CN113480680A - Method for preparing low-molecular-weight sodium polyacrylate dispersant by using waste water from butyl acrylate production - Google Patents
Method for preparing low-molecular-weight sodium polyacrylate dispersant by using waste water from butyl acrylate production Download PDFInfo
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Abstract
The invention discloses a method for preparing a low molecular weight sodium polyacrylate dispersant by using waste water in butyl acrylate production, which at least comprises the following steps: (1) adsorption impurity removal pretreatment; (2) regenerating the adsorbent; (3) membrane concentration; (4) oligomerization reaction; (5) and (3) evaporation and concentration: and in the evaporation concentration reactor, further concentrating the polymerization reaction liquid until the concentration is more than or equal to 40 percent to prepare the sodium polyacrylate dispersant with low molecular weight. The method has the advantages of simple process flow, easy operation and control, low investment, high benefit and low operation cost, and can create good environmental benefit, social benefit and economic benefit; the method not only can solve the problem of safe discharge of waste water in butyl acrylate production, but also can remove impurities from sodium acrylate in the waste water through adsorption, pretreatment, membrane concentration, free radical polymerization reaction and the like to obtain a byproduct sodium polyacrylate dispersant product with high quality and low molecular weight. Meanwhile, the water quality of the membrane concentrated effluent and the distilled condensate water can be reused as process water, and near zero emission is basically achieved.
Description
Technical Field
The invention relates to the field of industrial wastewater treatment, in particular to a method for preparing a low molecular weight sodium polyacrylate dispersant by using waste water from butyl acrylate production.
Background
Acrylic acid and esters thereof are important organic chemical raw materials, unique excellent performance characteristics of the acrylic acid and esters thereof are gradually recognized, and industrial derivatives thereof are increasingly widely applied. At present, the industry mainly adopts a direct gas phase oxidation method of propylene to produce acrylic acid, and different alcohols are subjected to esterification reaction to produce corresponding acrylic ester. Acrylic acid and esters thereof are increasingly widely used as high molecular polymer monomers in industry, can be used for manufacturing soft monomers of acrylate solvent type and emulsion type adhesives, can perform homopolymerization, copolymerization or graft copolymerization, and can be used for organic synthesis intermediates, coatings, adhesives, acrylic fiber modification, plastic modification, fiber and fabric processing, paper treating agents, leather processing, acrylic rubber and other aspects. For example, butyl acrylate (as well as methyl, ethyl, and 2-ethylhexyl acrylates) are soft monomers that can be copolymerized, crosslinked, grafted, etc., with various hard monomers such as methyl methacrylate, styrene, acrylonitrile, vinyl acetate, etc., and functional monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl ester, glycidyl ester, (meth) acrylamide, and derivatives thereof, to produce hundreds of acrylic resin products (mainly emulsion, solvent, and water soluble).
Butyl acrylate can generate a great amount of production wastewater with high salinity, high chroma and high organic concentration in the production process, and COD in the production wastewaterCrThe content is 5000-150000mg/L, the main component is 0.5-15% of sodium acrylate, the TDS (total dissolved solids) content is 3000-50000mg/L, the conductivity is 3000-130000 mu s/cm, and the impurity component of the trace polymerization inhibitor causes the chroma of the wastewater to be 50-600 times and other trace impurity components. If the waste water from butyl acrylate production is treated as industrial waste waterThe treatment difficulty is very high, the process is complex, the treatment cost is high, and a plurality of enterprises are difficult to bear high investment and operation and maintenance costs for environmental protection treatment of wastewater.
At present, the treatment of the wastewater generated in the production of acrylic acid and acrylic ester mainly adopts a direct incinerator incineration method, and the wet air has good water quality, and can reach the first-class discharge standard of Integrated wastewater discharge Standard (GB 8978-1996). However, because of the complex components in the acrylic acid and ester wastewater, when the dilution ratio is large, the biological toxicity is still hard to be reduced within the range of biological oxidation tolerance, and the acrylic acid and ester wastewater is not suitable for direct biological treatment, and generally special pretreatment means are required, such as "extraction pretreatment-coagulating sedimentation-biological treatment method" disclosed in CN105130060A, "polymerization reaction-coagulating sedimentation-biological treatment method" disclosed in CN105084607A, CN105129906A, and the like, and "coagulating sedimentation-polymerization reaction-biological treatment method" disclosed in CN105084608A, and the like. Overall, the physicochemical pretreatment-biological oxidation-advanced treatment combined method has complex treatment process flow, large engineering investment, large occupied area and relatively high operation and maintenance treatment cost. On the other hand, a large amount of sodium acrylate in the wastewater is not well utilized, so that resource waste is caused.
