SU1058899A1 - Method for biochemical purification of phenol-containing effluents - Google Patents

Abstract

1. A method of biochemical purification of phenol-containing waste waters, including the introduction of biogenic supplements, characterized in that, in order to reduce the commissioning period, simplify the process and increase the productivity of purification facilities 1X, biochemical purification is performed by microflora, including active and microflora, including active and microflora. on organic compounds, selected-., from a series including alcohols, acetone, sodium lactate, sucrose, or waste water holding them, after a period of adaptation, and grafting is carried out Niemi phenolic compounds in doses of 10-30 mg / L to complete the oxidation of each dose. 2. The method of claim 1, wherein the adaptation is carried out at 25-50 ° C and sodium acetate, pyrocatechin, organic 1 is used as biogenic additives (L compounds or wastewater, which grow .

Description

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with The invention relates to the biochemical treatment of wastewater and can be used for the treatment of wastewater containing phenolic compounds. A method of obtaining populations of selective activity is known by concluding that the concentrates of non-pathogenic microorganisms used in the compositions are obtained by release under natural conditions. microbial strains in immaculately functioning biological purification systems and by twisting with slow stirring in the presence of a nutrient solution with controlled content of 1. However, the procedure for isolating microorganism strains with the necessary and "useful features, properties-i, is long and difficult, and the constant removal of inoculated microorganisms from the buildings does not allow them to be highly concentrated, which lengthens the commissioning period, complicates the cleaning process. The closest to the proposed technical essence and dortifiable result is a method of biochemical purification of wastewater from phenols by a specially isolated strain of bacteria Pseudomonas aerugi nose L2J. The disadvantages of the method are the duration of the extraction procedure, as well as the low rate of oxidation, and no phenols when using an isolated strain of bacteria , namely 200-300 mg of phenol per day. The purpose of the invention is to reduce the commissioning period, simplify the process and increase the production: of the treatment plant. This goal is achieved by the fact that, according to the method of biochemical purification of phenol-containing eteric water, it is carried out in the presence of biogenic additives by microflora, s including activated sludge, previously grown on organic (Compounds selected from a number; including (Alcohol, acetone, sodium lactate, sucrose or wastewater, they are contained after the adaptation period, and the adaptation is carried out by introducing phenolic compounds in doses of 10-, 30 mg / l until the end of each dose is oxidized, and sodium acetate, pyrocatechol, organic compounds or Sewage., on which microflora is grown. The use of microflora phenolic compounds for purification, preliminarily grown on alcohols and other organic compounds or on waste waters containing them, after the period of adaptation allows noticeably reduce the volume and period of commissioning, since the growth of microflora on organic compounds that do not contain phenols, proceeds much more intensively. At the same time, the purification technology is simplified, since there is no need for laborious and lengthy work on isolating cultures of phenolic acid microorganisms and obtaining sufficient amount of their biomass. Adaptation of microflora to phenolic compounds, produced in accordance with the proposed method, does not reduce the ability of microflora, including activated sludge, to precipitate and to oxidize compounds or wastewater from which the microflora has been pre-grown. Adaptation by introducing phenolic compounds in doses of 10–30 mg / l makes it possible to shorten the adaptation period during commissioning, because if you add higher doses of NOLOV to samples that react to an excess of phenols in type 1 (sigmoid curves O | 1, and pH) , the adaptation rate decreases, with the latter, the residual amounts of phenolic compounds being oxidized at an increasing rate. The pattern of microflora of activated sludge, despite the apparent heterogeneity of the species composition, exhibits the highest activity in the oxidation of carbon sources into fairly narrow ones. temperature limits. Based on the fact that the temperature optimum for different samples of the microflora is active or located in different areas for the improvement of the microflora in order to accelerate it, a temperature range of 25-50 0 is adopted; Intensification of the adaptation process is also achieved by using sodium acetate, pyrocatechol, organic compounds, and long wastewater as biogenic additives. The use of biogenic additives accelerates the controlled adaptation of microflora to phenolic compounds, further shortens the commissioning period. The proposed method is carried out as follows. In a glass vessel, containing 0.1–1 l of microflora biomass, or in an aerotank mixer containing activated sludge, previously grown on organic compounds selected from a series of alcohols.

