JP5223338B2 - Wastewater treatment method - Google Patents

Description

  The present invention relates to a method for treating wastewater by adding a sulfiding agent to wastewater containing at least a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion, and removing the polyvalent metal ion as a sulfide. And an acrylic ester or methacrylic ester production method incorporating this wastewater treatment method.

  In general, an ester of acrylic acid or methacrylic acid (hereinafter abbreviated as (meth) acrylic acid) is an alcohol and (meth) in the presence of a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, etc. Manufactured by condensing with acrylic acid. This reaction proceeds while removing by-product condensed water out of the system. After completion of the reaction, the reaction product solution is washed with alkaline water, salt water, distilled water or the like for the purpose of removing the remaining catalyst and (meth) acrylic acid.

  Washing wastewater generated by washing the reaction product liquid contains a large amount of water-soluble organic compounds and has a high chemical oxygen demand (COD). Therefore, after performing the oxidative decomposition process which burns the water-soluble organic compound contained in the washing wastewater, the treated water is discharged into the river.

  During the condensation reaction between (meth) acrylic acid and alcohol, a metal compound may be added to the reaction solution as a polymerization inhibitor for the purpose of preventing polymerization of (meth) acrylic acid. When using the polymerization inhibitor consisting of a metal compound, the metal ion is dissolved in the washing waste water. In this case, it cannot be treated by wastewater treatment by combustion / discharge. Many metal compounds added as a polymerization inhibitor are copper compounds, specifically, cupric chloride and copper sulfate.

  Environmental standards based on the Water Pollution Control Law have been established for copper compounds and the like, and it is difficult to reduce the metal concentration of wastewater discharged after combustion below the legal standard by combustion treatment alone.

  As a conventional technique for removing metal from wastewater containing a metal compound, for example, there is a technique for treating etching wastewater. Patent Document 1 discloses a method of recovering an approximate oxide after converting copper ions contained in etching wastewater into an oxide using an oxidizing agent. Patent Document 2 discloses a method for treating an etching waste liquid that uses sodium sulfide to recover copper sulfide.

However, these documents do not describe that a water-soluble organic compound is contained in the etching waste liquid. It is difficult to apply the treatment methods described in these documents to washing wastewater such as a (meth) acrylic ester production reaction solution. These washing wastewaters contain polymerizable organic acids and / or polymers thereof. As a result, metal oxides and sulfides are present in a stably dispersed state in the washing waste water, and it is difficult to precipitate them and separate them from the washing waste water.
JP 2003-213346 A (Claim 1) JP-A-6-16421 (Claim 1)

  In wastewater containing a large amount of water-soluble polymerizable organic acid and the like, solid particles of oxides and sulfides of polyvalent metal ions are present in a stable dispersion state. Therefore, in this wastewater treatment, it is difficult to remove the polyvalent metal ions from the wastewater.

  An object of the present invention is to provide a wastewater treatment method for efficiently removing a polyvalent metal ion from a wastewater containing at least a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion, and the treatment of this wastewater. It is in providing the manufacturing method of the (meth) acrylic acid ester incorporating the method.

  The present inventors diligently aiming at the recovery of polyvalent metals from wastewater containing at least a water-soluble polymerizable organic acid and polyvalent metal ions, and the development of a combustion treatment method for wastewater after recovering the polyvalent metals. investigated. As a result, it has been found that when a polysulfide is insolubilized as a sulfide by adding a sulfiding agent to the wastewater, the polyvalent metal can be easily separated from the wastewater containing a water-soluble polymerizable organic acid or the like. Furthermore, it has been found that sludge containing a high concentration of polyvalent metal sulfide can be separated from the waste water by adding a flocculant or a filter aid to the waste water to which the sulfurizing agent is added. It has also been found that since the concentration of polyvalent metal ions in the wastewater from which sludge has been separated by this method is low, the wastewater can be discharged after combustion treatment. The present invention has been completed based on the above findings.

  The present invention for solving the above problems is described below.