At present, a series of patents have been paid attention to the acrylic acid and ester wastewater resource treatment method at home and abroad, so that valuable substances in wastewater can be recovered, and certain economic benefits are obtained, for example:
the prior art CN102267890 discloses a method for recovering acrylic acid from acrylic ester wastewater, which adopts a combined process of suspended matter removal pretreatment, primary extraction, secondary extraction and refining to extract and recover acrylic acid from acrylic ester production wastewater, can obviously reduce the content of acrylic acid in the wastewater and reduce the treatment difficulty and the treatment load of a subsequent treatment unit.
The prior art CN 10340817 discloses a method for treating (methyl) acrylic acid waste water and recovering sodium acetate, which is to adopt inorganic catalysts such as ferrous salt and the like to catalyze the polycondensation reaction of (methyl) acrylic acid under the heating condition to generate macromolecular high-boiling-point polymers. Toluene and acetic acid form a similar multi-component azeotrope to be carried out along with water evaporation, the condensed toluene can enter an oil-water separator to be separated and recovered, the water phase is neutralized by adding alkali, and the toluene is evaporated, concentrated, cooled and crystallized to recover crystallized sodium acetate.
The prior art CN 1903738A discloses an acrylic acid wastewater treatment process, which adopts a reverse osmosis membrane concentration-rectification combined process to recover and obtain acrylic acid, toluene, acetic acid and the like.
The prior art CN103588935A discloses a method for preparing a modified lignosulfonate water reducing agent by taking acrylic acid wastewater as a raw material, which comprises the steps of adding an oxidant into the acrylic acid wastewater for pretreatment, and then carrying out graft polymerization reaction on a lignosulfonate solution in a certain proportion, the acrylic acid wastewater and sodium sulfonate small monomers under the action of a catalyst and an initiation aid at a certain reaction temperature to obtain the modified lignosulfonate water reducing agent.
The prior art CN104773882A discloses a process for treating and recycling acrylic acid wastewater, which adopts an acrylic acid gas oxidation method, a wet catalytic oxidation method, a supercritical water oxidation method, an electrocatalytic oxidation method, an ozone catalytic oxidation method and the like or adopts a physicochemical pretreatment-biological oxidation-advanced treatment combined method and the like. The incineration process of the incinerator is adopted, the engineering investment is large, meanwhile, because high-calorific-value pollutants in the wastewater are few, the direct incineration of the wastewater not only consumes a large amount of fuel gas or fuel oil, and the energy consumption and the operating cost are high, but also sodium carbonate generated by incineration can erode the refractory material of the incinerator, so that the incinerator can not operate for a long period. By adopting a wet air oxidation method, a wet catalytic oxidation method, a supercritical water oxidation method, an electrocatalytic oxidation method, an ozone catalytic oxidation method and the like (such as CN 105236649A, CN 105236648A, CN105198118A, CN 105712459A, CN1948189A and the like in the prior art), the reactor has high manufacturing cost, large overall engineering investment, high treatment cost and high operation risk, and is difficult to accept by common enterprises.
At present, a series of patents concern the treatment of acrylic acid and its ester wastewater at home and abroad, for example:
the prior art CN1948189A discloses a method for treating acrylic acid wastewater by a post-electrolysis biological treatment process, which realizes the biochemical treatment of the acrylic acid wastewater, but the electrolysis used in the pretreatment of the method has high energy consumption and is not suitable for high-salinity acrylic ester wastewater.
The prior art CN102267890A discloses a method for recovering acrylic acid in acrylate wastewater by an extraction method, but the method has low recovery efficiency, effluent cannot meet biochemical requirements, and direct biochemical treatment after pretreatment is difficult to realize before further optimization.
The prior art CN 101786742a discloses a method for recovering macromolecular substances by polymerizing acrylic acid in acrylate wastewater and using membrane separation. The method uses a membrane method to separate macromolecular substances, has higher operation cost, has high salt content in the wastewater, is easy to block the membrane, and needs frequent cleaning.
The method is feasible by adopting a physicochemical pretreatment-biological oxidation-advanced treatment combined method, can reach the environment-friendly water quality standard of safe discharge, but because acrylic acid and ester wastewater contains substances with biotoxicity or biological inhibition, the wastewater treated by the biological method needs to be firstly treated by a certain pretreatment means, such as mixing and diluting with domestic sewage, so as to reduce the concentration of the substances which are difficult to degrade by organisms, such as acrylic acid, and then is treated by adopting a proper anaerobic and aerobic process. For example:
the prior art CN 206204105U discloses a butyl acrylate production wastewater treatment system, which comprises a water inlet pipeline, an adjusting tank, a coagulating sedimentation tank, an MVR, a Fenton oxidation tank, a primary sedimentation tank, a primary hydrolysis acidification tank, a primary aerobic tank, a middle sedimentation tank, a secondary hydrolysis acidification tank, a secondary aerobic tank, a secondary sedimentation tank, a sludge concentration tank, a sludge digestion tank, a plate-and-frame filter press, a sludge outward transportation pipeline and the like, wherein the biodegradability of the outlet water is good, the wastewater is sequentially subjected to nanofiltration treatment, primary electrodialysis treatment and secondary electrodialysis treatment, the concentrated outlet water of an electrodialysis system is subjected to subsequent rectification process or high-pressure reverse osmosis process, and the fresh outlet water returns to an acrylic acid absorption tower to be recycled as absorption water.
