CN112827215B - Cyclone extraction method and device for C5 petroleum resin polymerization liquid - Google Patents
Cyclone extraction method and device for C5 petroleum resin polymerization liquid Download PDFInfo
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Abstract
The invention relates to a rotational flow extraction method and a device for C5 petroleum resin polymerization liquid, and provides a rotational flow extraction method for C5 petroleum resin polymerization liquid, which comprises the following steps: (a) injecting C5 raw material polymerization liquid containing catalyst impurities wrapped with a resin layer and alkali liquor into a cyclone extraction separator together to remove the catalyst; (b) feeding the C5 raw material polymerization liquid without the catalyst obtained in the step (a) into a next-stage cyclone extraction separator to further remove the catalyst; and (c) the polymerization liquid from which the catalyst is further removed in the step (b) enters a standing layering tank for standing oil-water primary separation, wherein the water phase enters a sewage treatment system for treatment, the oil phase enters a coalescence dehydrator for deep dehydration, the deeply removed water phase enters the sewage treatment system, the deeply dehydrated oil phase polymerization liquid enters a settling tank to obtain crude resin liquid, and then the crude resin liquid is sent to the next unit for treatment to obtain a resin product. Also provides a C5 petroleum resin polymerization liquid cyclone extraction device.
Description
Technical Field
The invention belongs to the technical field of chemical production, in particular to the technical field of difficult-to-separate catalysts, and relates to a method for cyclone extraction of C5 petroleum resin polymerization liquid, which is suitable for removing catalysts and other impurities dissolved in other petroleum resin production polymerization liquid. Specifically, the present disclosure provides a method and apparatus for enhancing liquid-liquid extraction efficiency by a cyclone.
Background
The C5 petroleum resin is a chemical product produced by using the by-product carbon five petroleum resin component produced by petroleum cracking as raw material and through the processes of pretreatment, polymerization and distillation. The petroleum resin has the advantages of low price, good miscibility, low melting point, water resistance, ethanol resistance, chemicals resistance and the like, so the petroleum resin is widely applied to various industries and fields of rubber, adhesives, coatings, papermaking, printing ink and the like, wherein the polymerization of C5 petroleum resin is the most important factor influencing the quality of petroleum resin products. The polymerization process of C5 petroleum resin is mainly divided into two types: thermal polymerization process and catalytic polymerization process, because the catalytic polymerization process produces C5 petroleum resin with high quality, and is widely used in industrial production. Currently, anhydrous aluminum trichloride is generally selected as a catalyst in industry to produce C5 petroleum resin by a catalytic polymerization method. In many industrial processes, a large amount of polymer liquid containing inorganic substances is produced, and the inorganic substances are required to be removed for the refining and purification of products and the qualified discharge of the produced polymer liquid.
Extraction is a common method for effectively removing organic matters in water. In general industrial extraction equipment, an extractant and an extracted substance are stirred and mixed uniformly for a certain time, so that the extract is transferred between two phases, and then an oil phase and a water phase are separated by standing (gravity method) or other methods, so that the purpose of extraction and separation is achieved. The equipment required for realizing the process is huge, the process has low efficiency, and the oil content in the water phase or the water content in the oil phase is high, so that the complete separation is difficult.
At present, devices such as a gravity settling tank, a coalescence separator and the like are commonly used in industry for liquid-liquid separation operation. When a solute or a catalyst mixed in a raw material liquid is removed by a neutralization reaction, the raw material liquid is generally injected into a neutralization tank to perform a reaction, and the raw material liquid inevitably comes into contact with a neutralizing agent, so that a process of emulsifying the raw material liquid by water mixed in the neutralizing agent tends to occur during stirring in the neutralization tank. Meanwhile, new salt paste impurities are easily formed between the raw material liquid and the water.
The Chinese patent application CN109851715A discloses a hydrogenated petroleum resin and a preparation method thereof. The method is characterized in that AlCl in C5 petroleum resin liquid is added3The catalyst reacts with the added methanesulfonic acid to generate aluminum methylsulfonate after reaction, and AlCl is further realized3Compared with the neutralization reaction of NaOH alkali liquor, the removal of the methyl sulfonic acid is low in reaction efficiency, higher in raw material cost, more in waste water generated by the reaction, and increased in burden of post-treatment of waste water.
Chinese patent application CN1944484A discloses a method for removing AlCl from C5 petroleum resin production process3And a product purification method, wherein NaOH alkaline liquor is directly injected into the C5 petroleum resin liquid, and after uniform stirring and mixing, the residual NaOH alkaline liquor on the surface of the resin is washed away by clean water, thereby realizing the removal of aluminum trichloride. However, the method has the advantages that the consumption of NaOH alkali liquor is increased, the reaction is insufficient, the waste water discharge is increased due to the fact that too much NaOH alkali liquor is injected at one time, meanwhile, the emulsification is easy in the neutralization and stirring process, and salt paste is easy to form in the oil-water medium.
