JPS6222654B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating industrial wastewater containing phenols, particularly coke oven gas liquid wastewater or phenolic resin manufacturing wastewater, and more specifically, the present invention relates to a method for treating industrial wastewater containing phenols, particularly coke oven gas liquid wastewater or phenolic resin manufacturing wastewater, and more specifically, in the treatment, at least vinylpyridine is used as a monomer. The present invention provides a method for treating wastewater containing phenols, which comprises using a polymer compound obtained by copolymerizing the same with a crosslinking agent.

For example, coke oven gas liquid wastewater is used in the steel industry, city gas industry, chemical industry, etc. to extract ammonia from the gas liquid that is a by-product along with coke oven gas and coal tar that are generated when coke is manufactured by carbonizing coal. This is the liquid after removal or neutralization, and the wastewater contains 1000 to 5000 ppm of phenols as well as cyanide compounds and thiocyanide compounds, and the chemical oxygen demand reaches 5000 to 10000 ppm.

In addition, phenolic resin manufacturing wastewater is used to collect phenolic resins [e.g., phenolic resins, alkylphenol resins (cresol, xylenol, trimethylphenol, etc.), allylphenol resins,
This is wastewater generated during the production of alkenylphenol resins, polyhydric phenolic resins (resorcinol, etc.), polyphenol resins, modified phenolic resins, etc.), and the wastewater contains 1 to 10% by weight of phenols as well as formaldehyde. , methanol and catalysts, etc., and the chemical oxygen demand (COD) reaches more than 100,000 ppm.

As described above, industrial wastewater such as coke oven gas liquid wastewater and phenolic resin manufacturing wastewater contains large amounts of phenols, so strict regulations are in place for the disposal of these wastewaters from the perspective of environmental pollution. It is well known that Therefore, in order to dispose of these wastewaters, it is necessary to perform some kind of purification treatment. Furthermore, since these phenols are useful as intermediates for various industrial chemicals, it is necessary to perform a recovery treatment for these phenols from the viewpoint of resource conservation. Conventionally, activated sludge method, solvent extraction method, chemical treatment method, activated carbon treatment method, etc. have been used as the purification and recovery treatment method.
However, none of these methods is completely satisfactory. For example, the activated sludge method has the disadvantage that it cannot be directly applied to wastewater with a high concentration of organic matter (microorganisms in the sludge will die), while the solvent extraction method and chemical treatment method cannot completely remove or remove the organic matter in the wastewater. Not only is it difficult to treat, but conversely, the extraction solvent or chemical treatment agent gets mixed into the wastewater, so secondary purification treatment is required, and these methods cause air pollution, so countermeasures are required. There are drawbacks such as.

On the other hand, a method of adsorbing and removing phenols using a benzene-based ion exchange resin is also known. Although this method does not have the above-mentioned drawbacks, the adsorption amount of phenols is extremely low, and it also adsorbs other organic substances and metal ions that coexist with phenols in these wastewaters, and the phenols are Selectivity is also extremely low. Furthermore, it has the disadvantage that adsorbed phenols are not easily desorbed. That is, the phenols adsorbed on this ion exchange resin are not easily desorbed even when an aqueous alkaline solution, which is not preferred as a desorbent, is used, and the desorbed phenols undergo chemical changes, so they must be reused. It is also difficult.

In view of the current situation, the present inventors have conducted intensive research and found that a polymer compound obtained by using at least vinylpyridine as a monomer and copolymerizing this with a crosslinking agent overcomes the above-mentioned drawbacks. However, they found that it is extremely suitable as a phenol collection and collection material for industrial wastewater containing phenols, such as coke oven gas liquid wastewater and phenolic resin manufacturing wastewater, and have completed the present invention.

That is, the present invention uses at least vinylpyridine as a monomer, and uses a phenol collection material containing a polymer compound and/or an inorganic acid adduct thereof obtained by copolymerizing vinylpyridine with a crosslinking agent. The present invention relates to a method for treating wastewater containing phenols, which comprises bringing the wastewater into contact with industrial wastewater containing phenols.

To produce the polymer compound used in the present invention, generally, at least one vinyl pyridine and, optionally, a monomer other than the vinyl pyridine, and a crosslinking agent are suspended in an aqueous medium in the presence of a polymerization catalyst. The most preferred method is to obtain a spherical polymer by turbid polymerization, but emulsion polymerization or bulk polymerization may also be employed.

Vinylpyridines used as raw materials for producing the polymer compound according to the present invention include, for example, 2-
Vinylpyridine, 4-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine,
Examples include 2-(4-pyridyl)allyl alcohol.