The prior art CN 101269899A discloses a comprehensive treatment method of acrylic acid wastewater, which adopts a combined method of electrodialysis, biochemistry, extraction and rectification. Acrylic acid wastewater is sent into a pretreatment unit, the pretreated wastewater enters an electrodialyzer, dilute phase effluent of the electrodialyzer meets biochemical treatment requirements and then enters a biochemical treatment device, and the acrylic acid wastewater is discharged after reaching standards after biochemical treatment; the concentrated phase effluent of the electrodialyzer is concentrated to a certain concentration by second-stage, third-stage or fourth-stage electrodialysis, and then is sent to an extraction-rectification unit for recycling acetic acid, so that industrial first-stage acetic acid can be obtained.
The prior art CN102225976A discloses a method for preparing polyacrylic acid dispersant by using acrylic acid wastewater as raw material, which uses alkaline, acidic and neutral acrylic acid wastewater as raw material to prepare polyacrylic acid dispersant by free radical polymerization reaction.
The waste water produced by butyl acrylate production has high chroma, high salt content, high organic matter concentration, great treatment difficulty, complex process, high investment in treatment engineering and high operation cost. The existing treatment method or resource method for acrylic acid and ester production wastewater has the defects of relatively complex process flow, large engineering investment, high operation cost, large operation difficulty and the like, and is not suitable for treating butyl acrylate production wastewater.
Therefore, a method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production, which has the advantages of relatively simple operation, low investment cost and high return on investment, needs to be found.
Disclosure of Invention
The invention aims to provide a method for preparing a low molecular weight sodium polyacrylate dispersant by using butyl acrylate production wastewater, which has the advantages of relatively simple operation, low investment cost and high return on investment, aiming at the defects and shortcomings of the existing acrylic acid and ester production wastewater treatment technology.
In order to realize the aim, the invention provides a method for preparing a low molecular weight sodium polyacrylate dispersant by using waste water in butyl acrylate production, which comprises the following steps:
step (1), adsorption impurity removal pretreatment: pumping butyl acrylate wastewater into an adsorption impurity removal pretreatment reactor, adding an adsorption impurity removal decolorizing agent, stirring for 10-20 minutes, reacting until the chroma is reduced to below 10 times by a dilution multiple method, stopping reaction, and filtering; the effluent after pretreatment and filtration enters a membrane concentration reactor, and the filtered adsorption impurity removal decolorant enters a regeneration system;
step (2), adsorbent regeneration: the filtered adsorption impurity removal decolorizing agent enters a regeneration system, and the regenerated adsorption impurity removal decolorizing agent circularly enters a pretreatment reactor for recycling;
step (3), membrane concentration: the effluent after pretreatment, filtration and decoloration enters a reverse osmosis membrane for concentration, the reverse osmosis membrane concentrated effluent can be reused as process water for enterprises, and the concentrated solution enters a free radical polymerization reactor for polymerization;
step (4), oligomerization: pumping the membrane concentrate into a polymerization reactor, controlling the temperature of free radical polymerization to be 30-80 ℃ by a heating temperature control system, adding an initiation aid A and an initiation aid B, starting free radical polymerization for 60-300 minutes, and entering an evaporation concentration reactor;
and (5) evaporating and concentrating: and in the evaporation concentration reactor, further concentrating the polymerization reaction liquid until the concentration is more than or equal to 40 percent to prepare the sodium polyacrylate dispersant with low molecular weight.
Further, in the step (1), the pH value of the butyl acrylate production wastewater is 6-9, and the COD isCrThe content is 5000-150000mg/L, the main component of the butyl acrylate production wastewater is 0.5-15% of sodium acrylate, the TDS content is 3000-80000mg/L, the conductivity is 3000-130000 mu s/cm, and the chroma of the wastewater is 50-600 times and other trace impurity components caused by trace polymerization inhibitor impurity components.