  [1] A method of treating waste water containing a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion, after adding an alkali metal sulfide and / or hydrosulfide to the waste water A method for treating wastewater, wherein the produced sulfide of the polyvalent metal is separated.

  [2] The wastewater treatment method according to [1], wherein the alkali metal sulfide and / or hydrosulfide is sodium sulfide and / or sodium hydrosulfide.

  [3] The method for treating wastewater according to [1], wherein the water-soluble polymerizable organic acid is acrylic acid or methacrylic acid.

  [4] The wastewater treatment method according to [1], wherein the polyvalent metal ion is a copper ion.

  [5] The method for treating wastewater according to [4], wherein the addition amount of the alkali metal sulfide and / or hydrosulfide is equimolar or more with respect to copper ions.

  [6] The wastewater treatment method according to [1], wherein an alkali metal sulfide and / or hydrosulfide is added so that the oxidation-reduction potential of the wastewater is 0 mV or less.

  [7] The wastewater treatment method according to [1], wherein the wastewater is adjusted to pH 7 to 13.

  [8] A method for treating waste water containing a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion, wherein an alkali metal sulfide and / or hydrosulfide is added to the waste water. After the polyvalent metal ion is converted to sulfide, a flocculant or a filter aid is added to form a sludge containing the polyvalent metal sulfide, and then the sludge is dewatered by a solid-liquid separator to be used as wastewater. Wastewater treatment method for separating the polyvalent metal sulfide from the waste water.

  [9] The wastewater treatment method according to [8], wherein the flocculant is a nonionic and / or anionic organic flocculant.

  [10] A step of reacting acrylic acid or methacrylic acid with an alcohol in a solvent in the presence of a strongly acidic catalyst and a polymerization inhibitor copper ion to obtain a reaction product liquid containing an acrylic ester or methacrylic ester, and the reaction An acrylic ester or methacrylic acid having a step of washing the produced solution with washing water, separating the organic liquid containing an acrylic ester or methacrylic ester into a washing waste water containing copper ions, and a treatment step of the washing waste water In the method for producing an ester, the washing wastewater treatment step adds an alkali metal sulfide and / or hydrosulfide to the washing wastewater to form copper sulfide, and then adds a flocculant, A method for producing an acrylic ester or methacrylic ester, which is a step of coagulating and separating sludge containing slag.

  [11] A step of reacting acrylic acid or methacrylic acid with an alcohol in a solvent in the presence of a strong acidic catalyst and a copper ion as a polymerization inhibitor to obtain a reaction product liquid containing an acrylic ester or methacrylic ester, and the reaction An acrylic ester or methacrylic acid having a step of washing the produced solution with washing water, separating the organic liquid containing an acrylic ester or methacrylic ester into a washing waste water containing copper ions, and a treatment step of the washing waste water In the method for producing an ester, the washing wastewater treatment step includes adding an alkali metal sulfide and / or hydrosulfide to the washing wastewater to form copper sulfide, and then adding a filter aid, A method for producing an acrylic ester or methacrylic ester, which is a step of coprecipitation separation of sludge containing copper.

  [12] The method for producing an acrylic ester or methacrylic ester according to [10] or [11], wherein the treated waste water obtained by separating the sludge containing copper sulfide from the washed waste water is combusted.

  According to the method of the present invention, by adding a sulfiding agent to a wastewater containing a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion, the polyvalent metal ion can be easily converted into a sulfide from the wastewater. Can be removed. In the above method, when a sulfiding agent and a flocculant or a filter aid are used in combination, the polyvalent metal sulfide dispersed in the wastewater can be agglomerated and separated as sludge. In addition, polyvalent metal ions can be removed.

  According to the present invention, polyvalent metal ions contained in waste water can be recovered as sulfides and can be reused.

FIG. 1 is a process diagram showing a method for producing a (meth) acrylic acid ester of the present invention.

Explanation of symbols

2 Reaction process 4 Neutralization / washing process 6 Purification process 10 Wastewater tank 12 Sulfurization process 14 Solid-liquid separation process 16 Wastewater combustion process

  The present invention is a method for treating wastewater containing a water-soluble polymerizable organic acid and / or a polymer thereof and a polyvalent metal ion.

