Method for purification of phenol-containing sewage

专利摘要:
A process for treating waste water containing both phenolic compounds being toxic for methanogenic organisms and degradable non-phenolic compounds prior to its anaerobic purification as well as a process for detoxifying waste water containing phenolic compounds being toxic for aquatic organisms by subjecting said waste water to an oxidative treatment in such a way that no or virtually no precipitation is formed of the polyphenol compounds produced and virtually no influence is executed on the biochemical oxygen demand and the chemical oxygen demand of the waste water.
公开号:SU1711669A3
申请号:SU874202256
申请日:1987-03-19
公开日:1992-02-07
发明作者:Арон Файелд Джеймс
申请人:Пак Б.В. (Фирма)；
IPC主号:

专利说明:

The invention relates to the treatment of water and can be used in wastewater treatment of paper, cardboard and wood processing industry.
The aim of the invention is to increase the efficiency of the process while ensuring a high degree of purification.
In order to carry out the process, the wastewater is pretreated with oxidizing agents to a threshold concentration of phenols that does not cause inhibition of the methane-forming microflora, and then sent for biochemical purification under anaerobic conditions.
As oxidizing agents, air oxygen in neutral or alkaline media, hydrogen peroxide, ozone, as well as any of these oxidizing agents in the presence of phenoloxidase or laccase or microorganisms that secrete these enzymes in the presence of oxygen can be used.
The threshold concentration of phenols, which does not cause inhibition of the methane-forming microflora, is determined by the content in the solution of tannic acids capable of adsorption on the polyamide or protein.
In wastewater treatment, the detachments, which are derivatives of phenols, which contain chlorine, sulfo, nitro, and some other substituents in their molecules, before oxidation,
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they are biochemical processing under anaerobic conditions ..
Known methods of purification of wastewater from phenols involve their transformation into insoluble polymers, which can be removed by filtration, centrifugation or sedimentation, and subsequent biochemical purification during aeration.
The use of biochemical purification under anaerobic conditions, which is preferable for wastewater characterized by a COD value of 1000 mg 02 / l, is difficult, because in the course of the oxidation of phenols, compounds that have a toxic effect on the methanogenic bacteria used in anaerobic bacteria are formed. processes.
The maximum toxicity of the phenol derivatives formed during the polymerization process under the action of oxidizing agents is observed for molecular weights of 500-3000 corresponding to tannic acids.
With further increase in the degree of polymerization, the toxicity decreases again. :
Thus, the essence of the proposed method, which uses biochemical purification under anaerobic conditions, which requires less energy consumption and allows to obtain a useful product, methane, consists in obtaining, in the process of preliminary oxidative treatment, compounds that are non-toxic to meds-forming microflora. These compounds are derivatives of phenols with a molecular weight of 3000, but soluble in water.
FIG. 1 shows the dependence of the methanogenic toxicity of phenol derivatives on the degree of their polymerization; FIGS. 2 and 3 show data on the change in methanogenic toxicity of the treated solutions; in fig. 4 - correlation between the methanogenic toxicity of solutions and their affinity for proteins; in fig. 5 - the same, to polyamides.
Example 1. Solutions of pyrogallol and tannin concentration of 1 g / l are subjected to oxidation. The oxidation is carried out in the aeration process for 0-15 minutes at a pH of 7.4;
The methanegenic toxicity of the treated solutions is assessed by the activity of the sludge exposed to solutions for 19 days relative to control sludge, the activity of which is 0.5 g of COD / r solids active or all km. As a substrate, a solution of volatile fatty acid concentration of 4.2 g (COD) / l is used.
The oxidation of 1,2,3-trihydroxybenzene (pyrogallol) leads to a decrease in the methanogenic activity at the initial stage, since at this point toxic polymers are formed during the oxidative processing (Fig. 2).
During the oxidation of tannin (Fig. 3), which is a polymer consisting of nine units, the methanogenic activity increases, since the further polymerization process leads to the formation of non-toxic compounds. . Methanogenic toxicity of wastewater, and hence the threshold concentration that does not cause inhibition of methanogenic microflora, can be determined by determining the degree of affinity of the phenol derivatives formed during the oxidative treatment to proteins or polyamides. To do this, protein (glucosidase) or polyamide (polyvinylpyrrolidone) is introduced into the controlled solution obtained as a result of oxidative treatment, after which the degree of absorption of the solution in the UV region at a wavelength of 340 nm is measured.
EXAMPLE 2. Waste water obtained during wet removal of pine bark after filtration and dilution, characterized by a COD value of 1.8 g Og / l, pH 10.2, tannin concentration 420 mg / l, value the ratio of tannin to total phenol is 0.75.
Sewage is aerated for 0-48 hours; ...- .. .. ::
Fig. 5 presents data on the change in methanogenic toxicity of the treated water (graph 1), the concentration of tannins capable of adsorption1 on polyvinylpyrrolidone (graph 2), and the degree of absorption of solutions at a wavelength of 440 nm (graph 3) depending on aeration time : a - 0 h, b - 0.65 h, c - 3.25 h, g - 23 h, d-48h.
The pH of the treated water rises after 45 minutes of aeration to 9.6, at the end of aeration to 8.2.
As follows from FIG. 5, the change in the toxicity of tannic acids formed during the aeration of phenolic wastewater corresponds to the change in their affinity for polyvinylpyrrolidone. During the aeration process for 48 hours, the methanogenic toxicity of the treated water decreases to almost zero, although a decrease in the total concentration of phenols, as evidenced by UV absorption data for solutions
not happening. Thus, the treated water can be subjected to biochemical purification under anaerobic conditions,
In tab. Table 1 presents data on the effect of various methods of oxidizing treatment of extracts of birch bark on the reduction of COD, the content of phenols and the methanogenic toxicity of solutions.
The extract is obtained from 18 g of air-dried bark in 1 liter of water at 60 ° C.
The methane activity of the sludge is measured after a 14-day exposure to the treated extracts, diluted 2.5 times relative to control sludge.
Control sludge activity .720 mg COD / g solids activated sludge per sut.
In tab. 2 presents data on the effects of untreated and aerated for 16 h at a pH of 11.5 spruce bark extracts on carp fish.
The use of the proposed method for the treatment of wastewater improves the economics of the process by eliminating the need to isolate insoluble derivatives of phenols from solutions, as well as by using in the second stage of purification biochemical treatment under anaerobic conditions, which requires less energy and useful product is methane gas.