Further, in the step (2), the adsorption impurity removal decolorizing agent is one or a combination of more of granular activated carbon, powdered activated carbon, modified activated carbon, regenerated activated carbon, zeolite, modified zeolite, diatomite, modified diatomite, attapulgite, modified attapulgite, kaolin and modified kaolin, the adding amount is 0.2-3.0% of the mass of the waste water produced by butyl acrylate production, the adsorption impurity removal pretreatment reaction time is 5-60 minutes, and the adsorption impurity removal pretreatment reaction temperature is 10-90 ℃.
Furthermore, in the step (2), the regeneration mode of the adsorption impurity removal decolorizing agent is one or more of clear water backwashing regeneration, membrane filtration water backwashing regeneration, condensed water backwashing regeneration evaporated in the evaporation process, steam heating regeneration, Fenton reagent oxidation regeneration or ozone oxidation regeneration; in the step (3), after the membrane is concentrated, the concentration of concentrated-phase sodium acrylate is 15-25%.
Further, in the step (3), the concentration of the concentrated-phase sodium acrylate is 17% -21%, the oligomerization reaction process is a normal-pressure radical polymerization reaction, and the reactor is any one of a glass lining reactor, a stainless steel reactor or a carbon steel corrosion-resistant reactor.
Further, in the step (3), the reactor is a reactor with a heating constant temperature control system; in the step (4), the oligomerization reaction is a reaction system initiated by compounding an initiation aid a and an initiation aid B, wherein the initiation aid a is one or a combination of sodium persulfate, ammonium persulfate and potassium persulfate, and the initiation aid B is one or a combination of sodium bisulfite, ammonium bisulfite and potassium bisulfite.
Furthermore, in the step (4), the amount of the initiation aid A is 0.5-3.5% of the mass of the sodium acrylate in the butyl acrylate production wastewater, and the amount of the initiation aid B is 1.0-5.0% of the mass of the sodium acrylate in the butyl acrylate production wastewater; in the step (5), after evaporation and concentration, the concentration of the sodium polyacrylate in the concentrated phase is 30-60%,
further, in the step (5), the concentration of the sodium polyacrylate in the concentrated phase is 40-45%.
Further, in the step (5), part of water vapor is evaporated from the upper part of the evaporation concentration reactor, and after condensation, the evaporated water can be recycled to the production or directly discharged after reaching the standard.
The invention has the beneficial effects that:
due to the adoption of the technical scheme, the invention has the advantages of energy conservation, environmental protection, simple process flow, easy operation and control, low investment, low operation cost and the like, and can create good environmental benefit, social benefit and economic benefit.
The invention not only solves the problem of safe discharge of waste water in butyl acrylate production, but also forms a byproduct sodium polyacrylate dispersant product with high quality and low molecular weight by the technical means of adsorption impurity removal pretreatment, membrane concentration, free radical polymerization reaction and the like. Meanwhile, the water quality of the membrane concentrated effluent and the distilled condensate water can be reused as process water, and near zero emission is basically achieved.
Compared with the prior art, particularly the technology for treating the waste water generated in the butyl acrylate production by adopting the conventional waste water treatment process, the method has the following remarkable advantages:
(1) according to the water quality characteristics of the butyl acrylate production wastewater, the adsorption, impurity removal and decoloration pretreatment of the butyl acrylate production wastewater is strengthened to obtain a high-quality sodium polyacrylate dispersant; the concentration of sodium acrylate in the wastewater is controlled in a reasonable range by concentration and filtration of a reverse osmosis membrane so as to improve the reaction efficiency of free radical polymerization; the method comprises the following steps of (1) obtaining a high-quality low-molecular-weight sodium polyacrylate solution by optimally controlling free radical polymerization reaction conditions; finally, concentrating the low molecular weight sodium polyacrylate solution to be within the industry standard concentration range through evaporation concentration to form a marketable product.
(2) From the aspect of economic benefit, the invention emphasizes a high value-added resource utilization technology, obtains the high-quality low-molecular-weight sodium polyacrylate dispersant from the butyl acrylate production wastewater, and the low-molecular-weight sodium polyacrylate dispersant is used as a dispersant, oil extraction oil aid, washing aid, high-efficiency water-reducing aid and the like commonly used in industry, and has wide application; meanwhile, the membrane concentration filtration effluent and the water evaporated by evaporation concentration are recycled to industrial enterprises, a zero-emission treatment mode is basically realized, the mode has obvious economic benefit, two products of reuse water and high-quality low-molecular-weight sodium polyacrylate can be formed, the income of process water and water cost and the income of high-added-value product sales are increased, the environment-friendly investment and operating cost of wastewater treatment are saved, and the investment income is high;
(3) from the view of environmental benefit, zero emission of waste water in butyl acrylate production can be basically realized, besides a large amount of reuse water and low-molecular-weight sodium polyacrylate products can be obtained, impurities in the waste water are adsorbed by the adsorbent, and then enter backwash water through different forms of regeneration, and then are converged into a plant-area domestic waste water treatment plant for treatment. The conventional process for treating the waste water generated in the butyl acrylate production needs to adopt combined processes of grating-materialization pretreatment-anaerobic treatment-anoxic treatment-aerobic treatment-advanced treatment and the like from the introduction of the prior background technology, particularly relates to a biochemical treatment process unit, has the advantages of large floor area, long process flow, large civil engineering and engineering investment and high operation and maintenance cost, and finally, even if the waste water is discharged after reaching the standard safely, a large amount of waste water is discharged into the ecological environment actually.