As the crosslinking agent, polyvinyl compounds having a plurality of ethylenically unsaturated groups are used, such as aromatic polyvinyl compounds such as divinylbenzene, divinyltoluene, and divinylnaphthalene, and aliphatic polyvinyl compounds such as ethylene glycol diacrylate and ethylene glycol dimethacrylate. Polyvinyl compounds and nitrogen-containing polyvinyl heterocyclic compounds such as divinylpyridine, divinylquinoline, and divinylisoquinoline are preferably used. These crosslinking agents can be used alone or in combination of two or more.

The amount of crosslinking agent used is based on vinylpyridine.
Preferably it is 0.5 to 50% by weight.

In addition to the above-mentioned vinylpyridines and polyvinyl compounds as crosslinking agents, the raw material monomers used in the production of the polymer compound according to the present invention include aromatic substances such as styrene, vinyltoluene, ethylvinylbenzene, vinylnaphthalene, and chlorostyrene. Group monovinyl compounds, methyl acrylate,
One or more of aliphatic monovinyl compounds such as methyl methacrylate and acrylonitrile, or nitrogen-containing heterocyclic compounds such as vinylisoquinoline can also be used in combination.

As the polymerization catalyst, catalysts commonly used in polymerization reactions of vinyl compounds, such as benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, 2,2'-azobisisobutyronitrile, etc., are preferably used. Ru. The amount of these catalysts used is preferably 0.01 to 5% by weight based on the total amount of raw material monomers.

The polymer compound according to the present invention can be used in either a gel type or a porous type, but when producing the latter, a porosity forming agent is added to the reaction system in addition to the above components. There is a need to. As such a porosity forming agent, for example, Japanese Patent Publication No. 46-40431
Monovinyl linear polymers as described in No.
Precipitating agents such as those described in Japanese Patent Publication No. 36-18791 or Japanese Patent Publication No. 37-13792 (for example, alkanols having 4 to 10 carbon atoms or higher aliphatic hydrocarbons such as heptane and isooctane), or 47-40315 (e.g. sulfosuccinic acid, bis-
2-ethylhexyl sodium, dodecylammonium sulfate), etc. can be used.

The polymer compound produced by the present invention has extremely high adsorption capacity for phenols, especially phenol, cresol, xylenol, etc., and its adsorption capacity is not affected by coexisting organic substances or metal ions. , it also has extremely high selectivity for phenols. moreover,
The adsorbed phenols can be treated with common organic solvents, such as aliphatic alcohols such as methanol, ethanol, isopropanol, aliphatic ketones such as acetone, methyl ethyl ketone, or methyl acetate,
It can be easily desorbed using an organic acid ester such as ethyl acetate. Since the desorbed and recovered phenols can be easily separated from the desorbent, they can be reused as phenols. As described above, one of the characteristics of the polymer compound of the present invention is that phenols can be easily desorbed using ordinary organic solvents. Desorption can also be carried out using an aqueous solution of an inorganic base.

The polymer compound according to the present invention can be used as it is or in the form of adding an inorganic acid such as hydrochloric acid, sulfuric acid or sulfuric acid. Furthermore, in actual wastewater treatment, it is possible to use only this polymer compound or its acid adduct as a collection agent for phenols;
It is also possible to use a material formed into an appropriate shape together with zeolite or graphite as a collection agent. In this specification, the phenol collection and collection material means all of these collection and collection agents containing the polymer compound according to the present invention.

The phenol collection and collection material according to the present invention includes:
It can also be used in combination with a suitable ion exchange resin, in which case organic substances other than phenols and/or contaminant ions can be removed all at once.

In order to carry out the method of the present invention, it is sufficient to simply bring the phenol collection and collection material according to the present invention into contact with wastewater, and for example, any method such as a flow treatment method, a merry-go-round treatment method, or a fluid treatment method can be used. It may also depend on A contact time of several seconds to several minutes is sufficient. Although there is no particular restriction on the contact temperature, the effect can be sufficiently exhibited at room temperature.

Furthermore, if the method of the present invention is used in combination with an activated sludge treatment method, an activated carbon treatment method, etc., it is also possible to reuse treated wastewater as industrial water.

As mentioned above, the wastewater treatment method of the present invention can be applied to all types of industrial wastewater containing phenols, but is particularly applicable to phenolic resin production wastewater and coke ovens produced as by-products when coke is produced from coal. Effective in treating gas liquid wastewater.

The wastewater treatment method of the present invention includes a method for removing phenols contained in industrial wastewater by adsorbing them onto a phenol collection and collection material, and a method for removing the phenols from the phenol collection and collection material. It also includes a method of desorption and recovery.