In order to solve the problems of catalyst removal, sewage treatment and the like in petroleum resin production, a large number of patents adopt externally added chemical agents to remove the catalyst through neutralization reaction, but the traditional neutralization reaction needs a large amount of added chemical agents, the chemical agents are easy to emulsify in the neutralization stirring process, salt paste is easy to form between a polymerization solution and water after the reaction, and meanwhile, the catalyst is wrapped by resin, so that the problems of low reaction efficiency and low catalyst removal efficiency are caused. Therefore, a set of efficient, economical, energy-saving, environment-friendly and reliable separation process needs to be developed, so that the catalyst in the polymerization liquid can be effectively separated and the consumption of the polymerization liquid can be reduced, the possibility of emulsification and salt paste formation in the neutralization reaction process can be avoided, the removal of the outer coating layer of the catalyst can be effectively realized, and the removal of the catalyst in the petroleum resin can be further efficiently realized.
Disclosure of Invention
The present disclosure provides a novel cyclone extraction method and apparatus for C5 petroleum resin polymerization liquid, which solves the problems existing in the prior art.
In one aspect, the present disclosure provides a cyclone extraction method of C5 petroleum resin polymerization liquid, comprising the following steps:
(a) injecting C5 raw material polymerization liquid containing catalyst impurities wrapped with resin layers and alkali liquor into a cyclone extraction separator together to remove the catalyst;
(b) feeding the C5 raw material polymerization liquid without the catalyst obtained in the step (a) into a next-stage cyclone extraction separator to further remove the catalyst; and
(c) and (b) allowing the polymerization solution from which the catalyst is further removed in the step (b) to enter a standing layering tank for standing oil-water primary separation, allowing the water phase to enter a sewage treatment system for treatment, allowing the oil phase to enter a coalescence dehydrator for deep dehydration, allowing the deeply removed water phase to enter the sewage treatment system, allowing the deeply dehydrated oil phase polymerization solution to enter a settling tank to obtain a crude resin solution, and allowing the crude resin solution to enter the next unit for treatment to obtain a resin product.
In a preferred embodiment, the method further comprises the steps of:
before the step (a), C5 raw material, polymerization liquid and catalyst are reacted in a polymerization reaction kettle, and the polymerization liquid of the C5 raw material containing a large amount of catalyst obtained by the reaction is sent to an ebullated bed separator to remove most of the catalyst, so that the polymerization liquid of the C5 raw material containing the catalyst impurities wrapped by a resin layer is obtained.
In another preferred embodiment, in step (a), the catalyst is AlCl3A solid catalyst; the alkali liquor is NaOH solution.
In another preferred embodiment, in step (a), the solid content of the catalyst in the polymerization solution at the inlet of the cyclone extraction separator is less than or equal to 8000mg/L, the viscosity of the polymerization solution is less than or equal to 22cp, and the particle size of the catalyst is less than or equal to 500 μm.
In another preferred embodiment, in step (a), in the cyclone extraction separator, the catalyst is desorbed from the outer resin layer under the action of the coupling of rotation and revolution, then the catalyst is sufficiently neutralized with alkali liquor through the extraction reaction, the precipitate phase generated through the neutralization reaction flows into the sewage treatment system through the bottom flow port, and the C5 raw material polymer solution from which the catalyst is removed flows into the next stage cyclone extraction separator through the overflow port.
In another preferred embodiment, after the separation by the cyclone extraction, the separation efficiency of the resin coated outside the catalyst is more than or equal to 90 percent, the catalyst separation efficiency of the polymerization solution of the C5 raw material is more than or equal to 90 percent, the usage amount of the neutralization alkali liquor is reduced by 85 percent, and the pressure loss of the cyclone extraction separator is 0.02-0.3 MPa.
In another preferred embodiment, the cyclone extraction separator adopts a multi-stage series structure, the size of the cyclone extraction separator is designed according to actual treatment capacity, the series stage is designed according to actual requirements, an overflow port of the previous stage of cyclone extraction separator is connected to an inlet of the next stage of cyclone extraction separator, and lye is injected in batches at the other inlet of each stage of cyclone extraction separator.
