CN112851836B - Emission reduction and consumption reduction method and device for cold polymerization production of C5 resin - Google Patents
Emission reduction and consumption reduction method and device for cold polymerization production of C5 resin Download PDFInfo
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Abstract
The disclosure relates to a method and a device for reducing emission and consumption of a C5 resin cold polymerization production, and provides a method for reducing emission and consumption of a C5 resin cold polymerization production, which comprises the following steps: (a) c5 raw material and polymerization liquid are mixed and flow into a polymerization reaction kettle with catalyst for reaction; (b) after the reaction, part of the mixed polymerization liquid flows back to the polymerization reaction kettle for recycling, part of the mixed polymerization liquid flows into a cyclone separator for cyclone separation treatment, and the polymerization liquid containing high-content catalyst after the cyclone separation treatment flows back to the polymerization reaction kettle for recycling through a bottom flow port of the cyclone separator; (c) feeding the polymerization liquid of the supernatant at the overflow port of the cyclone separator into a fluidized bed separator for deep purification treatment so as to remove a small amount of residual catalyst in the polymerization liquid of the supernatant; and (d) the purified polymerization liquid after deep purification treatment enters a neutralization reaction kettle for neutralization reaction. Also provides a device for reducing emission and consumption in the cold polymerization production of C5 resin.
Description
Technical Field
The disclosure belongs to the field of comprehensive treatment of environmental pollution, and relates to an emission reduction and consumption reduction method for a C5 petroleum resin cold polymerization production process, which is suitable for separation and online activity recovery and reuse of a catalyst in a polymerization solution. Specifically, the disclosure provides a method and a device for reducing emission and consumption in the production process of petroleum resin cold polymerization.
Background
The petroleum resin is solid or viscous liquid polymer prepared by separating and polymerizing cracking C5, C9 and dicyclopentadiene (DCPD) fractions which are byproducts of an ethylene device and are used as raw materials. It is an indispensable tackifying component for many adhesives, such as hot melt adhesives and pressure sensitive adhesives. Since the last century, the research and development of petroleum resins has been attracting attention and interest, and since the research of petroleum resins in the united states was started in 1910, the Picco company and the Esso company collaborated to produce C5 petroleum resin in 1954. The Picco corporation realized the industrialization of aliphatic C5 petroleum resins in the last 90 th century. In the middle of the 70's last century, China began the study of petroleum resins. The Lanzhou petrochemical company uses C5-C9 fraction in the tar cracking process as raw materials to produce petroleum resin. The companies such as the chemical institute of the Chinese academy of sciences and the Shanghai petrochemical institute developed the C5 petroleum resin craft bag in succession, and established some small-sized C5 petroleum resin production devices. The C5 petroleum resin has low acid value, good compatibility, water resistance, ethanol resistance, chemical corrosion resistance, good thermal stability, good compatibility with organic matters and viscosity regulation function, is widely applied to the industries of rubber, adhesives, coatings, traffic paints, printing ink, paper making and the like, and can also be used in new fields through modification. The development trend of the C5 petroleum resin is high-end, environment-friendly, specialized, differentiated and multipurpose.
However, the scale of the production device of petroleum resin in China is small, the product color is dark, the thermal stability is poor, the variety is single, and the application is greatly limited, so that the quality and the quantity are very necessary to be improved, and the production process needs to be improved. Various efforts have been made by researchers to address the problems involved. The invention patent CN102453217B of China proposes a petroleum resin hydrogenation and decoloration method, which adopts organic solvent to dissolve petroleum resin feeding for hydrogenation reaction in a fixed bed, a catalyst A high-capacity sulfur low-activity nickel-based catalyst is added in the fixed bed, and a catalyst B bed is filled with the high-activity nickel-based catalyst. Chinese invention patent CN102702435B proposes a method for dry cleaning and removing aluminum trichloride catalyst in petroleum resin, the method is that polymerization liquid containing aluminum trichloride after reaction, calcium hydroxide, liquid ammonia, argil and surfactant are sent into a neutralization kettle for primary neutralization reaction, and then sent into a neutralization buffer kettle for secondary neutralization reaction, dehydration and impurity treatment, the method can separate out the aluminum trichloride catalyst to obtain higher resin, but more calcium hydroxide and other neutralization reaction materials are used in the multiple neutralization reaction processes, and waste water is generated in the reaction process, and the later dehydration burden is increased. The Chinese patent application CN111909315A proposes a method for removing cationic catalyst in short-chain olefin petroleum resin, which is characterized in that the petroleum resin is added with 50-80% isopropanol water solution to carry out alcohol washing under the stirring state, thereby achieving the purpose of absorbing and removing the catalyst in the resin.