(4) From social benefit, the waste resources of sodium acrylate and wastewater in the wastewater are fully utilized and converted into resources of enterprises, so that waste is changed into valuable, and carbon emission is reduced.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
To facilitate a better understanding of the present invention, the following examples are set forth. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
The invention relates to a method for preparing a low molecular weight sodium polyacrylate dispersant by using waste water from butyl acrylate production, which comprises the following steps:
step (1), adsorption impurity removal pretreatment: taking 1000ml of butyl acrylate production wastewater, analyzing the wastewater to obtain COD in the wastewater, wherein the pH value of the wastewater is 8.32, and the water temperature is 45 DEG CCrThe content is 51253mg/L, the TDS content is 26730mg/L, the conductivity is 51560 mus/cm, and the chroma is 200 times.
Step (2), adsorbent regeneration: and (2) carrying out adsorption impurity removal and decoloration pretreatment by using 200-mesh diatomite, wherein the adding amount of the diatomite is 1.5%, and after the reaction time of the adsorption impurity removal pretreatment is 30 minutes, filtering is carried out to obtain the butyl acrylate production wastewater with the chroma being 8 times.
Step (3), membrane concentration: and pumping the filtered butyl acrylate production wastewater to a reverse osmosis membrane filter, and concentrating the membrane until the concentration of sodium acrylate is 18%, filtering out water by the membrane is 710ml, and concentrating the solution to 290 ml.
Step (4), oligomerization: the remaining 290ml of the 18% strength sodium acrylate aqueous waste solution was transferred to a 500ml polymerization reaction flask, the temperature of the solution was electrically heated to 70 degrees centigrade, and then 4.7ml of 20% strength ammonium persulfate and 6.5ml of 40% strength sodium bisulfite were slowly added to the reaction flask while stirring at 250rpm for 30 minutes, and then the reaction was continued for 180 minutes, and the reaction was stopped.
Step (5), the reacted solution was transferred to a distillation flask equipped with a condenser, and 150ml of water was condensed by distillation. 140ml of concentrated solution in the distillation flask is the sodium polyacrylate dispersant with low molecular weight. Part of water vapor is evaporated from the upper part of the evaporation concentration reactor, and after condensation, the evaporated water can be recycled on production or directly discharged after reaching the standard.
Example 2
Embodiment 2 applies the same technical principle as embodiment 1, except that specifically:
in the step (1), adsorption impurity removal pretreatment: taking 1000ml of butyl acrylate production wastewater, analyzing the wastewater to obtain COD in the wastewater, wherein the pH value of the wastewater is 8.32, and the water temperature is 45 DEG CCrThe content is 51253mg/L, the TDS content is 26730mg/L, the conductivity is 51560 mus/cm, and the chroma is 200 times.
In step (2), the adsorbent is regenerated: carrying out adsorption impurity removal and decoloration pretreatment by using 200-mesh powdered activated carbon, adding 5g of the powdered activated carbon, reacting for 10 minutes, and filtering to obtain the butyl acrylate production wastewater with the chromaticity 5 times.
In step (3), membrane concentration: and pumping the filtered butyl acrylate production wastewater to a reverse osmosis membrane filter, concentrating the membrane until the concentration of sodium acrylate is 15%, filtering out 660ml of water by the membrane, and concentrating the 340ml of solution.
In step (4), oligomerizing: the sodium acrylate solution with the concentration of 15% is transferred into a 500ml polymerization reaction flask, the temperature of the solution is electrically heated to 55 ℃, then 4.0ml of sodium persulfate with the concentration of 20% and 6.8ml of sodium bisulfite with the concentration of 40% are slowly added into the reaction flask under the condition of stirring at the rotating speed of 250rpm, the adding time is 30 minutes, then the reaction is continued for 220 minutes, and the reaction is stopped.
In step (5), the reacted solution was transferred to a distillation flask equipped with a condenser, and 205ml of water was condensed. 145ml of concentrated solution in the distillation flask is the sodium polyacrylate dispersant with low molecular weight.