In another aspect, the present disclosure provides a C5 petroleum resin polymer liquid cyclone extraction device, comprising:
a multi-stage series-connected cyclonic extraction separator for performing the steps of: (a) injecting C5 raw material polymerization liquid containing catalyst impurities wrapped with resin layers and alkali liquor into a cyclone extraction separator together to remove the catalyst; and (b) sending the C5 raw material polymerization liquid without the catalyst obtained in the step (a) to a next-stage cyclone extraction separator to further remove the catalyst; and
the device comprises a standing layering tank connected with a cyclone extraction separator, a coalescent dehydrator connected with the standing layering tank, and a settling tank connected with the coalescent dehydrator, wherein the settling tank is used for carrying out the following steps: (c) and (b) allowing the polymerization solution from which the catalyst is further removed in the step (b) to enter a standing layering tank for standing oil-water primary separation, allowing the water phase to enter a sewage treatment system for treatment, allowing the oil phase to enter a coalescence dehydrator for deep dehydration, allowing the deeply removed water phase to enter the sewage treatment system, allowing the deeply dehydrated oil phase polymerization solution to enter a settling tank to obtain a crude resin solution, and allowing the crude resin solution to enter the next unit for treatment to obtain a resin product.
In a preferred embodiment, the apparatus further comprises:
a bubbling bed separator connected to the cyclonic extraction separator, and a polymerization reactor connected to the bubbling bed separator for performing the steps of: before the step (a), C5 raw material, polymerization liquid and catalyst are reacted in a polymerization reaction kettle, and the polymerization liquid of the C5 raw material containing a large amount of catalyst obtained by the reaction is sent to an ebullated bed separator to remove most of the catalyst, so that the polymerization liquid of the C5 raw material containing the catalyst impurities wrapped by a resin layer is obtained.
In another preferred embodiment, the bottom of the cyclone extraction separator is provided with a vortex plate, and the rotating speed is 100-.
Has the advantages that:
1) the method combines the liquid-liquid cyclone separation method and the extraction method, and makes up for the AlCl3The catalyst is wrapped by resin and can not be fully released to complete neutralization reaction, and simultaneously the defects that the catalyst is easy to emulsify in the neutralization stirring process and salt paste (insoluble in oil and water) is easy to form in the oil-water are overcome, and the two separation methods complement each other.
2) The method of the invention utilizes liquid-liquid rotational flow to extract, and the three-dimensional turbulent flow field in the cyclone has strong vortex diffusion effect, thereby reducing the solute mass transfer resistance in the continuous phase and strengthening the interface mass transfer rate.
3) The method of the invention enables the micro-droplets of the NaOH dilute alkali solution in the cyclone to follow the continuous phase to move along the spiral line under the action of drag force, centrifugal force and the like, so that the continuous phase and the dispersed phase have very long mixed contact length, thereby improving the probability of the dispersed phase capturing solute particles in the continuous phase and finally enhancing the liquid-liquid extraction efficiency.
4) The method of the invention utilizes the strong fluid shearing action in the cyclone, and the cyclone can be used as a scrubber to remove the resin coating layer adhered on the impurity particles such as the catalyst, so that the catalyst can better react with the extraction liquid to remove the extraction liquid.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification to further illustrate the disclosure and not limit the disclosure.
FIG. 1 is a schematic overall process flow diagram of a cyclone extraction of C5 petroleum resin polymerization liquid according to a preferred embodiment of the present disclosure.
FIG. 2 is a schematic diagram of a cyclonic extraction separator apparatus according to a preferred embodiment of the present disclosure.
FIG. 3 is a schematic diagram of a cyclone extraction process flow of C5 petroleum resin polymerization liquid according to a preferred embodiment of the present disclosure.
Detailed Description
The inventors of the present application have conducted extensive and intensive studies with respect to the tendency to form a salt paste between a polymerization solution and water in the production of C5 petroleum resin and the neutralization of AlCl3High alkali liquor consumption of catalyst and AlCl3The difficult problems that the catalyst cannot be effectively removed in the later period of being wrapped by the resin layer and the oil phase is acidic due to the release of the catalyst in the later period are solved by adopting the mode of serially connecting a plurality of liquid-liquid cyclone extraction separators and injecting NaOH alkali liquor into each separator in batches, so that the problem that AlCl cannot be effectively removed due to the fact that NaOH alkali liquor is too high in one-time injection manner is avoided3Problems with the catalyst; simultaneously realizes AlCl through the coupling action of rotation and revolution in the cyclone3The effective removal of the resin coating layer outside the catalyst realizes the effective removal of the AlCl coated by the resin in the C5 raw material polymerization liquid3The catalyst is completely removed, the method is simple and effective, and the problems of incomplete separation and short equipment operation period in the existing method are solved.