acetone, sodium lactate, sucrose, or on the water containing these compounds, lower any type of dissolved oxygen sensor, such as EG-152-003, or a pH meter sensor connected to a potentiometer, for example, KPS-4

The vessel is preliminarily lowered to the bottom 1: a flowed capillary or a ceramic sprayer connected to an overhead line, and under aeration conditions, the dynamics of the Oj or pH values are recorded on the chart tape.

To speed up the process of adaptation of the microflora to phenolic compounds, the temperature of the sample or the contents of the aeration tank mixer is kept constant within 25-50 O. Since the adaptation is controlled by O2 or pH indicators, the curves recorded on the chart tape should reflect the starvation of the microflora, and it should not contain organic compounds, the oxidation of which would make it difficult to control the process. To ensure that the Oj or jQH curves reflect the state; endogenous respiration, compounds are introduced into microflora samples or into the aerotank-mixer, on which microflora was previously grown at the rate of 1-30 Mg / l (by substance or VPK), and in the case of a hungry condition, the pointer of the analyzer of the dissolved oxygen analyzer stops movement towards saturating concentration or. shifting towards lower O2 content. The movement of the pH indicator depends on whether neutral organic compounds or organic acid salts are added. In any case, the deviation of the pointer OJ. or pH indicates the exhaustion of substrates and the possibility to start, the introduction of substrates. After the start of the movement of the O or pH indicators towards the increased value of the parameters, 510 min should pass in order for the microflora sample (activated sludge) to contain a high initial amount of oxygen (starting concentration O), and the available carbon dioxide was largely removed. Upon completion of the oxidation of the first dose of phenols (10 mg / l), which may take from 15-20 minutes to an hour and more, curves 02 or pH, as a result of a decrease in Og consumption and release of carbon dioxide, begin to move in the opposite direction.

As a result of the adaptation to the oxidation of subsequent doses of phenols, the required weight is less than the time, i.e. adaptation goes with increasing speed .. The speed of adaptation of microflora to phenolic compounds

increases even more if sodium acetate, pyrocatechin, and organic compounds or wastewater are introduced at the same time as phenolic compounds, and the microflora is pre-treated.

Provided that a sample of microflora or activated sludge is heated to a constant temperature (25-50s), the adaptation process lasts 2-6 hours.

Example 1 Conducting microflora of activated sludge to oxidize artificial effluent containing 400 mg / l butanol to m-creaeol microflora. Activated sludge was obtained on an aerotank mixer model with a period of aeration of 5.5 h (D 0,. When adapting, activated sludge (dry matter concentration 1.92 g / l) is aerated in a volume of 1 l with an air flow rate of 1.5 l / mpn, then 2 l / min. The temperature of the microflora sample is maintained automatically at a constant temperature of 35 ° C, and the pH when added to doses of phenolic and other organic compounds is 7, -8.02.

Oxygen consumption curves are recorded on the analyzer of dissolved oxygen EG-152-003 at a speed of movement of a chart tape of 60 mm / h. The course of adaptation is presented in Table. one.

Based on the time from the introduction of the substrate to the beginning of the oxygen pointer movement in the direction of saturation, taking into account the inertia of the instrument, the rate of its oxidation is calculated.

Experimental data (series 1) on adaptation to m-cresol show that at T 35 ° C, the adaptation process takes place with a sharply increasing rate and after 3 hours the oxidation of 10 mg / l m-cresol (point 20) requires only 1.5 minutes together 35 min

After a total of 140 mg / l of m-cresol is oxidized, a dose of 10 mg / l of m-cresol is used by microorganisms as a carbon source at the same rate (400 mp / l) as the dose of 10 mg / l butanol, t . organic compound, in which the microflora of activated sludge was pre-grown in a continuous culture mode.

