CN110746527A - Treatment method of (methyl) acrylic acid wastewater - Google Patents

Treatment method of (methyl) acrylic acid wastewater Download PDF

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Publication number
CN110746527A
CN110746527A CN201911095366.0A CN201911095366A CN110746527A CN 110746527 A CN110746527 A CN 110746527A CN 201911095366 A CN201911095366 A CN 201911095366A CN 110746527 A CN110746527 A CN 110746527A
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acrylic acid
waste water
wastewater
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treating
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CN110746527B (en
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王跃川
徐燕
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention discloses a method for treating (methyl) acrylic acid wastewater, which comprises the steps of adding a vinyl monomer and an initiator into the (methyl) acrylic acid wastewater, converting the (methyl) acrylic acid wastewater into a polymer in a gel form by illumination, and dehydrating and drying to obtain a high-water-absorptivity material. The method for treating the acrylic acid wastewater has the advantages of low energy consumption, high efficiency and simple process, and can realize resource utilization of the wastewater generated in the production of (methyl) acrylic ester.

Description

Treatment method of (methyl) acrylic acid wastewater
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for treating acrylic acid wastewater.
Background
The (meth) acrylic acid contained in the industrial wastewater generated in the production of (meth) acrylic esters is difficult to biodegrade, the treatment cost of the direct incineration method is too high, and the discharge after dilution causes huge damage to the water environment, so that harmless treatment is required. The treatment methods for (meth) acrylic acid-based wastewater include three methods of physical, chemical and biological methods, all of which require multi-step treatment that is time-consuming and high in running cost.
The prior treatment mode, application No. CN201710930729.2, application No. 20171009 patent of invention, discloses a comprehensive treatment method of acrylic ester production wastewater, which comprises the steps of adding at least one chain transfer agent of aliphatic mercaptan, carbon tetrachloride, sodium formate, inorganic phosphate, octanol, isopropanol, propanol or butanol, adding at least two radical initiators of ammonium persulfate, sodium persulfate, potassium persulfate, sodium bisulfite, ammonium bisulfite, potassium bisulfite, hydrogen peroxide, ferrous chloride, cumene hydroperoxide or benzoyl peroxide, carrying out polymerization reaction at 45-85 ℃ for 4-9 hours, filtering with a sodium filtration/ultrafiltration membrane, or adding an organic solvent to precipitate a polymer, filtering and separating to obtain a solid serving as a scale inhibitor, fractionating a liquid part to obtain an organic solvent, and concentrating and incinerating the residual wastewater. However, polyacrylic acid obtained by the chemical treatment has low molecular weight, and wastewater is difficult to separate.
Further, an invention patent with application No. CN201510595251.3, filed No. 20150917, discloses a method for photocatalytic treatment of acrylic ester wastewater, which employs a high-pressure mercury lamp or a KrF ultraviolet excimer laser with a main wavelength of 254nm to irradiate the wastewater treated with persulfate or hydrogen peroxide, then adds a polyvalent metal ion compound as a precipitant to flocculate the acrylic acid polymer in the wastewater, and then filters out the precipitate, wherein the removal rate of acrylic acid in the wastewater is about 77% -88%. Although the treatment process is greatly simplified, the acrylic acid in the wastewater is not recycled.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a method for treating (methyl) acrylic acid wastewater, which has the advantages of low energy consumption, high efficiency and simple process, adopts photopolymerization to convert methacrylic acid, acrylic acid, methacrylate or acrylate in the (methyl) acrylic acid wastewater into a polymer in a gel form, and then dehydrates and dries the polymer to obtain the super absorbent resin which can be used as a super absorbent material required by moisture retention, water absorption and water prevention in the aspects of environmental protection, agriculture, forestry and the like.