  The present invention can be applied to a waste liquid containing water-soluble polymerizable organic acid and / or a polymer thereof in various amounts. When the polymerizable organic acid is (meth) acrylic acid, it can be preferably applied to the total organic carbon in terms of sodium (meth) acrylate (hereinafter referred to as TOC) containing 1 to 15% by mass in the waste water.

  As the polymerizable organic acid, (meth) acrylic acid, oxalic acid, itaconic acid, maleic acid, crotonic acid, cinnamic acid, 2-phenylacrylic acid, fumaric acid, mesaconic acid, citraconic acid, aconitic acid, glutaconic acid, etc. And polybasic acid-modified products of these polymerizable organic acids. Among these, the present invention is a method that can be preferably applied to wastewater containing (meth) acrylic acid.

  Examples of the polyvalent metal ions include copper ions, iron ions, cadmium ions, lead ions, mercury ions, and zinc ions. Among these, the present invention is a method that can be preferably applied to wastewater containing copper ions.

  In the present invention, an alkali metal sulfide and / or hydrosulfide is used as the sulfiding agent. As an alkali metal, sodium and potassium are preferable. Specific examples of the compound include sodium sulfide, sodium hydrosulfide, and potassium sulfide. These can be used alone or in combination of two or more.

  The addition amount of the sulfiding agent is preferably equimolar or more, and more preferably 1.0 to 2.0 times the molar amount of the metal ions contained in the waste water, as the total amount of each sulfiding agent. The sulfiding agent added to the waste water can be either an aqueous solution or a solid.

  When the concentration of metal contained in the wastewater is unknown, it is desirable to manage the addition amount of the sulfiding agent based on the oxidation-reduction potential. In that case, in order to completely convert the polyvalent metal ions into sulfide, it is preferable to add an alkali metal sulfide and / or hydrosulfide until the oxidation-reduction potential of the wastewater becomes 0 mV or less.

  In order to prevent the generation of hydrogen sulfide, the pH of the wastewater is preferably adjusted in advance from 7 to 13 and more preferably from 8 to 12 before the addition of the sulfurizing agent.

  After adding a sulfiding agent to the waste water, the sulfides of polyvalent metal ions can be separated from the waste water using known means such as filtration and centrifugation.

  In waste water containing a water-soluble polymerizable organic acid and / or polymer thereof, metal sulfide particles are more stably dispersed in a colloidal state than in waste water not containing them. In such wastewater, it may be difficult to precipitate the metal sulfide and separate it from the wastewater. In this case, a metal sulfide floc can be formed by using a flocculant. Alternatively, the metal sulfide particles can be coprecipitated with the filter aid by using a filter aid and then separated from the waste water as sludge.

  Examples of the flocculant include inorganic flocculants such as aluminum sulfate, polyaluminum chloride, ferric chloride, and polyiron chloride; sodium poly (meth) acrylate and (meth) acrylic acid and (meth) acrylamide copolymer Anionic organic flocculants such as polyacrylamide; and nonionic organic flocculants such as polyacrylamide. The nonionic organic flocculant may be a copolymer of (meth) acrylamide with a small amount (5 mol% or less) of (meth) acrylic acid.

  Among these, it is preferable to use an anionic or nonionic organic flocculant from the viewpoint of excellent cohesiveness. In addition, the cationic organic flocculant is inferior in the flocculence compared with the anionic or nonionic organic flocculant.

  The amount of the organic flocculant added is preferably 1 to 100 mg / L, and more preferably 2 to 30 mg / L.

  The molecular weight of the organic flocculant is preferably 500,000 to 30 million, more preferably 1 million to 20 million.

  Commercially available products can also be used for the flocculant, such as Aron Flock A-101, A-104, A-106 (manufactured by Toagosei Co., Ltd.), Diafloc AP350M, AP825B, AP825C, Anionic organic flocculants such as AP784, AP805C, AP410C, AP771C (above, manufactured by Daianitrix); Aron Flock N-101, N-107, N-207 (above, manufactured by Toagosei Co., Ltd.) Nonionic organic flocculants such as Diafloc NP800 (manufactured by Daianitrix) can be used.