Aiming at the problems of consumption reduction of petroleum resin catalysts and emission reduction of wastewater, the removal and reuse of the catalysts in the polymerization liquid after reaction are particularly important, and aiming at the problems, a large number of patents of the invention adopt external chemical agents for neutralization reaction, but a large amount of catalysts are consumed in the neutralization reaction process, and a large amount of water is generated at the same time, so that the problems of difficult dehydration of the polymerization liquid in the later period, large amount of wastewater discharge and the like are solved. Therefore, it is necessary to develop an efficient, economical and reliable separation method to recover the activity of the catalyst in the polymerization solution and separate and recycle the catalyst to reduce consumption, reduce the addition of the neutralization chemical agent in the subsequent reaction or realize no addition, reduce the generation of the neutralization water to reduce the generation of high-concentration wastewater in the later period, and finally achieve the purposes of reducing the consumption of the catalyst, recycling resources, reducing the addition of the chemical agent and reducing the discharge of high-concentration wastewater.
Disclosure of Invention
The invention provides a novel method and a device for reducing emission and consumption of C5 resin cold polymerization production, provides a separation method and key equipment by adopting a series combination of a liquid-solid cyclone separator and a fluidized bed separator aiming at the problems of high consumption of catalyst, high consumption of neutralization alkali and large discharge amount of high-concentration high-salinity wastewater in C5 petroleum resin production, invents the method and the device for reducing emission and consumption in the process of strengthening the C5 petroleum resin cold polymerization production by using the liquid-solid cyclone separator and the fluidized bed separator, realizes the purposes of reducing the consumption of catalyst by 80 percent, reducing the consumption of neutralization sodium hydroxide alkali liquor by 95 percent and reducing the emission of high-concentration wastewater by 80 percent, realizes the purposes of removing impurities such as catalyst in polymerization liquid and reducing the addition of chemical agents, has simple and effective method, solves the problems of more chemical agents added currently, large catalyst consumption, difficult removal of waste water by-products, low product quality and the like.
In one aspect, the present disclosure provides a method for reducing emission and consumption in the cold polymerization production of C5 resin, comprising the following steps:
(a) c5 raw material and polymerization liquid are mixed and flow into a polymerization reaction kettle with catalyst for reaction;
(b) after the reaction, part of the mixed polymerization liquid flows back to the polymerization reaction kettle for recycling, part of the mixed polymerization liquid flows into a cyclone separator for cyclone separation treatment, and the polymerization liquid containing high-content catalyst after the cyclone separation treatment flows back to the polymerization reaction kettle for recycling through a bottom flow port of the cyclone separator;
(c) feeding the polymerization liquid of the supernatant at the overflow port of the cyclone separator into a fluidized bed separator for deep purification treatment so as to remove a small amount of residual catalyst in the polymerization liquid of the supernatant; and
(d) and the purified polymer liquid after the deep purification treatment enters a neutralization reaction kettle for neutralization reaction.
In a preferred embodiment, the method further comprises the steps of:
(e) and (3) allowing the polymer solution obtained after the neutralization reaction 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 a 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 another preferred embodiment, in step (a), the catalyst is AlCl3A solid catalyst.
In another preferred embodiment, in step (b), the solid content of the catalyst in the mixed polymerization liquid at the inlet of the cyclone separator is less than or equal to 8000mg/L, the viscosity of the polymerization liquid is less than or equal to 22cp (centipoise), and the particle size of the catalyst is less than or equal to 250 μm; the separation efficiency of the cyclone separator is more than or equal to 80 percent, the catalyst is recycled more than or equal to 80 percent, and the pressure loss is 0.05MPa to 0.20 MPa.
In another preferred embodiment, in step (b), the cyclone separator is operated continuously, the mixed polymerization solution is subjected to catalyst separation under cyclone separation, and meanwhile, the rotational flow and revolution coupling effect in the cyclone separator enables the catalyst micro-interface to pulsate and oscillate, so that reaction byproducts adhered to the catalyst pore channels and the micro-interface are separated; and updating the catalyst micro-interface, recovering the activity on line and refluxing to the polymerization reaction kettle to promote the reaction.
In another preferred embodiment, in step (c), the solid content of the catalyst in the supernatant polymerization liquid flowing into the boiling bed separator from the overflow port of the cyclone separator is less than or equal to 1600mg/L, the viscosity of the supernatant polymerization liquid is less than or equal to 22cp, and the particle size of the catalyst is less than or equal to 250 μm; the operation period of the fluidized bed separator is more than 8 hours, the solid content of the catalyst in the outlet polymerization liquid is less than or equal to 10mg/L, and the pressure loss is 0.05 MPa-0.30 MPa.