Example 3
Example 3 applies the same technical principle as example 1, except that specifically:
in the step (1), adsorption impurity removal pretreatment: taking 5000ml of butyl acrylate production wastewater, analyzing the wastewater to obtain COD in the wastewater, wherein the pH value of the wastewater is 8.36, and the water temperature is 35 DEG CCrThe content is 126720mg/L, the TDS content is 98740mg/L, the conductivity is 107320 mus/cm, and the chroma is 500 times.
In step (2), the adsorbent is regenerated: carrying out adsorption impurity removal and decoloration pretreatment by using 200-mesh powdered activated carbon, adding 50g of the powdered activated carbon, reacting for 15 minutes, and filtering to obtain the butyl acrylate production wastewater with the chromaticity being 10 times.
In step (3), membrane concentration: and pumping the filtered butyl acrylate production wastewater to a reverse osmosis membrane filter, concentrating the membrane until the concentration of sodium acrylate is 19%, filtering out 1700ml of water by the membrane, and obtaining 3300ml of concentrated solution.
In step (4), oligomerizing: transferring the 19% sodium acrylate solution into a 5000ml polymerization reaction flask, electrically heating the solution to 60 ℃, then slowly adding 50ml of 20% ammonium persulfate and 75ml of 40% sodium bisulfite into the reaction flask while stirring at 235rpm, wherein the adding time is 60 minutes, then continuing to react for 240 minutes, and stopping the reaction.
In step (5), the reacted solution was transferred to a distillation flask equipped with a condenser, and 1850ml of water was condensed out. 1570ml of the concentrated solution in the distillation flask is the sodium polyacrylate dispersant with low molecular weight.
Example 4
Example 4 applies the same technical principle as example 1, except that specifically:
in the step (1), adsorption impurity removal pretreatment: pumping butyl acrylate wastewater into an adsorption impurity removal pretreatment reactor, adding an adsorption impurity removal decolorizing agent, stirring for 20 minutes, reacting until the chroma is reduced to below 10 times by a dilution multiple method, stopping reaction, and filtering; the effluent after pretreatment and filtration enters a membrane concentration reactor, and the filtered adsorption impurity removal decolorant enters a regeneration system; the pH value of the butyl acrylate production wastewater is 6, and the COD isCrThe content of the waste water is 5000mg/L, the main component of the waste water in the production of the butyl acrylate is sodium acrylate with the content of 0.5 percent, the TDS content is 80000mg/L, the conductivity is 130000 mu s/cm, and the chroma of the waste water is 600 times and other trace impurity components are caused by trace polymerization inhibitor impurity components.
The adsorption impurity removal decolorant is a combination of various materials of granular activated carbon, modified activated carbon, regenerated activated carbon, zeolite, modified diatomite, attapulgite, modified attapulgite, kaolin and modified kaolin, the adding amount of the adsorption impurity removal decolorant is 0.2% of the mass of the waste water produced by butyl acrylate production, the adsorption impurity removal pretreatment reaction time is 5 minutes, and the adsorption impurity removal pretreatment reaction temperature is 90 ℃.
In step (2), the adsorbent is regenerated: the filtered adsorption impurity removal decolorizing agent enters a regeneration system, and the regenerated adsorption impurity removal decolorizing agent circularly enters a pretreatment reactor for recycling;
the regeneration mode of the adsorption impurity removal decolorizing agent is backwashing regeneration by clear water;
in step (3), membrane concentration: the effluent after pretreatment, filtration and decoloration enters a reverse osmosis membrane for concentration, the reverse osmosis membrane concentrated effluent can be reused as process water for enterprises, and the concentrated solution enters a free radical polymerization reactor for polymerization; after membrane concentration, the concentration of concentrated sodium acrylate was 15%. The concentration of the concentrated-phase sodium acrylate is 21%, the oligomerization process is a normal-pressure free radical polymerization reaction, and the reactor is a glass lining reaction kettle. The reactor is a reactor with a heating constant temperature control system;
in step (4), oligomerizing: pumping the membrane concentrate into a polymerization reactor, controlling the temperature of free radical polymerization to be 30 ℃ by a heating temperature control system, adding an initiator A and an initiation aid B, starting the free radical polymerization, controlling the free radical polymerization time to be 60 minutes, and entering an evaporation concentration reactor;
the oligomerization process is a reaction system initiated by compounding an initiator A and an initiation aid B, the initiator A is potassium persulfate, and the initiation aid B is a combination of two of ammonia bisulfite and potassium bisulfite.