  Examples of the filter aid include diatomaceous earth filter aids such as Radiolite (manufactured by Showa Chemical Co., Ltd.) and Celite (manufactured by Jhons-Manille); be able to.

  The effect of reducing the copper concentration in the filtrate is higher when an anionic or nonionic organic flocculant is used than when a filter aid is used. Therefore, it is preferable to use an anionic or nonionic organic flocculant for the treatment of waste water containing a water-soluble polymerizable organic acid or a polymer thereof and a polyvalent metal ion.

  The concentration of the water-soluble polymerizable organic acid or the polymer thereof in the wastewater in which the metal sulfide particles are stably dispersed is about 0.5 to 200 g / L.

  Hereinafter, an example of a method for producing a (meth) acrylic acid ester incorporating the wastewater treatment method of the present invention will be described with reference to the process diagram of FIG.

  In FIG. 1, in the reaction step 2, a condensation reaction between (meth) acrylic acid and raw material alcohol is performed. It is preferable that the reactor which reacts (meth) acrylic acid and alcohol is equipped with a heater and a stirrer.

  In the reactor, raw material (meth) acrylic acid, raw material alcohol, catalyst, reaction solvent (toluene), polymerization inhibitor, hypophosphorous acid and / or sodium hypophosphite, activated carbon and the like are stored in advance. Examples of the catalyst include p-toluenesulfonic acid and sulfuric acid, and examples of the polymerization inhibitor include cupric chloride or copper sulfate. The reaction liquid containing these components is heated by a heater while being stirred by a stirrer.

  Raw material alcohol is, for example, methanol, ethanol, propanol, butanol, octanol, 2-ethylhexanol, alkyl ether of alkylene glycol, alkylene oxide modified phenol, alkylene oxide modified nonylphenol, alkylene oxide modified p-cumylphenol, alkylene oxide modified 2 Monohydric alcohols such as ethylhexanol; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, tris- (2-hydroxyethyl) isocyanurate, tricyclodecane Methylol, alkylene glycol, neopentyl glycol, tricyclo Candimethylol, glycerin, diglycerin, alkylene oxide modified bisphenol S, alkylene oxide modified bisphenol F, alkylene oxide modified bisphenol A, alkylene oxide modified glycerin, alkylene oxide modified diglycerin, alkylene oxide modified trimethylolpropane, alkylene oxide modified ditrimethylolpropane And polyhydric alcohols such as alkylene oxide modified pentaerythritol, alkylene oxide modified dipentaerythritol, alkylene oxide modified neopentyl glycol, and polyester. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  (Meth) acrylic acid and alcohol are dehydrated and condensed by being heated in the presence of a catalyst in the reactor to produce (meth) acrylic acid ester. Water by-produced by the condensation reaction of (meth) acrylic acid and alcohol is azeotroped with the solvent toluene, discharged from the upper part of the reactor, and sent to the rectification column. Then, it rises while being rectified in the rectification tower, and is distilled from the top of the rectification tower.

  Azeotropic gas (water and toluene) distilled from the top of the rectification column is sent to a condenser and condensed in the condenser. The condensed mixture of water and toluene is sent from the condenser to the separator. Since water and toluene are hardly soluble to each other, they are separated into two layers in the separator.

  The upper toluene separated in the separator is returned to the top of the rectifying column and refluxed in the rectifying column. The lower layer water separated in the separator is taken out from the bottom of the separator and sent to the waste water tank 10.

  After completion of the reaction, the reaction product liquid containing (meth) acrylic acid ester in the reactor is sent to the neutralization / washing step 4.