The examples described below relate to the above-mentioned methods for treating phenolic resin manufacturing wastewater and coke oven gas liquid wastewater, but it is understood that the present invention is applicable only to these specific industrial wastewaters. must not.

Example 1 800 g of commercially available 4-vinylpyridine purified by simple distillation under reduced pressure and 80 g of commercially available divinylbenzene
g was suspended in 600 ml of a 15% aqueous sodium formate solution (12 g of hydroxycellulose was used as a suspension stabilizer), 8 g of benzoyl peroxide was added thereto, and the mixture was reacted at 80° C. for 5 hours. After the reaction was completed, the mixture was thoroughly washed with water to obtain about 1200 ml of bead-shaped crosslinked polymer.

Fill a column with a diameter of 4 cm with 1000 ml of the above cross-linked polymer, and produce novolak phenolic resin factory wastewater (COD 125,000 ppm) containing 42,400 ppm of phenols.
was passed through the tube at a rate of 3000 ml/hr for 1.7 hours. The concentration of phenols in wastewater treated in this way is
5ppm, the amount of phenols adsorbed on the crosslinked polymer is
220g, and the COD of the treated wastewater was 49490ppm.

Next, stop the flow of waste water and add methanol to 2000 ml.
The solution was passed for 2 hours at a rate of ml/hr. Methanol was distilled off from the effluent, and 216 g of phenols were recovered. The desorption rate of phenols with methanol is 98
It was %.

Example 2 Commercially available 2-methyl-5-vinylpyridine 1460
A mixture of 870 g of commercially available divinylbenzene, 380 g of isooctane and 33 g of benzoyl peroxide was mixed with 5100 g of water and 1000 g of sodium chloride.
g, 19 g of sodium nitrite and 28 g of hydroxycellulose. The suspension mixture was gradually warmed to 80°C over 1 hour and maintained at this temperature for 7 hours. After cooling and filtering, the obtained granular polymer was thoroughly washed with methanol and then water to obtain a white opaque crosslinked polymer (porous resin).
Obtained 5500ml.

1,000 ml of this crosslinked polymer was filled into a glass tube, and wastewater from a cresol resin manufacturing factory containing 14,000 ppm of cresols was passed through the tube at a rate of 3,000 ml/hr for 2.3 hours. The cresol concentration in the wastewater treated in this manner was 5 ppm, and the amount of cresol adsorbed onto the crosslinked polymer was 98 g.

Then stop the flow of waste water and add acetone to 2000 ml.
The solution was passed for 2 hours at a rate of ml/hr. Acetone was distilled off from the effluent, and 98 g of cresol was recovered. The desorption rate of cresol by acetone was 100%.

Example 3 300 g of commercially available 2-vinylpyridine, commercially available 4-vinylpyridine
100 g of vinylpyridine and 100 g of commercially available divinylbenzene were suspended in 3000 ml of a 20% aqueous sodium chloride solution (hydroxycellulose was used as a suspension stabilizer).
(12g used), plus 8g of benzoyl peroxide.
was added and reacted at 80°C for 8 hours. After the reaction was completed, the granular crosslinked polymer obtained was thoroughly washed with methanol and then with water to obtain 800 ml of bead-like polymer.

A glass tube was filled with 600 ml of this crosslinked polymer, and wastewater from a resorcinol resin manufacturing factory containing 40,000 ppm of resorcinol was passed through the tube at a rate of 2,400 ml/hr for 1 hour. The concentration of resorcinol in the wastewater treated in this manner was 5 ppm, and the amount of resorcinol adsorbed onto the crosslinked polymer was 98 g.

Next, stop the flow of waste water and add 1200 ml of ethyl acetate.
The solution was passed for 2 hours at a rate of ml/hr. Ethyl acetate was distilled off from the effluent, and 89 g of resorcinol was recovered. The recovery rate of resorcinol with ethyl acetate is
It was 91%.

Example 4 200 g of 5-ethyl-2-vinylpyridine, 136 g of commercially available divinylbenzene, 59 g of isooctane,
A mixture of 2 g of benzoyl peroxide and 3.4 g of lauroyl peroxide was suspended in a mixture of 800 g of water, 234 g of sodium chloride, 2.9 g of sodium sulfite and 4.25 g of hydroxyethyl cellulose. This suspension mixture was gradually heated and then reacted at 80°C for 8 hours. After the reaction, the obtained polymer was thoroughly washed with methanol and then with water.
720 ml of a white opaque crosslinked polymer was obtained. Sulfuric acid was added to the crosslinked polymer by immersing it in 1000 ml of a 20% by weight aqueous sulfuric acid solution for 2 hours.