权利要求:
Claims (4)
[1]
Invention Formula
t. The method of purification of phenol-containing wastewater, including a preliminary
five
0
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treatment and subsequent biochemical purification, characterized in that, in order to increase the efficiency of the process while ensuring a high degree of purification, the pretreatment is carried out by oxidizing the phenols to a threshold concentration that does not cause inhibition of the methane-forming microflora, and the biochemical purification is carried out under anaerobic conditions x
[2]
2. A method according to claim 1, characterized in that the oxidation of phenols is carried out with atmospheric oxygen in neutral or alkaline media and / or hydrogen peroxide, or ozone, or one of said oxidizing agents in the presence of phenol oxidase or laccase, or microorganisms that secrete phenol oxidase or laccase
[3]
3. Method according to paragraphs. 1 and 2, so that the threshold concentration of phenols, not causing the inhibition of methane-forming microflora, is determined by the content of tannic acids in the solution, capable of adsorption on polyamide or protein.
[4]
4. A method according to claim 1-3, wherein, in the treatment of wastewater containing substituted phenols, prior to the treatment with oxidizing agents, preliminary biochemical purification is carried out under anaerobic conditions.
Table 1
The continuation of the table.1.
 After 14 days, the methanogenic activity is absent. After 14 days, methanogenic activity was detected. Similar results were obtained with ozone treatment. By biological oxidants are meant microorganisms that secrete laccase or phenol oxidase. Similar results were obtained using these enzymes directly.
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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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NL8600723A|NL8600723A|1986-03-20|1986-03-20|METHOD FOR PURIFYING WASTE WATER.|

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