  In the neutralization / washing step 4, alkaline water is added to the reaction product solution in the neutralization tank and stirred. By this operation, (meth) acrylic acid, catalyst, etc. contained in the reaction product liquid are neutralized, and the dimerized (meth) acrylic acid is decomposed. Thereafter, the solution in the neutralization tank is allowed to stand. By this standing operation, the solution in the neutralization tank is divided into an organic layer containing toluene and (meth) acrylic acid ester, and an alkaline water layer containing sodium (meth) acrylate, raw material alcohol, copper ions, catalyst salt, and the like. To be separated. Thereafter, the alkaline water layer is discharged from the lower end of the neutralization tank and stored in the waste water tank 10 as washing waste water.

  The washing waste water stored in the waste water tank 10 is sent to the sulfidation treatment step 12 together with the lower layer water separated by the separator in the reaction step described above. In the sulfidation treatment step, sodium sulfide and / or sodium hydrosulfide is added to the washing waste water and the lower layer water and stirred. By this operation, copper ions contained in the washing wastewater are converted into sulfides.

  Thereafter, if desired, a flocculant or a filter aid is added and stirred, and then sludge containing copper sulfide fine particles is precipitated.

  In the solid-liquid separation step 14, the precipitated sludge is sent to a solid-liquid separator and dehydrated.

  The supernatant liquid of sludge containing organic compounds such as sodium (meth) acrylate and raw material alcohol and the discharged liquid discharged from the solid-liquid separator 16 are sent to the waste water combustion process 16. As for the effluent, an organic compound contained in the effluent is burned in a wastewater combustion furnace and subjected to oxidative decomposition treatment.

  On the other hand, the organic layer separated from the alkaline water layer in the neutralization / washing step 4 is sent to the purification step 6. In the refinement | purification process 6, the solvent removal process and filtration of an organic layer are performed and (meth) acrylic acid ester is obtained.

  In the above description, the case where toluene is used as an azeotropic solvent of by-product water is shown, but the solvent which is insoluble or hardly soluble in water and forms an azeotropic mixture with water is used instead of toluene. It is also possible to do. Examples of such a solvent include benzene, xylene, cyclohexane, n-hexane, n-heptane, trichloroethane, tetrachloroethylene, methyl chloroform, diisopropyl ether and the like.

  Examples of the solid-liquid separator used for sludge dehydration include a vacuum filter, a filter press, a belt press, a screw press, and a centrifugal dehydrator. Because of its high dewatering rate and easy maintenance, filter presses and belt presses are most suitable for dewatering sludge containing metal sulfides.

  In the above description, the case where alkaline water is used for washing the reaction product liquid has been described as an example, but distilled water, NaCl solution, or the like can be used for washing the reaction product liquid. In the case of treating wastewater generated by washing using these, it can be treated in the same manner as alkaline water.

  Examples of the (meth) acrylic acid ester that can be produced using the wastewater treatment method of the present invention include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, penta Erythritol hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol Propane / tri (meth) acrylate, trimethylolpropane / tetra (meth) acrylate, ditrimethylolpropane / tri (meth) acrylate, ditrimethylolpropane / Tora (meth) acrylate, alkylene oxide modified trimethylolpropane / tri (meth) acrylate, alkylene oxide modified bisphenol A / di (meth) acrylate, alkylene oxide modified nonylphenol mono (meth) acrylate, alkylene oxide modified p-cumylphenol -Mono (meth) acrylate, polyester (meth) acrylate, etc. can be mentioned. Each waste water generated during the production of these (meth) acrylic acid esters can be subjected to a sulfidation process, a solid-liquid separation process, and a waste water combustion process alone or in combination.

  The acrylic acid ester described in Examples 1 to 4 and Comparative Examples 1 and 2 was produced, and the resulting reaction product liquid was washed to obtain each washing wastewater (pH 8 to 10) having the following composition. About each washing | cleaning wastewater, the wastewater treatment described in Examples 1-4 and Comparative Examples 1 and 2 was performed.