A glass tube was filled with 600 ml of the sulfuric acid-added polymer, and the same phenolic resin manufacturing factory wastewater as in Example 1 was passed through the tube at a rate of 1000 ml/hr for 1.9 hours. The concentration of phenols in the wastewater treated in this way was 5 ppm, and the amount of phenols adsorbed on the crosslinked polymer was 132 g.

Next, the flow of waste water was stopped, and isopropanol was flowed at a rate of 1200 ml/hr. Isopropanol was distilled off from the effluent, and 69 g of phenols were recovered. The desorption rate of phenols by isopropanol was 89%.

Example 5 Two glass columns were each filled with 500 ml of the crosslinked polymer produced in Example 1, and these were connected in series. Waste water from a resol-based phenolic resin manufacturing factory containing 42,000 ppm of phenol was PHed with sulfuric acid.
After adjusting the temperature to 6.2, the solution was passed at a rate of 1500 ml/hr for 4.5 hours. The phenol concentration in the wastewater thus treated was 5 ppm, and the amount of phenol adsorbed by the crosslinked polymer in the first column was 250 g.

Next, the flow of waste water was stopped, and methanol was flowed only through the first column at a rate of 1000 ml/hr for 2 hours. Methanol was distilled off from the effluent, and 247 g of phenol was recovered. The desorption rate of phenol by methanol was 99%.

Example 6 1000ml of porous crosslinked polymer produced in Example 2
was immersed in 1000 ml of 30% aqueous hydrochloric acid solution for 3 hours to prepare a hydrochloric acid adduct. To 1000ml of this polymer,
1000 ml of Novolak's phenolic resin factory wastewater containing 30000 ppm of phenol was added and stirred for 3 hours. The concentration of phenol in the wastewater treated in this way was 450 ppm.

When the polymer adsorbing phenol was added to 1000 ml of a 3N-NaOH aqueous solution and stirred for 2 hours, the concentration of phenol in this aqueous solution was 28,960 ppm. The elution rate was 95%.

Example 7 200ml of porous crosslinked polymer prepared in Example 3
was added to 400 ml of wastewater from a phenolic resin manufacturing factory containing 3000 ppm of allylphenol and stirred for 3 hours. The concentration of allylphenol in the wastewater treated in this way was 20 ppm. When the polymer adsorbing allylphenol was added to 200 ml of a 3N-H ₂ SO ₄ aqueous solution and stirred for 2 hours, the concentration of allylphenol in this aqueous solution was 5423 ppm. The elution rate is
It was 91%.

Example 8 1000ml of bead-shaped crosslinked polymer produced in Example 1
was packed into a column with a diameter of 4 cm, and the phenols
Coke oven gas liquid wastewater containing 1380ppm (COD:
3500ppm) was passed through the tube at a rate of 3000ml/hr for 9.2 hours. The concentration of phenols in the wastewater treated in this manner was 5 ppm, the amount of phenols adsorbed onto the crosslinked polymer was 38 g, and the COD of the treated wastewater was 210 ppm.

Next, stop the flow of waste water and add methanol to 2000 ml.
The solution was passed for 2 hours at a rate of ml/hr. Methanol was distilled off from the effluent, and 37 g of phenols were recovered.
The desorption rate of phenols by methanol was 98%.

Example 9 A glass tube was filled with 1000 ml of the crosslinked polymer produced in Example 2, and coke oven gas liquid wastewater was passed through the tube in the same manner as in Example 8 for 10 hours. The concentration of phenols in the wastewater treated in this way was 5 ppm, and the amount of phenols adsorbed to the crosslinked polymer was 41g.
COD was 195ppm.

Then stop the flow of waste water and add acetone to 2000 ml.
The solution was passed for 2 hours at a rate of ml/hr. Acetone was distilled off from the effluent, and 41 g of phenols were recovered. The desorption rate of phenols by acetone was 100%.

Next, the treated solution containing 5 ppm of phenols was passed through a column packed with 100 ml of ion exchange resin Duolite A-1010 (manufactured by Diamond Shamlok Co., Ltd.) at a rate of 300 ml for 1 hour.
Ammonium thiocyanate in wastewater treated in this way was reduced from 570ppm to 0.5ppm, and
COD decreased to 18ppm.