The technical concept of the invention is as follows:
will contain AlCl3Respectively injecting polymerization liquid of the catalyst and NaOH solution into the cyclone extraction separator from two inlets, mixing the two inlets, and accelerating AlCl in the C5 polymerization liquid through the vortex diffusion effect of an internal flow field and the autorotation motion of liquid drops in the flow field3The migration process of the catalyst to NaOH leads AlCl to be generated through neutralization reaction3Catalyst removalIn the form of falling AlCl3The resin coating outside the catalyst can be separated by centrifugal force due to the density difference between the resin coating and the resin coating; meanwhile, the catalysts are injected into the multistage liquid-liquid cyclone extraction separator in batches, so that the emulsification process in the neutralization and stirring process can be effectively reduced, and the clean C5 polymerization solution enters the next unit to participate in the copolymerization reaction. The invention effectively improves the purity and the product quality of the C5 raw material liquid by using the liquid-liquid cyclone extraction separator; AlCl in polymerization liquid3The catalyst is reduced by 90 percent, the emission of high-concentration wastewater is reduced by 80 percent, and the usage amount of the neutralized alkali liquor is reduced by 85 percent.
In a first aspect of the present disclosure, there is provided a C5 petroleum resin polymerization liquid cyclone extraction method, comprising the steps of:
will contain AlCl3Respectively injecting C5 raw material polymerization solution of catalyst impurities (coated with resin layer) and NaOH solution into cyclone extraction separator from two inlets, and introducing AlCl into the cyclone extraction separator3The desorption of the outer coating resin layer of the catalyst is realized under the coupling action of rotation and revolution, then the catalyst can fully generate neutralization reaction with NaOH solution through extraction reaction, aluminum hydroxide precipitation phase generated through the reaction flows into a sewage treatment system through a bottom flow port, and most AlCl is removed3C5 raw material polymerization liquid of the catalyst flows into a next-stage cyclone extraction separator through an overflow port, and further desorption process is carried out in the next-stage cyclone extraction separator; after the same separation process of the next stage, the clean C5 raw material polymerization liquid is sent to a rear-end separation device for oil-water separation.
In the disclosure, under the action of shear stress of a swirling flow field, droplets with large particle size are broken into small droplets, and the droplets move along a spiral line along with a continuous phase (polymerization liquid) under the action of drag force, centrifugal force and the like; simultaneously due to AlCl3The catalyst and the resin coating layer often have density difference, namely the catalyst and the resin coating layer are different in centrifugal force, namely solute particles and the coating layer are separated by centrifugal force in the cyclone extraction separation;
the droplets being in motion and being forced between the two phases mainly by convective diffusion caused by turbulent pulsation of the continuous phaseMass transfer, namely, the AlCl in the polymerization liquid3The catalyst and NaOH dilute alkali liquor are subjected to neutralization reaction to realize AlCl in the polymerization solution3Removing the catalyst; and
meanwhile, dispersed phase liquid drops generate autorotation motion under the action of a flow field shearing force, so that a strong internal circulation flow is formed in the liquid drops, the surface updating of the micro liquid drops and the convection in the liquid drops are accelerated, the mass transfer resistance of the inner sides of the liquid drops is reduced, and the mass transfer rate in the liquid drops is increased.
In the disclosure, the viscosity of the polymer solution at the inlet of the cyclone extraction separator is less than or equal to 22cp, the solid content of the catalyst is less than or equal to 8000mg/L, and the particle size of the catalyst is less than or equal to 500 μm.
In the present disclosure, the AlCl-containing3After the polymerized liquid of the catalyst is extracted and separated by cyclone, AlCl is added3The separation efficiency of the resin coated outside the catalyst is more than or equal to 90 percent, and C5 raw material polymerization liquid AlCl3The separation efficiency of the catalyst is more than or equal to 90 percent, the usage amount of the neutralized alkali liquor is reduced by 85 percent, and the pressure loss is 0.02-0.3 MPa.
In the disclosure, the underflow port of the cyclone extraction separator is connected to a sewage treatment system, the overflow port of the cyclone extraction separator is connected to the inlet of the next stage of cyclone extraction separator, and the overflow port of the last stage of cyclone extraction separator is connected to an oil-water separator; the cyclone extraction separator continuously operates, and the extraction separation process is strengthened by utilizing the autorotation and revolution coupling in the cyclone extraction separator.
In the present disclosure, the oil-water separation includes: and (3) allowing the polymer solution to enter a standing layering tank for standing oil-water primary separation, allowing the water phase to enter a sewage treatment system for treatment, allowing the oil phase to enter a coalescence dehydrator for deep dehydration, allowing the deeply-removed water phase to enter the sewage treatment system, allowing the deeply-dehydrated oil phase polymer solution to enter a settling tank to obtain a crude resin solution, and conveying the crude resin solution to the next unit for treatment to obtain a resin product.
In the present disclosure, the AlCl-containing3The polymerization liquid of the C5 raw material containing catalyst impurities (a resin layer is wrapped outside the polymerization liquid) is obtained by reacting the C5 raw material, the polymerization liquid and the catalyst in a polymerization reaction kettle, and feeding the polymerization liquid of the C5 raw material containing a large amount of the catalyst obtained by the reaction into a boiling bed separator to remove most of the catalyst.