In the process of adaptation, a 23-fold increase in the activity of the microflora in relation to m-cresol occurs.

Example 2. For the oxidation of m-cresol, the microflora of activated sludge is used to oxidize a mixture of 500 mg / l of sucrose and 75 mg / l of butanol with an aeration period of 5.5 h (, 18) on the model of an aerotank-mixer.

Conditions: active sludge concentration 2.62 g / l, aeration 1.5 l / min, T 35c, pH values when substrates are added 7.2-7.72.

The adaptation process (series II) begins with the addition of 10 mg / l of an aqueous solution of m-creaeol, which takes 45 minutes to oxidize. Subsequent doses of m-cresol are introduced simultaneously with butanol or sugar and are oxidized for increasingly shorter periods of time, i.e. with an increasing rate of 13.57, 83, 75, 103 ... 219 mg / l-h Since the oxidation of phenolic compounds in this way is reversible / suppressed by an excess of the substrate, the value of the oxidation rate of 30 mg / l of m-cresol does not contradict the results of the experiment. After 3 hours of adaptation, m-cresol oxidizes at a rate of the same order as butanol and 1/2 time with a lower rate than sucrose. In the process of adaptation, a 17-fold increase in the activity of the microflora in relation to m-cresol occurs, - ... Example 3. A microflora grown previously in periodic mode on sodium lactate is used to oxidize phenol. The biomass concentration is 1.64 g / l, aeration 1.5 l / min, T, pH when substrates are applied is 8.6-8.7. In tab. Figure 1 shows the values of the rates of oxidation of phenol introduced into the microflora sample simultaneously with sodium p lactate (Mi series). In the process of adaptation, there is a 3-fold increase in the activity of microflora with respect to phenol. Example 4. The m-cresol is oxidized by microflora grown in batch mode on ethanol (2.8 g / l, aeration 1.5 l / min, T, pH with addition of susbrates 6.6-6.9). In the process of 3-hour adaptation, a 17-fold increase in microflora activity in relation to m-cresol occurs. After adaptation, m-cresol is oxidized at a rate of the same order as ethanol (series) V, table. one). Example 5. The significance for the adaptation process of doses of a phenolic compound of 10.30 and 100 mg is determined. Conditions: The biomass concentration of micro flora grown on butanol is 3.8 g / l T 27 ° C, aeration 1.5 l / min. It took 1 hour and 23 minutes to oxidize m-creeol introduced into the sample with doses of 10 and 100 mg / l, i.e. The average oxidation rate is 78.7 mg / L. Approximately the same amount of m-cresol (120 mg / l), applied in doses of 10 and 30 mg / l, was oxidized for a total of 57 minutes and 50 seconds at an average rate of 124.5 mg / l of us. Example 6, The essence of the adaptation process of doses of a phenolic compound of 10, 30 and 50 mg / l is determined. Experimental conditions: 3.92 g / l, 1.5 l / min. It takes 2 hours and 3 minutes to oxidize the first dose of OO mg / l m-cresol, grown on butanol, for an oxidation of the second dose 50 mg / l 45 minutes. In the case when m-cresol is applied in doses of 10 mg / l, the first 50 mg / l of m-cresol are oxidized for 43:24, 13.5, 10.5, and 9 minutes respectively or for a total of 1 40 h, the following 50 mg / l of m-cresol, introduced into the sample with doses of 10.30 and 10 mg / l, are oxidized for 8.24 and 6 min (total 38 min), i.e. 100 mg / L of m-cresol, delivered in doses of 50 mg / l, takes 2 hours and 48 minutes, and doses of 10-30 mg / l, 2 hours and 18 minutes. Example 7 The effect of stimulation of adaptation is determined by introducing into mi-i crophlora grown on butanol, simultaneously with m-cresol of organic compounds. The result of the experiment on stimulation of adaptation: if you add 10 mg / l butanol as the first dose, and 10 mg / l butanol and 30 mg / l sodium acetate as the next dose, the adaptation rate increases by 35-100%. The data presented in Table. 