Example 10 600 ml of the crosslinked polymer produced in Example 3 was filled into a glass tube, and phenols were added in the same manner as in Example 8.
Coke oven gas liquid wastewater containing 2430ppm (COD:
7100ppm) was passed at a rate of 2400ml/hr for 3.6 hours. The concentration of phenols in the wastewater thus treated was 5 ppm, the amount of phenols adsorbed onto the crosslinked polymer was 21 g, and the COD of the treated wastewater was 390 ppm.

Next, stop the flow of waste water and add 1200 ml of ethyl acetate.
The solution was passed for 2 hours at a rate of ml/hr. Ethyl acetate was distilled off from the effluent, and 19 g of phenols were recovered.
The desorption rate of phenols by ethyl acetate was 91%.

Example 11 600 ml of the sulfuric acid addition crosslinked polymer obtained in Example 4 was filled into a glass tube, and the same coke oven gas liquid wastewater as in Example 10 was passed through the tube at a rate of 1000 ml/hr for 7.5 hours.
The concentration of phenols in the wastewater treated in this manner was 5 ppm, the amount of phenols adsorbed onto the crosslinked polymer was 18 g, and the COD of the treated wastewater was 320 ppm.

Next, the flow of waste water was stopped, and isopropanol was flowed at a rate of 1200 ml/hr for 2 hours. Isopropanol was distilled off from the effluent, and 18g of phenols were obtained.
was recovered. The desorption rate of phenols by isopropanol was 100%.

Example 12 Two glass columns were each filled with 500 ml of the crosslinked polymer produced in Example 1 and connected in series, containing 1380 ppm of phenols.
Coke oven gas liquid wastewater (COD: 3500ppm)
The liquid was passed for 14 hours at a rate of 1500 ml/hr. The concentration of phenols in wastewater treated in this way was 5ppm,
The amount of phenols adsorbed by the crosslinked polymer in the first column was 26 g.

Next, the flow of waste water was stopped, and methanol was flowed only through the first column at a rate of 1000 ml/hr for 2 hours. Methanol was distilled off from the effluent, and 26 g of phenols were recovered. The desorption rate of phenols by methanol was 100%.

Example 13 500ml of porous crosslinked polymer prepared in Example 2
was immersed in 700 ml of 30% aqueous hydrochloric acid solution for 3 hours to prepare a hydrochloric acid adduct. 200ml of this polymer,
The mixture was added to 1000 ml of coke oven gas liquid wastewater containing 1380 ppm of phenols and stirred for 3 hours. The concentration of phenol in wastewater treated in this way is
It was 84ppm.

Claims (1)

[Claims] 1. A phenol collection and collection material using at least vinylpyridine as a monomer and containing a polymer compound obtained by copolymerizing this with a crosslinking agent and/or an inorganic acid adduct thereof A method for treating industrial wastewater containing phenols, the method comprising: contacting with industrial wastewater containing phenols. 2. The method according to item 1, wherein the industrial wastewater containing phenols is coke oven gas liquid wastewater or phenolic resin manufacturing wastewater obtained by removing or neutralizing ammonia from coke oven gas liquid. 3 Vinylpyridines are 2-vinylpyridine, 4
- The first or second term selected from vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-methyl-6-vinylpyridine, and 2-(4-pyridyl)allylic alcohol. The method described in any of the above. 4. The method according to any one of items 1 to 3, wherein the crosslinking agent is a compound having a plurality of ethylenically unsaturated groups. 5 The compound having multiple ethylenically unsaturated groups is divinylbenzene, divinyltoluene, divinylnaphthalene, ethylene glycol diacrylate,
5. The method according to item 4, wherein the compound is selected from the group consisting of ethylene glycol dimethacrylate, divinylpyridine, divinylquinoline, and divinylisoquinoline. 6 Monomers other than vinylpyridines include styrene, vinyltoluene, ethylvinylbenzene,
6. The method according to claim 1, wherein one or more monomers selected from the group consisting of vinylnaphthalene, chlorostyrene, methyl acrylate, methyl methacrylate, acrylonitrile, and vinylisoquinoline are used. 7. The method according to any one of Items 1 to 6, wherein the polymer compound has a porous structure. 8. The method according to any one of items 1 to 6, wherein the polymer compound has a gel type structure. 9. The method according to item 1, wherein the phenols adsorbed on the phenol collection and collection material are desorbed from the polymer compound using a desorption material to recover the phenols. 10. The method of item 9, wherein the desorbent is selected from the group consisting of aliphatic ketones, aliphatic alcohols, and organic acid esters. 11. The method according to item 1, which uses an activated sludge treatment method, an activated carbon treatment method, a solvent extraction treatment method, and/or an ion exchange resin treatment method.