravity condition, greatly improved alkylated reaction speed, reduce in the charging alkane/alkene than and the material recycle ratio, in the acquisition high conversion, obtain the product of high 94～100 octane value; Energy loss-rate traditional method in the production process can reduce by 20%～50%, and ionic liquid can separate simply and recover catalytic activity, and technological process does not produce pollutents such as discarded solvent, waste water, is a kind of environmental protection, energy-conservation technological process.
Description of drawings
Fig. 1 processing method operating process of the present invention synoptic diagram.
Fig. 2 cyclical operation schematic flow sheet of the present invention.
The structural representation of Fig. 3 internal-circulation type revolving bed device of the present invention.
The structural representation of Fig. 4 outer circulation type revolving bed device of the present invention.
Embodiment
As shown in Figure 2, the reaction unit that is used for processing method of the present invention comprises: rotary drill reactor 1, alkane alkene pump 2, alkane alkene jar 3, condenser 4, rectifying tower 5, separating tank 6, catalyst tank 7, catalyst pump 8 and interchanger 9.The wherein preferred structure of revolving bed device reactor such as Fig. 3, Fig. 4, shown in, it comprises motor 10, reactor shell, by rotor, the rotating packed bed that packing layer is formed, catalyzer shower nozzle 11, rotor 12, catalyst charge pipe 13, liquid level control meter 14, liquid outlet 15, alkane alkene feed-pipe 17, alkane alkene shower nozzle 18, charging opening 19 and nitrogen inlet 20, wherein, rotating packed bed is positioned at reactor shell top, lower housing portion is a container for storing liquid, in reactor center whipping appts 16 is housed, can the reaction mass of container for storing liquid be stirred, prevent material layering and make that the composition of circulation fluid is inhomogeneous in reactor.Circulating reaction for the realization response material, can connect and compose the rotating bed recirculation reactor to container for storing liquid and feed liquid recycle pump 21, the tail pipe ingress of recycle pump is associated with mixing tank 22, have alkane alkene feed liquid suction port 23 and ionic liquid import 24 on the mixing tank, reacted feed liquid and ionic liquid mix at mixing tank, the discharge port of recycle pump connects the feed-pipe 13 of rotating packed bed, recycle pump is delivered to rotating packed bed to mixed feed liquid and is carried out circulating reaction, liquid level control meter 14 is housed, the residence time of control feed liquid on container for storing liquid.
When above-mentioned recycle pump discharge port directly connects rotating packed bed feed-pipe 13 at inside reactor, form the inner circulation structure (see figure 2), be suitable for the less relatively response situation of reaction heat;
Be serially connected with the interchanger portion 25 that is positioned at outside the reactor between above-mentioned recycle pump discharge port and rotating packed bed feed-pipe 13, form outer circulation structure (see figure 3), it is relatively large to be suitable for reaction heat, needs the reaction of heat exchange.
The preferred taper mixing of above-mentioned mixer structure suction inlet structure (seeing Fig. 3, Fig. 4), be that the recycle pump material sucking port is a bell 23, wherein be with the ionic liquid charging mouth of pipe 22, recycle pump directly mixes partial reaction feed liquid and ionic liquid and is pumped into the feed-pipe 13 of rotating packed bed.
The container for storing liquid of above-mentioned revolving bed device reactor of the present invention also can not connect recycle pump, constitutes the reactor of once finishing reaction.