[Composition of washing wastewater]
TOC (in terms of sodium acrylate) 5-7% by mass
Copper chloride 0.1-0.4% by mass
Sodium sulfate 8-14% by mass
Sodium hydroxide 0.5-1.0% by mass
The used flocculant A or B is a prototype, the details of which are as follows.
(Flocculant A) Anionic flocculant composed of acrylamide / sodium acrylate copolymer, sodium acrylate 27 mass%, average molecular weight of about 13 million, white powder, bulk specific gravity 0.65 g / cc
(Flocculant B) Nonionic flocculant made of acrylamide / sodium acrylate copolymer, sodium acrylate 3% by mass, average molecular weight about 11 million, white powder, bulk specific gravity 0.65 g / cc
Example 1
After performing dehydration condensation reaction (esterification reaction) by the method described in 1) and 2) below, the reaction product solution was neutralized and washed with water.
1) 29 parts by mass of pentaerythritol (hereinafter abbreviated as “parts”), 73 parts of acrylic acid, 2 parts of sulfuric acid as a catalyst, 0.4 parts of copper chloride as a polymerization inhibitor, and 70 parts of toluene as an organic solvent The total reaction solution was 15 t. The reaction solution was heated to conduct esterification reaction to obtain a mixture of pentaerythritol tri, tetra, penta and hexaacrylate.
2) 36 parts of dipentaerythritol, 73 parts of acrylic acid, 3 parts of sulfuric acid as a catalyst, 0.8 part of copper chloride as a polymerization inhibitor, 60 parts of toluene as an organic solvent, and the whole reaction liquid was made 15 t. . The reaction solution was heated for esterification reaction to obtain a mixture of dipentaerythritol tri, tetra, penta and hexaacrylate.

  The resulting reaction product liquid containing various acrylate mixtures was washed with washing water to obtain each washing wastewater. Washing water used was a 100 g / L sodium hydroxide aqueous solution and tap water.

  As washing waste water after neutralization and washing with water, 20% by weight of washing waste water obtained by the reaction of 1) and 80% by weight of washing waste water obtained by the reaction of 2) were used.

  1 L (Cu; 5 mmol to 25 mmol) of the obtained washing waste water * The amount of copper chloride used in each reaction has a range, and the value varies depending on the timing of draining the waste liquid. Was adjusted to pH 12 with a 20% by mass aqueous sodium hydroxide solution. Next, about 30 ml (25 mmol) of a 4.5 mass% sodium hydrosulfide solution was added to make the oxidation-reduction potential of the wastewater 0 mV. Furthermore, the aqueous solution of the flocculant A was added to the wastewater as a solid content so as to be 30 mg / L, mixed, and allowed to stand. The SV30 (solid content volume after standing for 30 minutes) at this time was 20%.

  Thereafter, the waste water was suction filtered using a filter paper (5C) to separate the solid content. The filterability was good, and SS (suspended substance) of copper sulfide was not confirmed in the filtrate, and the copper concentration in the filtrate was 1 mg / L.

  In addition, when a pilot test (cleaning wastewater 200 L) was performed under these conditions, good results were obtained for both the filter press and the belt press. A good copper sulfide sludge having a copper concentration of 0.5 mg / L and a water content of 50% was obtained.

Example 2
After the esterification reaction was carried out by the following methods 1) and 2), the reaction solution was neutralized and washed with water.
1) 32 parts of trimethylolpropane, 73 parts of acrylic acid, 2 parts of p-toluenesulfonic acid as a catalyst, 0.1 part of copper chloride as a polymerization inhibitor, 100 parts of toluene as an organic solvent, A total amount of 15 t was used. The reaction solution was heated to conduct esterification reaction to obtain trimethylolpropane triacrylate.
2) 63 parts of ditrimethylolpropane, 80 parts of acrylic acid, 5 parts of p-toluenesulfonic acid as a catalyst, 0.2 part of copper chloride as a polymerization inhibitor, 80 parts of toluene as an organic solvent, The total was 15 t. The reaction solution was heated to carry out an esterification reaction to obtain a mixture of ditrimethylolpropane tri and tetraacrylate.

  The obtained reaction product liquid containing various acrylate mixtures was washed with washing water to obtain washing waste water. Washing water used was a 100 g / L sodium hydroxide aqueous solution and tap water.