The technical scheme adopted by the invention is as follows:
the method for treating (meth) acrylic acid wastewater of the present invention comprises the steps of:
A. adding a vinyl monomer and an initiator into (methyl) acrylic acid wastewater to obtain a solution;
B. irradiating the solution with light to initiate polymerization to obtain a gel polymer;
C. the polymer was separated off.
In the above method, the (meth) acrylic acid waste water in step a refers to fractional distillation waste water generated during the esterification reaction of acrylic acid or methacrylic acid, and a washing liquid generated by washing the esterification reaction product with caustic soda, soda ash or potassium hydroxide solution, wherein the washing liquid mainly contains one or more of methacrylic acid, acrylic acid, methacrylate or acrylate, and methacrylate or acrylate mainly refers to sodium salt or potassium salt thereof. The wastewater contains not only methacrylic acid, acrylic acid, methacrylate or acrylate but also a catalyst for esterification, a stabilizer, a raw material alcohol and a product (meth) acrylate, and is complicated in composition. Direct thermal polymerization, such as the disclosed process mentioned in the above section, produces little gel and is difficult to separate directly, and the product does not possess high water absorption properties and is not a useful superabsorbent material. The applicant finds that methacrylic acid, acrylic acid, methacrylate and acrylate in the wastewater can be conveniently and efficiently converted into gel products by adopting a photopolymerization method in one step, and the gel products are further dehydrated and dried to form super absorbent resin which can be used as a super absorbent material, and the water produced by dehydration and drying can be returned to production and use, so that the harmless and recycling treatment and use of the wastewater are realized.
Furthermore, the content of methacrylic acid, acrylic acid, methacrylate or acrylate in the (meth) acrylic acid wastewater is 1 w-20 w% of the mass of the aqueous solution, and the content of methacrylic acid, acrylic acid, methacrylate or acrylate varies greatly depending on the production process and the raw materials used for the esterification reaction. The addition of water soluble vinyl monomer can promote the photopolymerization of waste water, regulate and raise the water absorbing performance, and the gel polymer is easy to separate and has high water absorbing performance. Suitable vinyl monomers include monofunctional monomers such as acrylamide, acrylic acid and salts thereof, methacrylic acid and salts thereof, vinyl and substituted vinyl sulfonic acids and salts thereof; small amounts of polyfunctional vinyl monomers may also be added to control the degree of crosslinking of the resulting polymer, such as methylene bisacrylamide, ethylene glycol diallyl ether, diethylene glycol diallyl ether, butanediol diallyl ether, polyglycol diallyl ether, trimethylolpropane triallyl ether, ethoxylated trimethylolpropane triallyl ether and the like. The dosage of the monofunctional vinyl monomer can reach 0-30 w%, preferably 0-20 w% of the wastewater, and excessive addition of the monofunctional vinyl monomer causes the utilization value of methacrylic acid, acrylic acid, methacrylate and acrylate in the wastewater to be low; the amount of polyfunctional monomer used should not be too large, which would affect the water absorption properties of the product, and is preferably in the range of 0 to 5% w of the amount of waste water.
Further, the photoinitiator is a photoinitiator which generates free radicals after illumination, and comprises: aryl ketones, such as substituted and unsubstituted benzophenones, for example: 4-hydroxybenzophenone, 4- (2-hydroxyethyl) -oxybenzophenone, 4-hydroxyfluorenone, 4- (2-hydroxyethyl) -oxyfluorenone, biphenyl benzophenone, fluorenone, naphthyl phenyl ketone, camphorone, thioxanthone, and the like; substituted and unsubstituted benzoin ethers, 2-hydroxy-2-methyl-1-phenyl-propanone-1, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-dimethoxy-, 2-diphenylethan-1-one, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, and the like, and combinations thereof. The photoinitiator may be dissolved in the vinyl monomer or a small amount of solvent, such as ethanol, acetone, etc., and then added to the photopolymerization solution. Preferably a photoinitiator sensitive to the wavelength range of 280-410nm, and the dosage of the photoinitiator is 0.08-2 w percent of the mass of the wastewater.
Preferably, the waste water and the aqueous solution added with the vinyl monomer, particularly the acrylic acid or the methacrylic acid, can be neutralized by alkaline solution, so that the pH value of the waste water is 4-10, the acid neutralization degree of the waste water is more than 60 percent, the corrosivity of the waste water on equipment is reduced, and the water absorption rate and the water absorption speed of the obtained polymer as the super absorbent resin are adjusted and controlled.