The present invention realizes alkylated reaction in said apparatus, reactive mode can adopt circulation or acyclic mode, and wherein preferred circulating reaction technology process is:
With alkane alkene pump 2 mixing raw material of Trimethylmethane in the alkane alkene jar 3 and C3-C5 alkene is sprayed into rotating packed bed by alkane alkene feed-pipe and alkane alkene shower nozzle, simultaneously the ionic liquid in the catalyst tank 7 is sprayed into rotating packed bed by catalyst charge pipe 13 and catalyzer shower nozzle 11, in the packing layer of rotating packed bed, carry out alkylated reaction, charging intermediate ion liquid and fresh feed volume ratio are controlled at 0.1～1.5, the alkane of initial feed/alkene mol ratio is 1: 1～8: 1, keep total alkane/alkene mol ratio β=10～300 in the reaction mass during circulating reaction, temperature of reaction is 8～40 ℃, reaction pressure is 0.3～1.0MPa, the rotating speed of rotating bed rotor is 100～2500rpm, reacted feed liquid is thrown out of and is pooled in the container for storing liquid of reactor lower part, reacted partial material, after entering mixing tank and fresh ionic liquid mixing, returning rotary filler layer continues to mix with fresh reaction mass, realize the circulating reaction of material, after the volume of material in the reactor reaches certain amount, open the outlet valve of reactor container for storing liquid, regulating rate of discharge makes volume of material keep certain, and the mean residence time of control material in reactor is controlled at≤1～10min, the residence time of material, the material that leaves reactor enters separating tank 6 to be separated by the control of liquid level control meter.The isolated ionic liquid in separating tank bottom is pumped back to catalyst tank 7, recycles.Enter rectifying tower 5 at isolated alkylate oil in separating tank top and Trimethylmethane, the isolated Trimethylmethane of rectifying tower cat head is returned the Trimethylmethane storage tank by pump, recycles.Obtain product-alkylate oil at the bottom of the tower.
The circulating reaction of above-mentioned reaction mass, can take inner loop mode: promptly reacted partial material, after passing through mixing tank 22 and fresh ionic liquid mix, in reactor, directly pump into catalyst charge pipe 13, return rotary filler layer and continue to mix, react with fresh reaction mass, inner loop mode is suitable for the less relatively response situation of reaction heat;
The circulating reaction of above-mentioned reaction mass, can take the outer circulation mode: reacted partial material is mixed at mixing tank with fresh ionic liquid, leave reactor after the mixing, after carrying out heat exchange in the interchanger portion 25 outside reactor, pump into catalyst charge pipe 13, return and continue in the packing layer of rotation to mix with fresh reaction mass.
The enforcement of processing method of the present invention also can be adopted acyclic mode (see figure 1), the alkane of raw material/alkene mol ratio is β=10～300, after the volume of material in the reactor reaches certain amount, open the outlet valve of reactor container for storing liquid, regulating rate of discharge makes volume of material keep certain, and by liquid level control meter 14 mean residence time of material in reactor is controlled at≤1～10min, the material that leaves reactor all enters separating tank 6 to be separated.Acyclic mode is suitable for the situation that the residence time requires weak point.
Below by embodiment above-mentioned embodiment is further specified.
Embodiment 1: carry out the non-circulating type alkylated reaction by flow process shown in Figure 1.With nitrogen reaction system is pressurized to 0.5MPa, with alkane alkene pump 2 mixing raw material of the Trimethylmethane in the alkane alkene jar 3 and 2-butylene, 1-butylene and iso-butylene is sprayed into rotating packed bed by alkane alkene feed-pipe 17 and alkane alkene shower nozzle 18, the volumetric flow rate of raw material alkane alkene is 80L/h, and the mol ratio of alkane alkene is 150: 1 in the raw material.Simultaneously the ionic liquid in the catalyst tank 7 is sprayed into rotating bed by catalyst charge pipe 13 and catalyzer shower nozzle 11, ionic liquid and reaction raw materials feeding rate (volume) are than being 0.5.Ionic liquid and reaction raw materials be the living reaction of hybrid concurrency mutually in the rotating bed packing layer, be thrown out of afterwards and be pooled in the reactor, after the volume of material in the reactor reaches certain amount, open the reactor outlet valve, regulate rate of discharge and make volume of material keep certain, and by the 14 control residence time of material in reaction system of liquid level control meter be 1min.The material that leaves reactor enters separating tank 6 to be separated.The isolated ionic liquid in separating tank bottom is pumped back to catalyst tank 7, recycles.Enter rectifying tower 5 at isolated alkylate oil in separating tank top and Trimethylmethane, the isolated Trimethylmethane of rectifying tower cat head is returned the Trimethylmethane storage tank by pump, recycles.Obtain product-alkylate oil at the bottom of the tower.Temperature of reaction is controlled at 25 ℃, and the rotating speed of rotating bed is controlled at 1200rpm.Catalyst system therefor is the room temperature acidic ion liquid, be with the hydrohalogen of the amine that contains alkyl or the hydrohalogen and the metal halide prepared in reaction of pyridine, the nitrogen-atoms of the halogenide of the described amine that contains alkyl or the hydrohalogen of pyridine is saturated by four substituting groups, and wherein have at least one to be hydrogen atom and at least one alkyl substituent, metal halide is selected from the muriate of aluminium, copper, iron and zinc.The octane value of gained alkylate oil is 95.5 (research octane number (RON)s).