In a second aspect of the present disclosure, there is provided a C5 petroleum resin polymer liquid cyclone extraction device, comprising:
multistage series cyclone extraction separator for separating liquid containing AlCl3Respectively injecting C5 raw material polymerization solution and NaOH solution containing catalyst impurities (coated with resin layer) into cyclone extraction separator3The desorption of the outer coating resin layer of the catalyst is realized under the coupling action of rotation and revolution, then the catalyst can fully generate neutralization reaction with NaOH solution through extraction reaction, aluminum hydroxide precipitation phase generated through the reaction flows into a sewage treatment system through a bottom flow port, and most AlCl is removed3C5 raw material polymerization liquid of the catalyst flows into a next-stage cyclone extraction separator through an overflow port, and further desorption process is carried out in the next-stage cyclone extraction separator; and
the device comprises a standing and layering tank connected with a cyclone extraction separator, a coalescent dehydrator connected with the standing and layering tank, and a settling tank connected with the coalescent dehydrator, wherein the settling tank is used for sending a polymerization solution into the standing and layering tank for standing oil-water primary separation, a water phase enters a sewage treatment system for treatment, an oil phase enters the coalescent dehydrator for deep dehydration, the deeply removed water phase enters the sewage treatment system, the oil phase polymerization solution after deep dehydration enters the settling tank to obtain a crude resin solution, and then the crude resin solution is sent into the next unit for treatment to obtain a resin product.
In the present disclosure, the apparatus further comprises:
a boiling bed separator connected with the cyclone extraction separator, and a polymerization reaction kettle connected with the boiling bed separator, wherein the polymerization reaction kettle is used for reacting C5 raw material, polymerization liquid and catalyst in the polymerization reaction kettle, and the polymerization liquid of the C5 raw material containing a large amount of catalyst obtained by the reaction is sent to the boiling bed separator to remove most of the catalyst, so as to obtain the AlCl-containing catalyst3Catalyst impurities (which are wrapped with a resin layer) of a C5 raw material polymerization solution.
In the disclosure, a vortex plate is arranged at the bottom of the cyclone extraction separator, and the rotating speed is 100-3000 r/min.
In the disclosure, the cyclone extraction separator adopts a series structure of a plurality of liquid-liquid cyclone extraction separators, the size of the cyclone extraction separator is designed according to the actual treatment capacity, the series number of stages is designed according to the actual requirement, an overflow port in the previous stage of cyclone extraction separator is connected to the inlet of the next stage of cyclone extraction separator, and NaOH alkali liquor is injected into the other inlet of each stage of cyclone extraction separator in batches.
Reference is made to the accompanying drawings.
FIG. 1 is a schematic overall process flow diagram of a cyclone extraction of C5 petroleum resin polymerization liquid according to a preferred embodiment of the present disclosure. As shown in FIG. 1, contains AlCl3The polymerization liquid of the catalyst is used as the separated liquid and is injected into the cyclone extraction separator from the left inlet of the cyclone extraction separator 1-1, the NaOH solution is used as the extracting agent and is injected from the right inlet of the cyclone extraction separator 1-1, the NaOH solution is broken into small liquid drops by the liquid drops with large particle size under the action of the shear stress of the cyclone field, meanwhile, the liquid drops move upwards along a spiral line in a flow channel outside a separation ring along with the polymerization liquid under the action of drag force, centrifugal force and the like, and AlCl is adopted in the process3The catalyst is gradually extracted from the polymerization liquid into small liquid drops of the NaOH solution, the mixed liquid is settled to the bottom in a flow channel inside the separating ring when reaching the top of the cyclone extraction separator 1-1, and a vortex diffusion effect is generated by a vortex plate at the bottom to reduce the mass transfer resistance of solute in the continuous phase and strengthen the effect of mass transfer rate outside the interface; the generated polymer liquid (oil phase) after the extraction and neutralization processes are finished flows into the next stage of cyclone extraction separator 1-2, the cyclone extraction separator 1-3 and the like from the overflow port through the outlet plate, and the process is repeated for a plurality of times to gradually improve AlCl3The separation effect of the catalyst.