Further, since the photopolymerization reaction is fast, the photopolymerization and the thermal polymerization can be combined and sequentially performed as the temperature of the system increases as the polymerization proceeds, thereby increasing the degree of the polymerization. In one embodiment, a photoinitiator and a thermal initiator are added simultaneously, the temperature of the system is automatically raised by using the polymerization heat of the photopolymerization reaction, and the thermal initiator is started to initiate the polymerization of the remaining monomers, so that the conversion rate of the methacrylic acid, the acrylic acid, the methacrylate and the acrylate in the system and the added vinyl monomer is increased. Water soluble thermal initiators may be used, including persulfates, such as ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and water soluble azo initiators, such as the agents azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline. For persulfate and hydrogen peroxide, reducing agents can be compounded to properly reduce the onset temperature of the initiator, and usable reducing agents include sulfite, ferrous chloride and the like, and the use method and the use amount of the reducing agents can be inquired by a person skilled in the art from related information.
Further, the light source used for initiating polymerization by light irradiation includes UV lamp and LED lamp, including polar and electrodeless mercury lamp, low-pressure fluorescent lamp, moth-killing lamp, germicidal lamp, plate-burning lamp, etc., preferably including UV lamp or LED lamp with emission wavelength of 280-. As a preferred embodiment, before the irradiation with light, an inert gas such as nitrogen, argon or the like may be introduced to remove oxygen, so that the oxygen content in the solution should be less than 100ppm, in particular less than 50ppm, and then the methacrylic acid, acrylic acid, methacrylate or acrylate or the like in the waste water is polymerized by the irradiation with light.
In summary, the advantages of the method for treating (meth) acrylic acid wastewater of the present invention are manifold:
1. the photopolymerization is used for decomposing the thermal initiator instead of heating to initiate polymerization, so that the efficiency is high, the operation is convenient, the heating step is omitted, the energy consumption is saved, the treatment cost of the waste water is reduced, and the energy-saving effect is very obvious when a large amount of (methyl) acrylic acid waste water is treated;
2. the photopolymerization speed is high, the photopolymerization is usually completed within tens of seconds to minutes, the efficiency is high, and the conversion rate of methacrylic acid, acrylic acid, methacrylate or acrylate in wastewater is high;
3. the photopolymerization treatment process for the wastewater is easy to control, and the product is gel and is convenient to separate;
4. the polymerization product obtained by photopolymerization has high water absorption property, the water absorption multiplying power is more than 30, the polymerization product can be used as a water retention and water absorption material, the resource utilization of waste water is realized, and the polymerization product can be used as a water retention agent for agricultural planting, soil improvement, road slope treatment, water prevention, leakage stoppage and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following examples used 3 wastewaters from chemical plants for the production of (meth) acrylic acid esters, wastewater 1 having a sodium acrylate content of about 14.3 w%, a COD value of 104000, a pH value of 10, wastewater 2 having an acrylic acid content of about 1.2 w%, a COD value of about 9000 and a pH value of less than 2; the content of sodium methacrylate in the wastewater 3 is about 16w percent, the COD value is about 110000, and the pH value is 9; the dosage of the wastewater 1, the wastewater 2 and the wastewater 3 is 100 g.
Example 1
This example uses waste water 1, a 250ml three necked flask equipped with an electric stirrer, thermometer and nitrogen inlet and outlet tube was placed in a water bath, waste water 1 and 0.1 g of photoinitiator 2959(1 w%) were added, stirred, bubbled with nitrogen for 15 minutes, and the contents of the flask were converted to a white gelatinous solid by irradiation with an LED lamp 15cm from the glass flask for one minute. The gel was taken out and dried in an oven at 120 ℃ to obtain 16 g of a hard block having a water content of about 10 w%. The resulting mixture was ground into fine powder by an electric grinder, and the water absorption to pure water was 36 times as measured by a standard method.