Embodiment 2: carry out material internal recycle alkylated reaction by flow process shown in Figure 2.With nitrogen reaction system is pressurized to 0.4MPa, ionic liquid in the catalyst tank 7 is squeezed in the reactor by charging opening 19, ON cycle pump 21 after reaching certain liquid level, alkane alkene pump 2 sprays into rotating bed with the mixing raw material of the Trimethylmethane in the alkane alkene jar 3 and 2-butylene, 1-butylene and iso-butylene by alkane alkene feed-pipe 17 and alkane alkene shower nozzle 18, the volumetric flow rate of raw material is 80L/h, and ionic liquid and reaction raw materials feeding rate (volume) are than being 0.25: 1.Ionic liquid and reaction raw materials be the living reaction of hybrid concurrency mutually in packing layer.Be thrown out of afterwards and be pooled in the reactor, partial material in the reactor is sucked into cone mixer 22 by recycle pump, in cone mixer, mix with ionic liquid from catalyst tank 7, the rotating packed bed feed-pipe of mixed feed liquid by being connected with the pump discharge port, directly pump into rotary filler layer from inside reactor and carry out circulating reaction, after the volume of material in the reactor reaches certain amount, open the reactor outlet valve, regulate rate of discharge and make volume of material keep certain, and by the 14 control residence time of material in reaction system of liquid level control meter be 5min.The flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=100 in circulation fluid and the fresh feed mixed solution.The material that leaves reactor enters separating tank 6 to be separated.The isolated ionic liquid in separating tank bottom is pumped back to catalyst tank 7, recycles.Enter rectifying tower 5 at isolated alkylate oil in separating tank top and Trimethylmethane, the isolated Trimethylmethane of rectifying tower cat head is returned the Trimethylmethane storage tank by pump, recycles.Obtain product-alkylate oil at the bottom of the tower.Temperature of reaction is controlled at 15 ℃, and the rotating speed of rotating bed rotor is controlled at 900rpm, and the mol ratio of alkane alkene is 3: 1 in the fresh reactant raw material.Used ionic liquid is identical with embodiment 1.The octane value of gained alkylate oil is 95.7 (research octane number (RON)s).