  As washing waste water after neutralization and washing with water, a mixture of 40% by weight of washing waste water obtained by the reaction of 1) and 60% by weight of washing waste water obtained by the reaction of 2) was used.

  About the obtained washing wastewater, wastewater treatment was performed in the same manner as in Example 1 except that the flocculant B was used. The wastewater SV30 was 17%.

  Thereafter, the wastewater was suction filtered using a filter paper (5C), and solid-liquid separation was performed. Filterability was good, and SS of copper sulfide was not confirmed in the filtrate. The copper concentration in the filtrate was 2 mg / L.

Example 3
120 parts of alkylene oxide-modified trimethylolpropane, 100 parts of acrylic acid, 6 parts of p-toluenesulfonic acid as a catalyst, 0.2 part of copper chloride as a polymerization inhibitor, 200 parts of toluene as an organic solvent, and reaction solution Was used in a total amount of 15 t. The reaction solution was heated to conduct esterification reaction to produce alkylene oxide-modified trimethylolpropane triacrylate, and then the reaction solution was neutralized and washed with water to obtain washing waste water. Washing water used was 50 g / L sodium hydroxide aqueous solution and tap water.

  As washing waste water after neutralization and washing with water, 100% by mass of washing waste water from which the above reaction was obtained was used.

  About 25 ml of an 8.3 mass% sodium sulfide solution was added to 1 L of waste water to the obtained washing waste water, and the oxidation-reduction potential of the waste water was set to -30 mV.

  The flocculant A was added as solid content to 30 mg / L with respect to the wastewater, and the mixture was allowed to stand. SV30 was 20%.

  Thereafter, the waste water was suction filtered using a filter paper (5C) to separate the solid content. Filterability was good, and SS of copper sulfide was not confirmed in the filtrate. The copper concentration in the filtrate was 2 mg / L.

Example 4
1 L (Cu; 5 mmol to 25 mmol) of the same washing wastewater as in Example 1 was adjusted to pH 12 with a 20 mass% sodium hydroxide solution. Next, about 30 ml (25 mmol) of a 4.5 mass% sodium hydrosulfide solution was added to make the oxidation-reduction potential of the wastewater 0 mV.

  When the SV30 of the wastewater containing copper sulfide was measured, it was 70%, and a large amount of SS was also suspended in the supernatant.

  When solid-liquid separation of waste water was carried out using filter paper (5C), the filterability was good although it was not the level of Examples 1-3. A large amount of SS remained in the filtrate. The copper concentration of the filtrate was 320 mg / L.

  A filter aid (Radiolite # 200, manufactured by Showa Chemical Co., Ltd.) was added to the waste water containing copper sulfide after sulfidation treatment in an amount of 0.1%, and after stirring, the filter aid was separated by filtration. No SS was confirmed, and the copper concentration in the filtrate was 7 mg / L.

Comparative Example 1
The washing waste water obtained in the same manner as in Example 1 was adjusted to pH 7 with sulfuric acid, and then about 80 ml of an 8% by mass sodium hydrogen carbonate solution was added to 1 L of the waste water. Then, in order to accelerate | stimulate the production | generation of copper hydroxide, it heated to 70 degreeC and left to stand for 1 hour.

  The solution after the treatment was a solution containing a large amount of blue-green copper hydroxide SS.

  Subsequently, the flocculant A was added to this liquid so that it might become 30 mg / L with respect to wastewater by solid content, and it left still after stirring. In this case, SV30 was 100%, and sedimentation properties could not be confirmed.

  Thereafter, the washing wastewater to which the flocculant was added was suction filtered with a filter paper 5C to attempt solid-liquid separation. However, the filterability was poor, and the obtained filtrate was confirmed to have a greenish SS. The copper concentration in the filtrate was measured and found to be 420 mg / L.

  As the polymer flocculants, cationic polymer flocculants Aron Flock C-512L (manufactured by Toagosei Co., Ltd., average molecular weight of about 3.5 million) and Aron Flock C-525L (manufactured by Toagosei Co., Ltd., average molecular weight of about 5 million) are used. Although the same operation was performed using each, the same result as in the case of the flocculant A was obtained, and it was difficult to reduce the copper concentration in the filtrate.