In another preferred embodiment, in step (c), the ebullated-bed separator is operated intermittently, and after a certain period of continuous operation, plant-area circulating water or fresh water and plant-area compressed air or steam are reversely introduced to make the packing in the bed undergo suspension boiling to a fluidized state, and the bed is cleaned to realize regeneration; during back washing regeneration, fluidized filler enters a top three-phase separator, the filler and a catalyst are separated in a reinforced mode through particle rotation and revolution coupling in a cyclone field, meanwhile, a separation medium and a catalyst micro-interface vibrate and desorb surface adherends in a pulsating mode, the catalyst flows out of an overflow port of a fluidized bed separator to a storage tank, and the filler is backfilled to a bed layer.
On the other hand, the present disclosure provides a C5 resin condensation production emission reduction and consumption reduction device, the device includes:
a polymerization reaction kettle for mixing the raw material C5 and the polymerization solution in the step (a) and flowing into the polymerization reaction kettle with the catalyst for reaction;
the cyclone separator is connected with the polymerization reaction kettle and is used for refluxing part of mixed polymerization liquid to the polymerization reaction kettle for recycling after the reaction in the step (b), part of mixed polymerization liquid flows into the cyclone separator for cyclone separation treatment, and the polymerization liquid containing high-content catalyst after the cyclone separation treatment is refluxed to the polymerization reaction kettle for recycling through a bottom flow port of the cyclone separator;
the fluidized bed separator is connected with the cyclone separator and is used for feeding the supernatant polymerization liquid at the overflow port of the cyclone separator in the step (c) into the fluidized bed separator for deep purification treatment so as to remove a small amount of residual catalyst in the supernatant polymerization liquid; and
and (d) a neutralization reaction kettle connected with the boiling bed separator, wherein the neutralization reaction kettle is used for allowing the purified polymer liquid subjected to the deep purification treatment in the step (d) to enter the neutralization reaction kettle for neutralization reaction.
In a preferred embodiment, the apparatus further comprises:
and (e) a standing layering tank connected with the neutralization reaction kettle, a coalescent dehydrator connected with the standing layering tank, and a settling tank connected with the coalescent dehydrator, wherein the polymerized liquid obtained after the neutralization reaction in the step (e) enters the standing layering tank for standing oil-water primary separation, the water phase enters a sewage treatment system for treatment, the oil phase enters the coalescent dehydrator for deep dehydration, the water phase subjected to deep dehydration enters the sewage treatment system, the oil phase polymerized liquid subjected to deep dehydration enters the settling tank to obtain a crude resin liquid, and the crude resin liquid is sent to the next unit for treatment to obtain a resin product.
In another preferred embodiment, the cyclone separator adopts a liquid-solid cyclone structure, the size of the liquid-solid cyclone structure is designed according to the treatment capacity, and a plurality of cyclone separators are connected in parallel according to the treatment capacity and are made of acid-resistant and alkali-resistant materials; the material of the fluidized bed separator is acid-resistant and alkali-resistant material, the separating filler is acid-resistant and alkali-resistant material, and the particle size of the filler is selected according to the particle size of the catalyst in the treated polymerization liquid.
Has the advantages that:
1) the invention realizes more than 80% of AlCl by using a cyclone separation method3The activity of the catalyst is recovered and reused on line, thereby realizing the recycling of catalyst resources and reducing the consumption of the catalyst by 80 percent.
2) The invention utilizes the deep separation method of the boiling bed separator to achieve the clean removal (less than 10mg/L) of the residual catalyst in the polymerization liquid, thereby reducing the injection amount of NaOH alkali liquor in the back section by 95 percent.
3) The invention realizes the purification of the polymerization liquid by using a separation method of a cyclone combined fluidized bed, and adds a chemical agent NaOH alkali liquor for injection, so that the wastewater is reduced in the neutralization reaction process, and the discharge amount of high-concentration wastewater is reduced by 80%.
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 an exemplary diagram of the overall process flow of emission reduction and consumption reduction cyclone separation and ebullated bed depth separation in the production process of C5 petroleum resin according to a preferred embodiment of the present disclosure.
FIG. 2 is a schematic diagram of a cyclonic separator in accordance with a preferred embodiment of the present disclosure.
FIG. 3 is a schematic diagram of the separation and regeneration principle of the ebullated bed separator according to a preferred embodiment of the present disclosure.