FIG. 2 is a schematic diagram of a cyclonic extraction separator apparatus according to a preferred embodiment of the present disclosure. As shown in FIG. 2, contains AlCl3The polymerization liquid of the catalyst is used as the separated liquid to be injected from the left inlet 2-6 of the cyclone extraction separator 2-1, the NaOH dilute alkali liquid is used as the extractant to be injected from the right inlet 2-3 of the cyclone extraction separator 2-1, the NaOH dilute alkali liquid is broken into small liquid drops by the liquid drops with large particle size under the action of the shear stress of the cyclone field, and the liquid drops can follow the polymerization liquid under the action of drag force, centrifugal force and the like to form a separating ring2-4, the inner part of the flow passage moves upwards along a spiral line, and AlCl moves upwards in the process3The catalyst is gradually extracted from the polymerization liquid into small drops of NaOH dilute alkali liquor, the mixed liquid is settled to the bottom in a flow channel inside the separating ring when reaching the top of the cyclone extraction separator, and a vortex plate 2-2 at the bottom generates a vortex diffusion effect to reduce the mass transfer resistance of solute in the continuous phase and strengthen the effect of mass transfer rate outside an interface; the aluminum hydroxide precipitate and sodium chloride solution generated after the extraction and neutralization process is finished flows out to a sewage treatment system from a bottom flow port due to high density, the polymerization liquid (oil phase) flows into the next stage of circulation from an overflow port through an outlet plate 2-5, and the process is repeated for multiple times to gradually improve AlCl3The separation effect of the catalyst. The right drawing in fig. 2 is a top view of the left drawing and the section a-a in fig. 1.
FIG. 3 is a schematic diagram of a cyclone extraction process flow of C5 petroleum resin polymerization liquid according to a preferred embodiment of the present disclosure. As shown in FIG. 3, AlCl3Inputting the catalyst powder, the raw material C5 and the polymerization solution into a polymerization reaction kettle 3-1 through a pipeline to carry out cationic polymerization reaction, and extracting the polymerization reaction kettle 3-1 to the next unit while circulating; in the process, because the polymer reacts violently, an explosive polymer is easily generated to wrap the catalyst particles, so that the catalyst cannot participate in the reaction effectively; most of the reacted mixed polymer liquid is respectively circulated to a heat exchanger 3-2 through a pump for heat exchange and recycling, the rest small part of polymer liquid enters a boiling bed separator 3-8 for removing most of the catalyst, and then the cleaner polymer liquid is sent to a liquid-liquid cyclone extraction separator 3-3 for extraction and separation; after multi-stage cyclone extraction separation with NaOH dilute alkali liquor, the generated aluminum hydroxide precipitate and other heavy phases are discharged to a sewage treatment system through a bottom flow port; after multi-stage cyclone extraction separation, the C5 raw material polymerization liquid from which the AlCl3 catalyst is removed flows through an overflow port and flows through a heat exchanger 3-4 for heat exchange; the polymer liquid after heat exchange enters a standing layering tank 3-5 for oil-water separation, wherein the separated sewage flows into a sewage treatment system, the polymer liquid after primary water removal is injected into condensate and then flows into a coalescent dehydrator 3-6 for deep dehydration, the removed sewage also flows into the sewage treatment system, and the C5 raw material polymer liquid after deep dehydration finally enters a settling tank 3-7 after settling, a crude resin solution was obtained.
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 to limit 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:
in a process of 11 ten thousand ton/year petroleum resin production device, AlCl mixed in polymerization liquid generated in the last reaction is needed3And removing impurities of the catalyst. According to the method and the device, the liquid-liquid cyclone extraction method is adopted, and the C5 raw material polymerization liquid after extraction can completely realize AlCl3The specific operation process and effect of the removal of the catalyst are described as follows:
1. material Properties and associated parameters
Containing AlCl3The polymerization liquid of the C5 raw material of the catalyst is a liquid-solid mixture to be treated, wherein the C5 and the polymerization liquid are continuous phases, and NaOH dilute alkali liquid which is crushed into small droplets from large-particle-size droplets under the action of the shear stress of a rotational flow field is used as a disperse phase. The treatment capacity of the experimental device is 15-20t/h, the weight of the experimental device accounts for 60% under the operation state of the polymerization liquid, and the density is 805kg/m3Viscosity of 8.0cp, pressure of 0.6MPa, feed flow of 12t/h, operation temperature of 90 ℃, weight percentage of 40 percent under the operation state of NaOH dilute alkali liquor and density of 1000kg/m3Viscosity of 1cp, operating temperature of 90 ℃ and pressure of 1 MPa.
2. Liquid-liquid cyclone extraction separator
The cyclone extraction separator is formed by connecting 13 liquid-liquid micro-cyclones in parallel, the column section size of the cyclone is DN35 (the diameter is 35mm), and the treatment capacity reaches 15-20 t/h.