Comparative Example 2
To 1 L of washing wastewater obtained in the same manner as in Example 1, 50 ml of a 12% by mass sodium hypochlorite aqueous solution was added as an oxidizing agent to convert copper ions to copper oxide. The viscosity of the wastewater increased due to the addition of the oxidizing agent. Even when the flocculant A was added, the copper oxide did not aggregate, resulting in a viscous solution.

  In the SV30 measurement, no sedimentation property was confirmed. Suction filtration was performed using filter paper (5C), but solid-liquid separation could not be performed.

Claims (10)

A step of reacting acrylic acid or methacrylic acid and alcohol in a solvent in the presence of a strong acidic catalyst and a polymerization inhibitor copper ion to obtain a reaction product solution containing an acrylic ester or a methacrylate ester, and the reaction product solution Washing with washing water, separating the organic layer containing acrylic acid ester or methacrylic acid ester and washing waste water containing acrylic acid or methacrylic acid and / or a polymer thereof and copper ions; A method for producing an acrylic ester or a methacrylic ester having, after the cleaning wastewater treatment step generates copper sulfide by adding an alkali metal sulfide and / or hydrosulfide to the cleaning wastewater. Addition of a flocculant and coagulation and separation of sludge containing copper sulfide Production method. A step of reacting acrylic acid or methacrylic acid and alcohol in a solvent in the presence of a strong acidic catalyst and a polymerization inhibitor copper ion to obtain a reaction product solution containing an acrylic ester or a methacrylate ester, and the reaction product solution Washing with washing water, separating the organic layer containing acrylic acid ester or methacrylic acid ester and washing waste water containing acrylic acid or methacrylic acid and / or a polymer thereof and copper ions; A method for producing an acrylic ester or a methacrylic ester having, after the cleaning wastewater treatment step generates copper sulfide by adding an alkali metal sulfide and / or hydrosulfide to the cleaning wastewater. , Acrylic acid ester or methacrylic acid ester, which is a process of adding a filter aid to coprecipitate separation of sludge containing copper sulfide Manufacturing method. The method for producing an acrylic ester or methacrylic ester according to claim 1 or 2 , wherein the treated waste water obtained by separating the sludge containing copper sulfide from the washing waste water is combusted. The method for producing an acrylic ester or methacrylic ester according to any one of claims 1 to 3, wherein the concentration of acrylic acid or methacrylic acid and / or a polymer thereof in the washing waste water is 0.5 to 200 g / L. The method for producing an acrylic ester or methacrylic ester according to any one of claims 1 to 3, wherein the alkali metal sulfide and / or hydrosulfide is sodium sulfide and / or sodium hydrosulfide. The method for producing an acrylic ester or methacrylic ester according to any one of claims 1 to 3, wherein the addition amount of the alkali metal sulfide and / or hydrosulfide is equimolar or more with respect to copper ions. The method for producing an acrylic ester or methacrylic ester according to any one of claims 1 to 3, wherein an alkali metal sulfide and / or hydrosulfide is added so that the oxidation-reduction potential of washing wastewater is 0 mV or less. The method for producing an acrylic ester or methacrylic ester according to any one of claims 1 to 3, wherein the washing waste water is adjusted to pH 7-13. Process of cleaning waste water, after generating the vulcanization of copper with the addition of sulfides and / or hydrosulfide of an alkali metal to the washing waste liquid, prior to addition of the aggregating agent or filtering aid Ki硫 of copper to form a sludge containing, then acrylic acid ester according to any one of the steps der Ru claims 1 to 3 to separate the front Ki硫 of copper from the washing waste water by dehydrating the sludge by solid-liquid separator Or the manufacturing method of methacrylic acid ester . The method for producing an acrylic ester or methacrylic ester according to claim 9 , wherein the flocculant is a nonionic and / or anionic organic flocculant.

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