Detailed Description
After extensive and intensive research, the inventor of the application finds that for a polymerization liquid in the production process of petroleum resin, the viscosity is high, the catalyst content is high, and in a resource recycling system, the technology of recovering the catalyst activity by separating a cyclone separator, recycling a large amount of catalyst and deeply treating the polymerization liquid by a fluidized bed separator is combined, so that long-period stable operation can be realized, 80% of resources of catalyst materials can be recycled, the using amount of neutralizing alkali liquor is reduced by 95%, and the discharge amount of high-concentration wastewater is reduced by 80%, thereby developing high-efficiency, automatic and high-separation-efficiency separation equipment.
In a first aspect of the disclosure, a method for reducing emission and consumption of a cold polymerization production of C5 resin is provided, the method comprising the following steps:
(a) c5 raw material and polymerization liquid are mixed and flow into the reactor and AlCl is added3Uniformly mixing and reacting in a polymerization reaction kettle of the catalyst;
(b) part of mixed polymerization liquid after reaction reflows to the polymerization reaction kettle for recycling, part of mixed polymerization liquid flows into a cyclone separator for cyclone separation treatment, and the mixed polymerization liquid which is subjected to cyclone separation treatment contains high content AlCl3The polymerization liquid of the catalyst is taken as circulating liquid and flows back to the circulating system through a bottom flow port of the cyclone separator, and finally the polymerization reaction kettle participates in the next reaction; wherein the cyclone separator is operated continuously, and AlCl is added3The catalyst mixed polymerization liquid realizes catalyst separation under the cyclone separation, and meanwhile, the cyclone rotation and revolution coupling effect in the cyclone separator ensures that the catalyst micro interface pulsates and vibrates, so that reaction byproducts adhered to the catalyst pore channel and the micro interface are separated, the catalyst micro interface is updated, the activity is recovered on line and flows back to the polymerization reaction kettle to promote the reaction;
(c) the supernatant polymer liquid at the overflow port of the cyclone separator is sent to a fluidized bed separator for deep purification treatment, and a small amount of AlCl remaining in the supernatant polymer liquid is removed by utilizing a filler deep filtration mechanism3Impurities such as catalysts; wherein, after the boiling bed separator continuously runs for a certain time, a back flush water valve and an air valve are opened, and water and air are discharged,Under the condition of gas backwashing, the filter material in the fluidized bed separator is in a suspended boiling state, then enters a three-phase separator at the top in the fluidized bed separator for cyclone separation, in the three-phase separator, under the action of particle rotation and revolution coupling enhanced desorption, the micro-interface of a separation medium pulsates and vibrates, the interface of the separation medium is updated, the regenerated filler is backfilled to a bed layer from the bottom flow port of the three-phase separator, the catalyst is discharged to a storage tank from the overflow port of the top separator, and the regenerated liquid is discharged into a sewage tank; and
(d) and the purified polymer solution after the deep purification treatment enters a rear-end neutralization reaction kettle for neutralization reaction.
In the present disclosure, the method further comprises the steps of:
(e) and (3) allowing the polymer solution obtained after the neutralization reaction 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 a 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 disclosure, the temperature of the polymerization solution is 40-90 ℃, the mass content of catalyst particles in the polymerization solution at the outlet of the polymerization reactor is 0.1-2.5%, and the particle size is less than 1 mm.
In the present disclosure, AlCl in the cyclone inlet polymerization liquid3The solid content of the solid catalyst is less than or equal to 8000mg/L, the viscosity of the polymerization liquid is less than or equal to 22cp, and AlCl3The grain diameter of the catalyst is less than or equal to 250 mu m.
In the disclosure, the separation efficiency of the cyclone separator is more than or equal to 80%, the catalyst is recycled more than or equal to 80%, and the pressure loss is 0.05 MPa-0.20 MPa.
In the disclosure, the cyclone separator can continuously operate for a long time, the backflow flow is controlled by adjusting the outlet valve at the underflow opening, and the pressure drop is 0.01-0.2 MPa.
In the disclosure, the solid content of the supernatant polymerization liquid flowing into the fluidized bed separator from the overflow port of the cyclone separator is less than or equal to 1600mg/L, the viscosity of the supernatant polymerization liquid to be deeply separated is less than or equal to 22cp, the particle size of the catalyst in the supernatant polymerization liquid is less than or equal to 250 μm, and the catalyst content is less than 0.05 wt%.
In the present disclosure, the operation period of the ebullated bed separator is more than 8h, such as more than 12h, and the solid content in the outlet polymerization liquid is less than or equal to 10mg/L, so that the usage amount of the neutralization alkali liquor can be reduced by 95%, and the pressure loss is 0.02-0.30MPa, such as 0.05-0.30 MPa.