3. Carrying out the process
AlCl3Catalyst powder, raw material C5 and polymer liquid are conveyed into a polymerization reaction kettle through a pipeline to carry out cationic polymerization reactionShould then contain AlCl3Introducing the C5 raw material polymerization liquid of the catalyst into a liquid-liquid cyclone extraction separator for extraction and separation; performing cyclone extraction separation process on the polymerization solution and NaOH dilute alkali solution in a separator, and discharging heavy phases such as aluminum hydroxide precipitate generated by neutralization reaction from a bottom flow port to a sewage treatment system; removing part of AlCl3The C5 raw material polymerization liquid of the catalyst enters the inlet of the next stage cyclone extraction separator from the overflow port, the separation process is repeated in the next stage separator, and AlCl is completely removed after three times of cyclone extraction separation3The polymerization liquid of the C5 raw material of the catalyst is mixed with a small amount of water and then subjected to oil-water separation treatment, wherein the separated water phase flows into a sewage treatment system, and the oil phase forms crude resin liquid.
4. Analysis of results
After passing through a cyclone extraction separator, AlCl3The resin coating layer outside the catalyst can be completely removed, and AlCl mixed in the polymerization solution of the C5 raw material3The catalyst is completely removed by the neutralization reaction with NaOH alkali liquor during the extraction process. The inlet pressure of the cyclone extraction separator is 0.6MPa, the pressure loss is less than 0.2MPa, and the cyclone extraction separator continuously operates for a long time. The weight of the catalyst in the polymerization liquid without cyclone extraction accounts for 0.7 percent, and the AlCl in the polymerization liquid after the cyclone extraction process can be completely removed3Catalyst impurities.
Example 2:
the amine-base impurity carried by the raw material of a 2-thousand ton/year-scale MTBE (methyl tert-butyl ether) device C4 of ClarityI petrochemical company of China causes the service life of a catalyst to be rapidly reduced and seriously influences the operation cycle of a reactor. Aiming at the problem, the MTBE device of the chemical company Clarithromite adopts the cyclone extraction method to extract amine-base impurities contained in water by using a C4 extractant and remove impurities contained in raw material liquid, and the specific operation process and effect are described as follows:
1. material Properties and associated parameters
C4 is light phase medium, water is heavy phase medium, and the average treatment capacity of C4 raw material is 7.7-9.6t/h, the amount of water used for extracting amine alkali impurities is 79-90 kg/h. The extraction ratio (mass ratio of the extractant to the raw material) reaches about 0.01, and the mass transfer rate reaches 0.027-0.109 mol/(m)2·s)。
2. Liquid-liquid cyclone extraction separator
The cyclone extraction separator is formed by connecting 13 liquid-liquid micro-cyclones in parallel, the column section size of the cyclone is DN35 (the diameter is 35mm), and the treatment capacity reaches 15-20 t/h.
3. Carrying out the process
C4 raw material containing a large amount of amine alkali impurities from the bottom of a gas separation depropanizing tower is firstly premixed with softened water in a static mixer, so that the softened water is dispersed into small drops, and primary mass transfer is completed; then the mixture of the C4 raw material and softened water enters an oil dehydration type cyclone group, water drops in the micro cyclone are further sheared and broken, and autorotation is carried out under the shearing action of a flow field, so that mass transfer is strengthened. Through centrifugal separation of the liquid-liquid cyclone extraction separator, the heavy-phase water phase containing a large amount of amine alkali impurities is discharged from a bottom flow main pipe of the cyclone extraction separator group and enters a sewage treatment system, while the light-phase purified C4 raw material is discharged from an overflow main pipe of the cyclone extraction separator group and enters a raw material buffer tank, further sedimentation is carried out to reduce the water content in the raw material, and finally the raw material sequentially enters an ion filter and a reactor.
4. Analysis of results
The operation condition of the cyclone extraction separator of the MTBE device of the chemical company of the Clarithromite of the medium petroleum in the past 6 years is tracked and analyzed, the average treatment capacity of the raw material of the MTBE device C4 is 7.7-9.6t/h, the water quantity for extracting amine alkali impurities is 79-90kg/h, the extraction ratio reaches about 0.01, and the mass transfer rate reaches 0.027-0.109 mol/(m)2S). The unit is maintained once a year and every time all the catalyst in the unit is to be replaced. The first two protective filters filled with the same catalyst as the reactor are alternately used to consume and extract residual impurities, and finally the normal operation of the reactor is guaranteed. The catalyst replacement period of the two filters is kept stable at 40 days (15 days before the application of the cyclone separator), so that the stable operation of the reactor is effectively ensured.
The above-listed embodiments are merely preferred embodiments of the present disclosure, and are not intended to limit the scope of the present disclosure. That is, all equivalent changes and modifications made according to the contents of the claims of the present application should be considered to be within the technical scope of the present disclosure.
All documents referred to in this disclosure are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes or modifications to the disclosure may be made by those skilled in the art after reading the above teachings of the disclosure, and such equivalents may fall within the scope of the disclosure as defined by the appended claims.