Embodiment 3: carry out the outer circulation type alkylated reaction by flow process shown in Figure 2.With nitrogen reaction system is pressurized to 0.5MPa, ionic liquid in the catalyst tank 7 is squeezed in the reactor by charging opening 19, ON cycle pump 21 after reaching certain liquid level, alkane alkene pump 2 sprays into rotating bed with the mixing raw material of the Trimethylmethane in the alkane alkene jar 3 and 2-butylene, 1-butylene and iso-butylene by alkane alkene feed-pipe 17 and alkane alkene shower nozzle 18, the volumetric flow rate of raw material is 80L/h, and ionic liquid and reaction raw materials feeding rate (volume) are than being 0.25.Ionic liquid and reaction raw materials be the living reaction of hybrid concurrency mutually in packing layer.Be thrown out of afterwards and be pooled in the reactor, partial material in the reactor is sucked into cone mixer 22 by recycle pump, in cone mixer, mix with ionic liquid from the ion jar, mixed feed liquid detaches reactor by pump, after carrying out heat exchange in the interchanger 25 outside reactor, pump into catalyst charge pipe 13, return and continue in the packing layer of rotation to mix with fresh reaction mass.After the volume of material in the reactor reaches certain amount, open the reactor outlet valve, regulate rate of discharge and make volume of material keep certain, and the control residence time of material in reaction system is 2min.The flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=100 in circulation fluid and the fresh feed mixed solution.The material that leaves reactor enters separating tank 6 to be separated.The isolated ionic liquid in separating tank bottom is pumped back to catalyst tank 7, recycles.Enter rectifying tower 5 at isolated alkylate oil in separating tank top and Trimethylmethane, the isolated Trimethylmethane of rectifying tower cat head is returned the Trimethylmethane storage tank by pump, recycles.Obtain product-alkylate oil at the bottom of the tower.Temperature of reaction is controlled at 25 ℃, and the rotating speed of rotating bed rotor is controlled at 1000rpm.The mol ratio that enters into the fresh reactant raw material alkane alkene of rotating bed is 3: 1.Used ionic liquid is identical with embodiment 1.The octane value of gained alkylate oil is 96.2 (research octane number (RON)s).
Embodiment 4: operating method is identical with embodiment 3 with operating process, alkane in the stock liquid/alkene ratio is 5: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 0.5: 1, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=150 in circulation fluid and the fresh feed mixed solution.Temperature of reaction is 15 ℃, and pressure is 0.4MPa, and the residence time of material in reactor is controlled at 8min, and the rotating speed of rotating bed rotor is controlled at 800rpm, and used ionic liquid is identical with embodiment 1.The octane value of products obtained therefrom is 97 (research octane number (RON)s).
Embodiment 5: operating method is identical with embodiment 3 with operating process, alkane in the stock liquid/alkene ratio is 2: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 1: 1, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=10 in circulation fluid and the fresh feed mixed solution.Temperature of reaction is 8 ℃, and pressure is 0.3MPa, and the residence time of material in reactor is controlled at 3min, and the rotating speed of rotating bed rotor is controlled at 1800rpm, and used ionic liquid is identical with embodiment 1.The octane value of products obtained therefrom is 95.2 (research octane number (RON)s).
Embodiment 6: operational condition is identical with embodiment 4, but used ionic liquid is the combination of acidic ionic liquid, cation source is in the hydrohalogen of the amine that contains alkyl or the hydrohalogen of pyridine, and negatively charged ion is the composite anion that two or more metallic compound makes.The octane value of products obtained therefrom is 95.5 (research octane number (RON)s).
Embodiment 7: operating method is identical with embodiment 2 with operating process, alkane in the stock liquid/alkene ratio is 8: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 1: 1, temperature of reaction is 25 ℃, and pressure is 0.5MPa, and the residence time of material in reactor is controlled at 3min, the rotating speed of rotating bed is 2500rpm, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=300 in circulation fluid and the fresh feed mixed solution.Used ionic liquid is identical with embodiment 1.The octane value of gained alkylate oil is 96.4 (research octane number (RON)s).
Embodiment 8: operating method is identical with embodiment 3 with operating process, alkane in the stock liquid/alkene ratio is 8: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 0.1: 1, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=300 in circulation fluid and the fresh feed mixed solution.Temperature of reaction is 35 ℃, and pressure is 0.7MPa, and the residence time of material in reactor is controlled at 10min, and the rotating speed of rotating bed rotor is controlled at 100rpm, and used ionic liquid is identical with embodiment 1.The octane value of gained alkylate oil is 96.0 (research octane number (RON)s).
Embodiment 9: operating method is identical with embodiment 3 with operating process, alkane in the stock liquid/alkene ratio is 1: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 1.5: 1, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=200 in circulation fluid and the fresh feed mixed solution.Temperature of reaction is 40 ℃, and pressure is 1.0Pa, and the residence time of material in reactor is controlled at 1min, and the rotating speed of rotating bed rotor is controlled at 2500rpm, and used ionic liquid is identical with embodiment 1.