Example 2
In this example, wastewater 1 was used, 10 w% of AA, 0.08 w% of photoinitiator 819 and 0.2 w% of hydroxybenzophenone were added, the pH was adjusted to about 8 with alkaline water, the LED was illuminated for 120 seconds, and the rest of the procedure was the same as in example 1, and solids having a water content of about 10 w% were obtained in an amount of about 32 g and a water absorption of 112 times.
Example 3
This example uses waste water 1, 20 w% AA, sodium methallylsulfonate 2 w%, 2959 adjusted to a pH of about 4 with KOH 0.1 w% and azobisisobutylamidine hydrochloride 0.3 w%. The LED was illuminated for 60 seconds and then placed in a water bath at 80 ℃ for 4 hours. After drying treatment similar to example 1, 47 g of solids having a water content of about 10 w% and a water absorption of 500 times were obtained.
Example 4
In this example, wastewater 2 was used, AA20 w% and ethylene glycol diallyl ether 5% were added, 0.26 g of thioglycolic acid (-1 w% of monomer amount) was adjusted to pH 10 with alkaline water, 0.1 w% of photoinitiator 819 and 2 w% of hydroxybenzophenone were used, a medium pressure mercury lamp was irradiated for 180 seconds to obtain a gel-like product, 60ml of acetone was added and stirred, after squeezing out water, drying was carried out to obtain 40 g of solid with water content of about 10 w%, and the water absorption was 67 times.
Example 5
In this example, wastewater 2, AAw 10%, 0.2 w% methylenebisacrylamide and 0.4 w% 2959 were used, the pH was adjusted to about 3 with aqueous alkali, and a gel-like product was obtained by irradiation with a medium-pressure mercury lamp for 180 seconds, and after drying treatment similar to that of example 1, 17 g of a solid having a water content of about 10 w% was obtained, and the water absorption was 55 times.
Example 6
In this example, wastewater 3, 10 w% of AA, 0.1 w% of 2959, adjusted to pH 8 with alkaline water, LED illuminated for 120 seconds, and the rest of example 1 was dried to obtain about 36 g of solid with water content of about 10 w% and water absorption of 58 times.
Example 7
This example is a comparative example, which uses a simple thermal polymerization, a 250ml three-necked flask equipped with an electric stirrer, a thermometer and a nitrogen inlet pipe is placed in a water bath, 100 g of wastewater 1 and 0.1 g of a thermal initiator potassium persulfate are added, stirred and bubbled with nitrogen for 15 minutes, after a reaction at 80 ℃ for 3 hours and 88 ℃ for 3 hours in the water bath, the material in the flask is still a transparent aqueous solution sample, the solution is poured into 200ml of ethanol, the precipitated gel is separated out, 8 g of solid is obtained after drying, the solid is ground into fine powder by an electric pulverizer, the water absorption of the fine powder is about 1.5 times that of pure water according to a standard method, most of the powder is dissolved in water, and the remaining part weighs about 2 g after drying.
The vinyl monomers used in the above examples, Acrylic Acid (AA), sodium methallylsulfonate, methylenebisacrylamide, ethylene glycol diallyl ether, NaOH or KOH, the photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (2959), 4-hydroxybenzophenone, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (819), the water-soluble thermal initiator azo initiator azobisisobutylamidine hydrochloride (AIBA), potassium persulfate, thioglycolic acid, isopropanol, and the like, are commercially available; and the photopolymerisable lamp source is a medium-pressure mercury lamp with 1000W or an LED lamp with 9W total power and comprising 6 lamp beads with 365nm wavelength and 4 lamp beads with 395nm wavelength. The purity of the nitrogen is 99.995%, and the water absorption rate of the resin is determined by referring to the method of GB/T22905-2008 paper diaper super absorbent resin.