The dosage of the initiator A is 0.5 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater, and the dosage of the initiation auxiliary agent B is 5.0 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater;
in step (5), concentration by evaporation: in an evaporation concentration reactor, further concentrating the polymerization reaction liquid to a certain concentration (more than or equal to 40 percent) to obtain a colorless viscous low-molecular-weight sodium polyacrylate product; part of water vapor is evaporated from the upper part of the evaporation concentration reactor, and after condensation, the evaporated water can be recycled on production or directly discharged after reaching the standard. After evaporation concentration, the concentration of sodium polyacrylate in the concentrated phase is 30%.
Example 5
Example 5 applies the same technical principle as example 1, except that specifically:
in the step (1), adsorption impurity removal pretreatment: pumping butyl acrylate wastewater into an adsorption impurity removal pretreatment reactor, adding an adsorption impurity removal decolorizing agent, stirring for 10 minutes, reacting until the chroma is reduced to below 10 times by a dilution multiple method, stopping reaction, and filtering; the effluent after pretreatment and filtration enters a membrane concentration reactor, and the filtered adsorption impurity removal decolorant enters a regeneration system; the above-mentioned butyl acrylateThe pH value of the production wastewater is 9, CODCrThe content is 150000mg/L, the main component of the butyl acrylate production wastewater is sodium acrylate content 15%, the TDS content is 3000mg/L, the conductivity is 3000 mus/cm, and the chroma of the wastewater is 50 times and other trace impurity components caused by trace polymerization inhibitor impurity components. The adsorption impurity removal decolorant is attapulgite, the adding amount of the adsorption impurity removal decolorant is 3.0% of the mass of the waste water produced by butyl acrylate production, the reaction time of adsorption impurity removal pretreatment is 60 minutes, and the reaction temperature of the adsorption impurity removal pretreatment is 10 ℃.
In step (2), the adsorbent is regenerated: the filtered adsorption impurity removal decolorizing agent enters a regeneration system, and the regenerated adsorption impurity removal decolorizing agent circularly enters a pretreatment reactor for recycling; the regeneration mode of the adsorption impurity removal decolorizing agent is backwashing regeneration of condensed water evaporated in the evaporation process;
in step (3), membrane concentration: the effluent after pretreatment, filtration and decoloration enters a reverse osmosis membrane for concentration, the reverse osmosis membrane concentrated effluent can be reused as process water for enterprises, and the concentrated solution enters a free radical polymerization reactor for polymerization; after membrane concentration, the concentration of concentrated sodium acrylate was 25%. The concentration of the concentrated-phase sodium acrylate is 17%, the oligomerization process is a normal-pressure free radical polymerization reaction, and the reactor is a stainless steel reactor. The reactor is a reactor with a heating constant temperature control system;
in step (4), oligomerizing: pumping the membrane concentrate into a polymerization reactor, controlling the temperature of free radical polymerization to be 80 ℃ by a heating temperature control system, adding an initiator A and an initiation aid B, starting the free radical polymerization, controlling the free radical polymerization time to be 300 minutes, and entering an evaporation concentration reactor;
the oligomerization process is a reaction system initiated by compounding an initiator A and an initiation aid B, the initiator A is potassium persulfate, and the initiation aid B is a combination of two of ammonia bisulfite and potassium bisulfite.
The dosage of the initiator A is 3.5 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater, and the dosage of the initiation auxiliary agent B is 1.0 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater;
in step (5), concentration by evaporation: after evaporation concentration, the concentration of the sodium polyacrylate in the concentrated phase is 60%.
Example 6
Example 6 applies the same technical principle as example 1, except that specifically:
in the step (3), the reactor is a stainless steel reactor.
In the step (4), the dosage of the initiator A is 2.5 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater, and the dosage of the initiation assistant B is 4.0 percent of the mass of the sodium acrylate in the butyl acrylate production wastewater; in the step (5), after evaporation concentration, the concentration of the sodium polyacrylate in the concentrated phase is 50%.
Test example 1
After analysis, the index of the sodium polyacrylate dispersant obtained in the embodiment 1 of the invention is shown in table 1, and the sodium polyacrylate dispersant completely meets the standard requirements of HG/T2838-2018 'water treatment agent sodium polyacrylate'.
TABLE 1
Test example 2
After analysis, the index of the sodium polyacrylate dispersant obtained in example 2 is shown in table 2, and the sodium polyacrylate dispersant completely meets the standard requirements of HG/T2838-2018 'water treatment agent sodium polyacrylate'.
TABLE 2
Test example 3
After analysis, the index of the sodium polyacrylate dispersant obtained in example 3 is shown in table 3, and the sodium polyacrylate dispersant completely meets the standard requirements of HG/T2838-2018 'water treatment agent sodium polyacrylate'.