The octane value of products obtained therefrom is 95.0 (research octane number (RON)s).
Embodiment 10: operating method is identical with embodiment 1 with operating process, alkane in the stock liquid/alkene ratio is 300: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 1.5: 1, temperature of reaction is 8 ℃, and pressure is 0.3MPa, and the residence time of material in reactor is controlled at 10min, the rotating speed of rotating bed rotor is controlled at 2500rpm, and used ionic liquid is identical with embodiment 1.
The octane value of products obtained therefrom is 96.2 (research octane number (RON)s).
Embodiment 11: operating method is identical with embodiment 1 with operating process, alkane in the stock liquid/alkene ratio is 10: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 0.1: 1, temperature of reaction is 40 ℃, and pressure is 1.0MPa, and the residence time of material in reactor is controlled at 5min, the rotating speed of rotating bed rotor is controlled at 100rpm, and used ionic liquid is identical with embodiment 1.
The octane value of products obtained therefrom is 94.0 (research octane number (RON)s).
Embodiment 12: operating method is identical with embodiment 2 with operating process, alkane in the stock liquid/alkene ratio is 1: 1, volumetric flow rate is 80L/h, the volume ratio of ionic liquid and fresh feed is 0.667: 1, and temperature of reaction is 40 ℃, and pressure is 1.0MPa, the residence time of material in reactor is controlled at 8min, the rotating speed of rotating bed is 100rpm, and the flow of Control Circulation liquid makes that total alkane/alkene is than (mol ratio) β=10 in circulation fluid and the fresh feed mixed solution, and used ionic liquid is identical with embodiment 1.
The octane value of products obtained therefrom is 94.2 (research octane number (RON)s).
Claims (8)
1, a kind of alkylation reaction technique catalyzed by ion liquid, it is characterized in that: Trimethylmethane and C3～C5 alkene liquid reaction raw material and ionic-liquid catalyst enter rotating bed in proportion, in the packing layer of rotation, carry out alkylated reaction, the volume ratio of charging intermediate ion liquid and alkane alkene is controlled at 0.1～1.5: 1, keep total alkane/alkene mol ratio β=10～300 in the reaction mass in the reaction process, temperature of reaction is 8～40 ℃, reaction pressure is 0.3～1.0MPa, the rotating speed of rotating bed rotor is 100～2500rpm, the mean residence time of material in reactor is controlled at≤1～10min, and reacted product separates with raw material and ionic liquid.
2, reaction process according to claim 1, it is characterized in that: reaction mass adopts the circulating reaction mode, the alkane of initial feed/alkene mol ratio is 1: 1～8: 1, keeps total alkane/alkene mol ratio β=10～300 in circulating reaction material and the fresh feed mixed solution during circulating reaction.
3, reaction process according to claim 1, it is characterized in that: the circulating reaction mode is an internal recycle, that is: reacted partial material, by mixing tank with after fresh ionic liquid mixes, directly return rotary filler layer in the reactor and continue to mix, react with fresh reaction mass.
4, reaction process according to claim 1, it is characterized in that: the circulating reaction mode is outer circulation, that is: reacted partial material, by mixing tank with leave reactor after fresh ionic liquid mixes, outside reactor, carry out returning after the heat exchange in the packing layer of rotation and continue to mix, react with reaction mass.
5, a kind of reactor assembly that is used for the alkylation reaction technique catalyzed by ion liquid of claim 1, comprise reactor shell, charging opening and discharge port are arranged on the housing, have in the reactor shell by rotor, the rotating packed bed that packing layer is formed, feed-pipe is wherein arranged, the feed liquid shower nozzle, it is characterized in that, rotating packed bed is positioned at housing top, lower housing portion is a container for storing liquid, in reactor center whipping appts is housed, container for storing liquid and feed liquid recycle pump connect and compose the rotating bed recirculation reactor, the tail pipe ingress of recycle pump is connected with mixing tank, have alkane alkene feed liquid suction port and ionic liquid import on the mixing tank, reacted feed liquid and ionic liquid mix at mixing tank, the discharge port of recycle pump connects the feed-pipe of rotating packed bed, recycle pump is delivered to rotating packed bed to mixed feed liquid and is carried out circulating reaction, liquid level control meter is housed, the residence time of control feed liquid on container for storing liquid.