In the disclosure, the separation medium in the ebullated bed separator is selected from filler particles for matching treatment; the particle size distribution of the separating medium filler is respectively selected from different ranges of 0.5 mm-1 mm, 1 mm-1.6 mm, 1 mm-2 mm, 2 mm-4 mm and the like.
In the disclosure, the ebullated bed separator is operated intermittently, and after the ebullated bed separator continuously operates for a certain time, plant circulating water or fresh water and plant compressed air or steam are reversely introduced to enable the filler in the bed layer to be suspended and boiled to a fluidized state, and the bed layer is cleaned to realize regeneration; during back washing regeneration, fluidized filler enters a top three-phase separator, the filler and a catalyst are separated in a reinforced mode through particle rotation and revolution coupling in a cyclone field, meanwhile, a separation medium and a catalyst micro-interface vibrate and desorb surface adherends in a pulsating mode, the catalyst flows out of an overflow port of a fluidized bed separator to a storage tank, and the filler is backfilled to a bed layer.
In a second aspect of the present disclosure, there is provided an emission reduction and consumption reduction device for C5 resin cold polymerization production, the device comprising:
the polymerization reaction kettle is used for reacting the polymerization liquid, the raw materials and the catalyst;
the cyclone separator is connected with the polymerization reaction kettle and is used for enabling the polymerization liquid containing a large amount of catalysts to enter the cyclone separator for cyclone separation, and the concentrated polymerization liquid containing a large amount of catalysts after treatment returns to the circulating system through the bottom flow port;
the fluidized bed separator is connected with the cyclone separator and is used for feeding the supernatant polymerization liquid at the overflow port of the cyclone separator into the fluidized bed separator for deep purification and separation;
and the neutralization reaction kettle is connected with the boiling bed separator and is used for allowing the purified polymerization liquid subjected to the deep purification treatment to enter the neutralization reaction kettle for neutralization reaction.
In the present disclosure, the apparatus further comprises:
the device comprises a standing layering tank connected with a neutralization reaction kettle, a coalescent dehydrator connected with the standing layering tank, and a settling tank connected with the coalescent dehydrator, wherein a polymerization solution obtained after neutralization reaction enters the standing layering tank to carry out standing oil-water primary separation, a water phase enters a sewage treatment system to be treated, an oil phase enters the coalescent dehydrator to be deeply dehydrated, a deeply removed water phase enters the sewage treatment system, the deeply dehydrated oil phase polymerization solution enters the settling tank to obtain a crude resin solution, and then the crude resin solution is sent to the next unit to be treated to obtain a resin product.
In the disclosure, the cyclone separator adopts a liquid-solid cyclone structure, the size of the cyclone separator is designed according to the treatment capacity, and a plurality of cyclone separators are connected in parallel according to the treatment capacity; the material is acid-resistant and alkali-resistant material; the bottom flow port is connected to the circulating liquid interface, and the overflow port is connected to the inlet of the fluidized bed separator.
In the present disclosure, the material of the fluidized bed separator is acid-resistant and alkali-resistant material, the separation filler in the fluidized bed separator is also acid-resistant and alkali-resistant material, and the particle size of the filler is selected according to the particle size of the catalyst in the polymerization liquid to be treated.
In the disclosure, the fluidized bed separator adopts one or more granular separation media, the material has the effects of intercepting or adsorbing the catalyst, the separation media can be anthracite, activated carbon, carbon spheres and other separation media, and can also be a combination of various separation media, and the separation media has the effects of screening, intercepting, adsorbing and the like on the catalyst in the clean polymerization liquid at the overflow port of the cyclone separator, so that the content of the catalyst in the polymerization liquid is reduced, and the deep purification of the polymerization liquid is realized.
In the present disclosure, the polymerization liquid cyclone separator and the ebullated bed separator can be popularized to heterogeneous separation or deep purification separation of various waste liquids, catalysts carried by liquids with certain viscosity.
Reference is made to the accompanying drawings.