In a preferred embodiment, a chain transfer agent for radical polymerization is added to the wastewater containing multifunctional acrylate to control the degree of crosslinking and the molecular chain morphology of the polymer. Useful chain transfer agents include thiol compounds such as 2-mercaptoethanol, 3-mercaptopropanediol, 2-mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoimidazole, and carbon tetrabromide, hexabromoethane, isopropanol, and combinations thereof. The amount of the chain transfer agent may be 0 to 20% by weight, depending on the chain transfer agent used. For example, the amounts of mercaptans and isopropanol used as chain transfer agents vary greatly and one skilled in the art can find suitable amounts of chain transfer agents by correlation and comparative testing. The procedure of example 4 was followed using mercaptopropionic acid as chain transfer agent in an amount of 1 w% based on the mass of acrylic acid and its salts and monomers added to the wastewater in the system.
Super absorbent resins are a class of functional materials that can absorb tens to thousands of times their own weight, typical examples being high molecular weight polyacrylamides and polyacrylates. The water absorption rate of the polyacrylate super absorbent resin is influenced by the acid neutralization degree, the crosslinking degree, the ion concentration of absorbed water and the like of the resin, different application purposes have different requirements on the water absorption rate of the super absorbent resin, and the super absorbent resin has the water absorption rate at least higher than 30 times when being used as a water-retaining agent for agriculture, forestry and the like.
In the above examples 1 to 6, after the wastewater containing (meth) acrylic acid and its derivatives or salts is subjected to light treatment, the polymerization effect of acrylic acid, methacrylic acid, acrylate and methacrylate in the wastewater is good, almost no residue is left in the wastewater, and the water absorption rate of the super absorbent resin prepared from the wastewater is more than 30 times, and the water absorption rate of example 3 is more than 500 times, so that the water-retaining agent can be used for water retention for agricultural planting, soil improvement, road slope treatment, water prevention and leakage stoppage and the like. In comparative example 7, the remaining part of 8 g of the powder dissolved in water was dried again and weighed about 2 g, indicating that acrylic acid and acrylic acid salt remained in the wastewater more, the polymerization effect was poor, and the water absorption ratio was less than 10 times, which is not suitable as a water-retaining agent for the above-mentioned applications.
The above examples illustrate the principles and embodiments of the present invention, and the description of the above examples is only for the purpose of helping understanding the method for treating acrylic acid wastewater of the present invention and the core concept thereof. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (8)

1. A method for treating (meth) acrylic acid waste water, characterized by comprising the steps of:
A. adding a vinyl monomer and an initiator into (methyl) acrylic acid wastewater to obtain a solution;
B. irradiating the solution with light to initiate polymerization to obtain a gel polymer;
C. the polymer was separated off.
2. The method of treating (meth) acrylic acid waste water according to claim 1, wherein the (meth) acrylic acid waste water of step A contains one or more of methacrylic acid, acrylic acid, a methacrylate salt or an acrylate salt.
3. The method for treating (meth) acrylic acid waste water according to claim 1, wherein the initiator in the step A comprises a radical type photoinitiator.
4. The method for treating (meth) acrylic acid waste water according to claim 1, wherein the vinyl monomer in the step A comprises monofunctional acrylic acid, acrylamide, vinyl sulfonate, and polyfunctional vinyl monomer.
5. The method for treating (meth) acrylic acid waste water according to claim 4, wherein the amount of the monofunctional vinyl monomer added is 0 to 30 w% based on the amount of the waste water; the addition amount of the multifunctional vinyl monomer is 0-5 w% of the amount of the wastewater.
6. The method for treating (meth) acrylic acid waste water according to claim 2, wherein the content of methacrylic acid, acrylic acid, methacrylate or acrylate in the acrylic acid waste water is 1 w% to 20 w% based on the mass of the aqueous solution.
7. The method for treating (meth) acrylic acid waste water according to claim 1 or 3, wherein the photoinitiator is sensitive to light in a wavelength range of 280nm to 410nm, and the amount of the photoinitiator is 0.08 w% to 2 w% based on the mass of the solution.
8. The method for treating (meth) acrylic acid waste water according to claim 1, wherein the light source for light irradiation to initiate polymerization in the step B comprises a UV lamp or an LED lamp, and the light source emits light having a wavelength of 280nm to 415 nm.
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CN112535086A (en) * 2020-12-28 2021-03-23 江苏利田科技股份有限公司 Plant cultivation substrate and preparation method thereof

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