6, reactor assembly according to claim 5 is characterized in that: the recycle pump discharge port directly connects the feed-pipe of rotating packed bed at inside reactor, forms inner circulation structure.
7, reactor assembly according to claim 5 is characterized in that: be serially connected with the interchanger that is positioned at outside the reactor between recycle pump discharge port and the rotating packed bed feed-pipe, form the outer circulation structure.
8, reactor assembly according to claim 5, it is characterized in that: described mixing tank is a taper mixing suction inlet, that is: the recycle pump material sucking port is a bell, wherein is with the ionic liquid charging mouth of pipe, and recycle pump directly mixes partial reaction feed liquid and ionic liquid.
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| WO2020169079A1 (en) | 2019-02-21 | 2020-08-27 | 中国石油化工股份有限公司 | Alkylation reaction apparatus and reaction system, and liquid acid-catalyzed alkylation reaction method |
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| US8198499B2 (en) * | 2007-12-28 | 2012-06-12 | Chevron U.S.A. Inc. | Ionic liquid catalyzed alkylation process employing nozzles and system implementing such process |
| CN102108306B (en) * | 2009-12-28 | 2013-12-18 | 中国石油大学(北京) | Alkylation reaction method using ionic liquid as catalyst |
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| CN104549086B (en) * | 2013-10-24 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of alkylation reactor and alkylation process |
| CN104560144B (en) * | 2013-10-24 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of sectional feeding alkylation reaction method |
| CN104549110B (en) * | 2013-10-24 | 2016-04-13 | 中国石油化工股份有限公司 | Alkylation reactor and alkylation reaction technique method |
| CN104667856B (en) * | 2013-11-29 | 2016-04-27 | 中国石油化工股份有限公司 | Alkylation reactor and alkylation reaction method |
| CN106281432B (en) * | 2015-05-21 | 2017-11-17 | 北京化工大学 | It is a kind of to utilize the system and device and production method that sulfuric acid is catalyst preparation alkylate oil |
| US10279339B2 (en) * | 2016-11-02 | 2019-05-07 | Chevron U.S.A. Inc. | Integrated system to continuously inject small amounts of immiscible liquid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283255A (en) * | 1977-12-01 | 1981-08-11 | Imperial Chemical Industries Limited | Mass transfer process |
| CN1059105A (en) * | 1991-10-08 | 1992-03-04 | 北京化工学院 | Rotating bed super gravity field is strengthened transmission and reaction unit |
| CN1500764A (en) * | 2002-11-12 | 2004-06-02 | ʯ�ʹ�ѧ(����) | Preparing method for alkylate agent using compound ion as catalyst |
-
2005
- 2005-08-02 CN CNB2005100888343A patent/CN100348559C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283255A (en) * | 1977-12-01 | 1981-08-11 | Imperial Chemical Industries Limited | Mass transfer process |
| CN1059105A (en) * | 1991-10-08 | 1992-03-04 | 北京化工学院 | Rotating bed super gravity field is strengthened transmission and reaction unit |
| CN1500764A (en) * | 2002-11-12 | 2004-06-02 | ʯ�ʹ�ѧ(����) | Preparing method for alkylate agent using compound ion as catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169079A1 (en) | 2019-02-21 | 2020-08-27 | 中国石油化工股份有限公司 | Alkylation reaction apparatus and reaction system, and liquid acid-catalyzed alkylation reaction method |
| US11890589B2 (en) | 2019-02-21 | 2024-02-06 | China Petroleum & Chemical Corporation | Alkylation reaction apparatus, reaction system, and liquid acid catalyzed alkylation reaction process |
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