TABLE 3
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. A method for preparing a low molecular weight sodium polyacrylate dispersant by using waste water from butyl acrylate production is characterized by comprising the following steps:
step (1), adsorption impurity removal pretreatment: pumping butyl acrylate wastewater into an adsorption impurity removal pretreatment reactor, adding an adsorption impurity removal decolorizing agent, stirring for 10-20 minutes, reacting until the chroma is reduced to below 10 times by a dilution multiple method, stopping reaction, and filtering; the effluent after pretreatment and filtration enters a membrane concentration reactor, and the filtered adsorption impurity removal decolorant enters a regeneration system;
step (2), adsorbent regeneration: the filtered adsorption impurity removal decolorizing agent enters a regeneration system, and the regenerated adsorption impurity removal decolorizing agent circularly enters a pretreatment reactor for recycling;
step (3), membrane concentration: the effluent after pretreatment, filtration and decoloration enters a reverse osmosis membrane for concentration, the reverse osmosis membrane concentrated effluent can be reused as process water for enterprises, and the concentrated solution enters a free radical polymerization reactor for polymerization;
step (4), oligomerization: pumping the membrane concentrate into a polymerization reactor, controlling the temperature of free radical polymerization to be 30-80 ℃ by a heating temperature control system, adding an initiation aid A and an initiation aid B, starting free radical polymerization for 60-300 minutes, and entering an evaporation concentration reactor;
and (5) evaporating and concentrating: and in the evaporation concentration reactor, further concentrating the polymerization reaction liquid until the concentration is more than or equal to 40 percent to prepare the sodium polyacrylate dispersant with low molecular weight.
2. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the pH value of the butyl acrylate production wastewater is 6-9, and the COD isCrThe content is 5000-150000mg/L, the main component of the butyl acrylate production wastewater is 0.5-15% of sodium acrylate, the TDS content is 3000-80000mg/L, the conductivity is 3000-130000 mu s/cm, and the chroma of the wastewater is 50-600 times and other trace impurity components caused by trace polymerization inhibitor impurity components.
3. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the adsorption impurity removal decolorizing agent is one or a combination of more of granular activated carbon, powdered activated carbon, modified activated carbon, regenerated activated carbon, zeolite, modified zeolite, diatomite, modified diatomite, attapulgite, modified attapulgite, kaolin and modified kaolin, the adding amount is 0.2-3.0% of the mass of the waste water generated in the production of the butyl acrylate, the adsorption impurity removal pretreatment reaction time is 5-60 minutes, and the adsorption impurity removal pretreatment reaction temperature is 10-90 ℃.
4. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the regeneration mode of the adsorption impurity removal decolorizing agent is one or more of clear water backwashing regeneration, membrane filtration water backwashing regeneration, condensate water backwashing regeneration evaporated in the evaporation process, steam heating regeneration, Fenton reagent oxidation regeneration or ozone oxidation regeneration; in the step (3), after the membrane is concentrated, the concentration of concentrated-phase sodium acrylate is 15-25%.
5. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the concentration of the concentrated-phase sodium acrylate is 17% -21%, the oligomerization process is a normal-pressure free radical polymerization reaction, and the reactor is any one of a glass lining reaction kettle, a stainless steel reactor or a carbon steel corrosion-resistant reaction kettle.
6. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 5, wherein the method comprises the following steps: in the step (3), the reactor is a reactor with a heating constant temperature control system; in the step (4), the oligomerization reaction is a reaction system initiated by compounding an initiation aid a and an initiation aid B, wherein the initiation aid a is one or a combination of sodium persulfate, ammonium persulfate and potassium persulfate, and the initiation aid B is one or a combination of sodium bisulfite, ammonium bisulfite and potassium bisulfite.
7. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 6, wherein the method comprises the following steps: in the step (4), the dosage of the initiation aid A is 0.5-3.5% of the mass of the sodium acrylate in the butyl acrylate production wastewater, and the dosage of the initiation aid B is 1.0-5.0% of the mass of the sodium acrylate in the butyl acrylate production wastewater; in the step (5), after evaporation concentration, the concentration of the sodium polyacrylate in the concentrated phase is 30-60%.
8. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 7, wherein the method comprises the following steps: in the step (5), the concentration of the sodium polyacrylate in the concentrated phase is 40-45%.
9. The method for preparing the low molecular weight sodium polyacrylate dispersant by using the waste water from butyl acrylate production as claimed in claim 8, wherein the method comprises the following steps: in the step (5), part of water vapor is evaporated from the upper part of the evaporation concentration reactor, and after condensation, the evaporated water can be recycled on production or directly discharged after reaching the standard.
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| CN115626735A (en) * | 2022-10-28 | 2023-01-20 | 南通百川新材料有限公司 | Equipment and method for recycling sodium acrylate from acrylate wastewater |
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