FIG. 1 is an exemplary diagram of the overall process flow of emission reduction and consumption reduction cyclone separation and ebullated bed depth separation in the production process of C5 petroleum resin according to a preferred embodiment of the present disclosure. As shown in FIG. 1, a raw material C5, a polymerization liquid, and a catalyst(AlCl3) Conveying the mixture into a polymerization reaction kettle 1-1 through a pipeline for reaction, circulating part of mixed polymerization liquid after the reaction to a heat exchanger 1-2 for heat exchange and recycling through a pump, simultaneously, allowing part of the mixed polymerization liquid to enter a cyclone separator 1-3 for cyclone separation, separating a large amount of catalyst through the cyclone separator 1-3, then refluxing the catalyst from a bottom flow port to a circulating system for recycling, allowing cleaner polymerization liquid to flow out of an overflow port of the cyclone separator 1-3 and enter a fluidized bed separator 1-4 for deep purification treatment, allowing the cleaner polymerization liquid to flow into a neutralization reaction kettle 1-5 for neutralization reaction with injected NaOH dilute alkali solution, allowing the polymerization liquid after the neutralization reaction to enter a standing layering tank 1-7 for oil-water separation after heat exchange through a heat exchanger 1-6, allowing the separated sewage to enter a plant sewage treatment system for treatment, and adding a condensate into the polymerization liquid after primary water removal, and then entering a coalescence dehydrator 1-8, treating the deeply dehydrated water in a plant sewage treatment system, allowing the dehydrated oil-phase polymerization solution to enter a settling tank 1-9 for settling to obtain a crude resin solution, and performing series treatment on the crude resin solution to obtain a finished product of petroleum resin.
FIG. 2 is a schematic diagram of a cyclonic separator in accordance with a preferred embodiment of the present disclosure. As shown in figure 2, the cyclone separator mainly comprises a cyclone inlet 2-1, a cyclone cylinder 2-2, a cyclone cone 2-3, an overflow pipe 2-4, an underflow liquid seal pipe 2-5 and the like, when in normal operation, polymerization liquid containing a catalyst enters equipment from the cyclone inlet 2-1, the catalyst 2-6 gradually migrates towards the side wall 2-7 under the coupling action of a cyclone field and the revolution of particles, and the catalyst gradually migrates towards the side wall 2-7 because the catalyst is heavier than liquid phase polymerization liquid and also migrates downwards, and finally flows out through an underflow opening, and the clean polymerization liquid is light phase and flows out from the overflow pipe 2-4.
FIG. 3 is a schematic diagram of the separation and regeneration principle of the ebullated bed separator according to a preferred embodiment of the present disclosure. As shown in FIG. 3(a), the fluidized bed separator is mainly divided into a top cyclone 3-1, an equipment shell 3-2, a separation medium bed layer 3-3, a distributor 3-4 and the like, when in normal operation, a polymerization liquid containing a catalyst enters the equipment from a top inlet pipe, flows into the fluidized bed separation medium bed layer 3-3 through a feeding distributor for treatment, and flows out from the bottom through the distributor 3-4 after being cleaned and is sent to the next neutralization treatment process; when the device runs to enrich a large amount of catalyst in the bed layer, the device is switched to a back washing regeneration operation, regeneration water is introduced from the bottom of the device, and regeneration gas is introduced at the same time to boil the granular medium of the bed layer from bottom to top; as shown in fig. 3(b), the bed particle medium boiling 3-5 is that under the action of a cyclone field, the particle rotation omega 2 and revolution omega 1 are coupled (wherein tau is shear stress), the separation medium 3-6, the liquid drop 3-7 and the catalyst 3-8 are desorbed, the separation medium 3-6 is backfilled from the bottom of the three-phase cyclone separator to the boiling bed separator to form a bed layer, and the separated and desorbed catalyst 3-8 enters the storage tank along with the liquid drop 3-7 through a drain outlet and finally enters the sewage treatment plant for treatment.
Examples
The invention is further illustrated below with reference to specific examples. It is to be understood, however, that these examples are illustrative only and are not to be construed as limiting the scope of the present invention. Test methods without specifying specific conditions in the following examples are generally performed under conventional conditions or conditions recommended by the manufacturers. All percentages and parts are by weight unless otherwise indicated.
Example 1:
in an 11 ten thousand ton/year petroleum resin production device, according to the method of the invention, a cyclone separator and a boiling bed separator are adopted to carry out precise separation on C5 polymerization liquid, so that AlCl is reduced3The catalyst loss is 80%, the subsequent NaOH alkali liquor consumption is reduced by 95%, the subsequent high-concentration wastewater discharge is reduced by 80%, and the specific operation process and effect are described as follows:
1. material Properties and associated parameters
The polymer liquid to be treated in the production of petroleum resin is a liquid-solid mixture, and the polymer liquid contains solid AlCl3Catalyst, wherein the raw material C5 and the polymerization solution are continuous phases, and AlCl3The catalyst is dispersed phase, the viscosity of the polymerization liquid is 20cp, the temperature is 55 ℃, the pressure is 1.5MPa, and the liquid phase density is 805kg/m3The catalyst is AlCl3The catalyst content is 0.7 percent, the particle size of the catalyst is 100-1840 mu m, and the bulk density is 1660-1840kg/m3The treatment capacity is 15-20 t/h.