Claims (8)
1. A cyclone extraction method for C5 petroleum resin polymerization liquid comprises the following steps:
(a) injecting C5 raw material polymerization liquid containing catalyst impurities wrapped with a resin layer and alkali liquor into a cyclone extraction separator together to remove the catalyst;
(b) feeding the C5 raw material polymerization liquid without the catalyst obtained in the step (a) into a next-stage cyclone extraction separator to further remove the catalyst; and
(c) the polymerization liquid without the catalyst in the step (b) enters a standing layering tank for standing oil-water primary separation, wherein the water phase enters a sewage treatment system for treatment, the oil phase enters a coalescence dehydrator for deep dehydration, the deeply removed water phase enters the sewage treatment system, the oil phase polymerization liquid after deep dehydration enters a settling tank to obtain crude resin liquid, and then the crude resin liquid is sent to the next unit for treatment to obtain a resin product,
the method further comprises the following steps:
before step (a), C5 raw material, polymerization liquid and catalyst are reacted in a polymerization reaction kettle, and the C5 raw material polymerization liquid containing a large amount of catalyst obtained by the reaction is sent to an ebullated bed separator to remove most of the catalyst, so that the C5 raw material polymerization liquid containing the catalyst impurities wrapped by a resin layer is obtained.
2. The method of claim 1, wherein in step (a), the catalyzing is byThe agent is AlCl3A solid catalyst; the alkali liquor is NaOH solution.
3. The method of claim 1, wherein in step (a), the solid content of the catalyst in the polymerization solution at the inlet of the cyclone extraction separator is less than or equal to 8000mg/L, the viscosity of the polymerization solution is less than or equal to 22cp, and the particle size of the catalyst is less than or equal to 500 μm.
4. The method of claim 1, wherein in step (a), in the cyclone extraction separator, the catalyst is desorbed from the outer resin layer under the action of the rotation and revolution coupling, then the catalyst is sufficiently neutralized with alkali liquor through the extraction reaction, the precipitated phase generated through the neutralization reaction flows into a sewage treatment system through a bottom flow port, and the C5 raw material polymer solution from which the catalyst is removed flows into the next stage cyclone extraction separator through an overflow port.
5. The method of claim 1, wherein after the separation by the cyclone extraction, the separation efficiency of the resin coated outside the catalyst is more than or equal to 90 percent, the separation efficiency of the catalyst of the C5 raw material polymerization solution is more than or equal to 90 percent, the usage amount of the neutralized alkali liquor is reduced by 85 percent, and the pressure loss of the cyclone extraction separator is 0.02-0.3 MPa.
6. The method as set forth in claim 1, wherein the cyclone extraction separator is constructed in a multistage series structure, the size of the cyclone extraction separator is designed according to actual throughput, the number of stages in the series structure is designed according to actual requirements, an overflow port of the previous stage of the cyclone extraction separator is connected to an inlet of the next stage of the cyclone extraction separator, and lye is injected in batches at the other inlet of each stage of the cyclone extraction separator.
7. A C5 petroleum resin polymer liquid cyclone extraction device comprises:
a plurality of series-connected cyclone extraction separators (3-3) for carrying out the following steps: (a) injecting C5 raw material polymerization liquid containing catalyst impurities wrapped with a resin layer and alkali liquor into a cyclone extraction separator together to remove the catalyst; and (b) sending the C5 raw material polymerization liquid without the catalyst obtained in the step (a) to a next-stage cyclone extraction separator to further remove the catalyst; and
a standing layering tank (3-5) connected with the cyclone extraction separator (3-3), a coalescent dehydrator (3-6) connected with the standing layering tank (3-5), and a settling tank (3-7) connected with the coalescent dehydrator (3-6), for performing the following steps: (c) the polymerization liquid without the catalyst in the step (b) enters a standing layering tank for standing oil-water primary separation, wherein the water phase enters a sewage treatment system for treatment, the oil phase enters a coalescence dehydrator for deep dehydration, the deeply removed water phase enters the sewage treatment system, the oil phase polymerization liquid after deep dehydration enters a settling tank to obtain crude resin liquid, and then the crude resin liquid is sent to the next unit for treatment to obtain a resin product,
the device also includes:
a bubbling bed separator (3-8) connected to the cyclone extraction separator (3-3), and a polymerization reactor (3-1) connected to the bubbling bed separator (3-8), for performing the steps of: before the step (a), C5 raw material, polymerization liquid and catalyst are reacted in a polymerization reaction kettle, and the polymerization liquid of the C5 raw material containing a large amount of catalyst obtained by the reaction is sent to an ebullated bed separator to remove most of the catalyst, so that the polymerization liquid of the C5 raw material containing the catalyst impurities wrapped by a resin layer is obtained.
8. The apparatus as claimed in claim 7, wherein the cyclone separator is provided with a vortex plate at a rotation speed of 100-3000 r/min.
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