2. Cyclone separator
The cyclone separator is formed by connecting two cyclone tubes in parallel and in combination, the size of the cyclone tube is DN100 (the diameter is 100mm), and the treatment capacity of a single cyclone tube is 10-12 t/h.
3. Fluidized bed separator
The diameter of the fluidized bed separator is 1500mm, the particle size of bed layer filler is 1-2mm, the height of the particle bed layer is 1000mm, and the single treatment capacity is 15-30 t/h.
4. Carrying out the process
Polymerization liquid of C5 raw material and AlCl3The catalyst reacts in a polymerization reaction kettle, and the reacted catalyst contains a large amount of AlCl3The polymerization liquid of the catalyst enters a cyclone separator for concentration and separation, wherein the polymerization liquid contains high amount (80 percent) of AlCl3Pumping the catalyst polymerization liquid into a circulating system through a bottom flow port of the cyclone separator and feeding the catalyst polymerization liquid into a polymerization reaction kettle for recycling; the polymerization liquid on the overflow port of the cyclone separator enters a fluidized bed separator for deep purification treatment to remove a small amount of AlCl remaining in the clean polymerization liquid on the overflow port3The catalyst, after the fluidized bed separator runs for a certain time continuously, the back flush water valve and the air valve are opened, under the back flush action of water and gas, the filter material in the fluidized bed separator is in a suspended boiling state, then the filter material enters the three-phase separator at the top of the separator for cyclone separation, under the action of reinforced desorption of particle autorotation revolution coupling in the separator, the regenerated filler is backfilled to a bed layer from a low flow port of the cyclone, the catalyst is discharged to a storage tank from an overflow port of the separator at the top, and the regenerated liquid is discharged into a sewage tank; the clean polymerization liquid flows out from the bottom of the fluidized bed separator and enters a subsequent neutralization reaction kettle, and neutralization reaction is carried out by injecting NaOH alkali liquor; and generating a small amount of water after the neutralization reaction, and then subsequently performing oil-water separation treatment, wherein the water phase is discharged into a sewage treatment plant for treatment, and the oil phase forms crude resin liquid.
5. Analysis of results
After separation by the cyclone separator, more than 80% of the catalyst flows back to the circulating system through the underflow port of the cyclone separator and enters the polymerization reaction kettle for recycling, less than 20% of the catalyst flows through the fluidized bed separator along with the polymerization liquid for deep separation treatment, and the catalyst content in the clean polymerization liquid treated by the fluidized bed separator is lower than 10 mg/L; the inlet pressure of the cyclone separator is 1.5MPa, the pressure loss is less than 0.2MPa, the inlet pressure of the fluidized bed separator is more than 1.3MPa, and the pressure loss is less than 0.3 MPa; the cyclone separator continuously operates for a long time, the boiling bed separator continuously operates for more than 10 hours, the initial separation effect can be continuously kept after backwashing regeneration operation, and the separation efficiency exceeds 95 percent. The catalyst consumption is reduced by 80%, the catalyst content in the polymerization solution is reduced to be below 10mg/L, the required sodium hydroxide for neutralizing the alkali liquor is reduced by 95%, and further the discharge amount of high-concentration wastewater is reduced by 80%.
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 (10)
1. A method for reducing emission and consumption of C5 resin cold polymerization production comprises the following steps:
(a) c5 raw material and polymerization liquid are mixed and flow into a polymerization reaction kettle with catalyst for reaction;
(b) after the reaction, part of the mixed polymerization liquid flows back to the polymerization reaction kettle for recycling, part of the mixed polymerization liquid flows into a cyclone separator for cyclone separation treatment, and the polymerization liquid containing high-content catalyst after the cyclone separation treatment flows back to the polymerization reaction kettle for recycling through a bottom flow port of the cyclone separator; wherein the solid content of the catalyst in the mixed polymerization liquid at the inlet of the cyclone separator is less than or equal to 8000 mg/L;
(c) feeding the polymerization liquid of the supernatant at the overflow port of the cyclone separator into a fluidized bed separator for deep purification treatment so as to remove a small amount of residual catalyst in the polymerization liquid of the supernatant; and
(d) and the purified polymer liquid after the deep purification treatment enters a neutralization reaction kettle for neutralization reaction.
2. The method of claim 1, further comprising the steps of:
(e) and (3) allowing the polymer solution obtained after the neutralization reaction 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 a 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.
3. The process of claim 1 or 2, wherein in step (a), the catalyst is AlCl3A solid catalyst.
4. The method according to claim 1 or 2, wherein in step (b), in the mixed polymerization liquid at the inlet of the cyclone separator, the viscosity of the polymerization liquid is less than or equal to 22cp, and the particle size of the catalyst is less than or equal to 250 μm; the separation efficiency of the cyclone separator is more than or equal to 80 percent, the catalyst is recycled more than or equal to 80 percent, and the pressure loss is 0.05 MPa-0.20 MPa.
5. The method according to claim 1 or 2, wherein in the step (b), the cyclone separator is operated continuously, the mixed polymerization solution is subjected to catalyst separation under cyclone separation, and meanwhile, the rotational flow and the revolution in the cyclone separator are coupled, so that the catalyst micro-interface is subjected to pulsation oscillation, and reaction byproducts adhered to the catalyst pore channels and the micro-interface are separated; the micro interface of the catalyst is updated, the activity is recovered on line and flows back to the polymerization reaction kettle to promote the reaction.
6. The method of claim 1 or 2, wherein in step (c), the solid content of the catalyst in the supernatant polymerization liquid flowing into the boiling bed separator from the overflow port of the cyclone separator is less than or equal to 1600mg/L, the viscosity of the supernatant polymerization liquid is less than or equal to 22cp, and the particle size of the catalyst is less than or equal to 250 μm; the operation period of the fluidized bed separator is more than 8 hours, the solid content of the catalyst in the outlet polymerization liquid is less than or equal to 10mg/L, and the pressure loss is 0.05 MPa-0.30 MPa.
7. The method of claim 1 or 2, wherein in step (c), the ebullated-bed separator is operated intermittently, and after a certain period of continuous operation, plant-area circulating water or fresh water and plant-area compressed air or steam are reversely introduced to make the packing in the bed undergo suspension boiling to a fluidized state, and the bed is cleaned to realize regeneration; during back washing regeneration, fluidized filler enters a top three-phase separator, the filler and a catalyst are separated in a reinforced mode through particle rotation and revolution coupling in a cyclone field, meanwhile, a separation medium and a catalyst micro-interface vibrate and desorb surface adherends in a pulsating mode, the catalyst flows out of an overflow port of a fluidized bed separator to a storage tank, and the filler is backfilled to a bed layer.
8. A device for reducing emission and consumption of C5 resin cold polymerization production comprises:
a polymerization reaction kettle (1-1) for mixing the raw material C5 and the polymerization solution in the step (a), flowing into the polymerization reaction kettle with the catalyst and reacting;
the cyclone separator (1-3) is connected with the polymerization reaction kettle (1-1) and is used for refluxing part of mixed polymerization liquid to the polymerization reaction kettle for recycling after the reaction in the step (b), part of mixed polymerization liquid flows into the cyclone separator for cyclone separation treatment, and the polymerization liquid containing high-content catalyst after the cyclone separation treatment is refluxed to the polymerization reaction kettle for recycling through a bottom flow port of the cyclone separator;
the fluidized bed separator (1-4) is connected with the cyclone separator (1-3) and is used for feeding the polymerization liquid at the overflow port of the cyclone separator in the step (c) into the fluidized bed separator for deep purification treatment so as to remove a small amount of residual catalyst in the polymerization liquid at the supernatant; and
and the neutralization reaction kettle (1-5) is connected with the boiling bed separator (1-4) and is used for introducing the purified polymerization liquid subjected to the deep purification treatment in the step (d) into the neutralization reaction kettle for neutralization reaction.
9. The apparatus of claim 8, further comprising:
a standing layering tank (1-7) connected with the neutralization reaction kettle (1-5), a coalescent dehydrator (1-8) connected with the standing layering tank (1-7), and a settling tank (1-9) connected with the coalescent dehydrator (1-8), wherein the polymerized liquid obtained after neutralization reaction in the step (e) enters the standing layering tank for standing oil-water primary separation, the water phase enters a sewage treatment system for treatment, the oil phase enters the coalescent dehydrator for deep dehydration, the deeply removed water phase enters the sewage treatment system, the deeply dehydrated oil phase polymerized liquid enters the 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.
10. The apparatus of claim 8 or 9, wherein the cyclone separator is a liquid-solid cyclone structure, which is sized according to the throughput, and is formed by connecting a plurality of cyclone bodies in parallel according to the throughput, and is made of acid-resistant and alkali-resistant materials; the material of the fluidized bed separator is acid-resistant and alkali-resistant material, the separating filler is acid-resistant and alkali-resistant material, and the particle size of the filler is selected according to the particle size of the catalyst in the treated polymerization liquid.
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