2 .. Example 8. The effect of stimulation of adaptation is determined by introducing organic compounds into the microflora grown in continuous mode on acetone. In the experiment with the introduction of substrates as the first dose, in addition to 10 mg / l of m-cresol, 30 mg / l of pyrocatechol and 30 mg / l of sodium acetate are added, as the second dose of 10 mg / l of acetone and 60 mg / l of sodium acetate, as the fourth 30 mg / l of acetone. The introduction of additional organic compounds increases the rate of adaptation by 29-200%. The data are presented in Table 3. Example .9. By the time from the introduction of m-cresol into 1 microflora grown in acetone in the continuous mode until the start of the pH-meter indicator towards higher values, the effect on the adaptation of the heating of the microflora from 20 to will be determined. H., The first four doses of m-cresol introduced are oxidized at 35 ° C at a rate 2 times greater than at 20 ° C. The fifth dose of m-cresol is oxidized at the same temperature () and in both cases at the same rate. However, in the case of preheating, a gain in time is obtained, since the total time of ghptation at 2 hours and 35 minutes, and at 1 hour and 11 minutes. The data presented in Table. 4. Adaptation of the sample grown on acetone to m-cresol is continued after adding 400 mg / l of m-cresol over the next 4 hours, doses of 10 and 30 mg / l of m-cresol are oxidized at a rate of (respectively) 340 and 360 mg / at one o'clock. Chemical oxygen consumption (COD) of the liquid phase of the sample after oxidation of 470 mg / l of m-cresol, 30 mg / l of acetone and 10, mg / l of formaldehyde increases compared with the control by 35 mg of O / l, since the COD of the applied amount of m-cresol , determined by the bichromate method, is 1175 mg O / l, almost all the amount of m-cresol introduced is used for energy and construction purposes. After completion of the adaptation test, the oxidation rate of 30 mg / l of acetone is 278 mg / l, i.e. adapted 14 microflora does not lose the ability to oxidize the compound on which it was grown. ,, - Prier 10. Determine the effect of stimulation of adaptation to m-cresol by introducing biogenic additives. For the experiment, microflora of activated sludge is used, which, on an aerotank-mixer model, oxidizes an artificial drain containing 1 l in. Extra water 500 mg of methanol (aeration period 7h). The experiment on the adaptation of microflora to m-cresol was carried out at concentration. or - 2.92 g / l, aeration 1 l / # 1H, T “. Stimulation is carried out immediately after the first dose of m-cresol, successively 10 mg / l formaldehyde, 30 mg / l methanol, 30 mg / l formaldehyde and 30 mg / l sodium acetate. After the second dose has been applied (10 mg / l}. M-cresol, 30 mg / l of methanol, formaldehyde and sodium acetate are added successively. The third and fourth doses of m-cresol are oxidized without the addition of organic compounds. The stimulation effect from the addition of additional substrates is 25-90%. The data are presented in Table 5. When implementing the proposed method, the following should be taken into account. Features: The introduction of active phacroflora into the samples of the microflora or doses of any of the cresols always increases with respect to phenol, when introduced into The microflora of the dose of phenol does not always show the same Cs1 as high activity as cresols, but in any case it rises with the removal of the methyl group from the hydroxyl, i.e., in the row o-cresol, m-crezrel, p-cresolr after With the accelerated adaptation to phenolic compounds, each microflora sample grown on alcohols and other organic compounds reacts to a phenol concentration of 10-100 mg / l, as well as to the localization of the methyl group, which allows considering samples of mixed microflo1% 1 active silt as homogeneous According to the characteristics due to the exchange of genetic information and the desire to monoculture microflora. I Considering that the likelihood of successful adaptation is enhanced if microorganisms dispose of compounds of similar structure, the proposed method can be used for detoxification and wastewater treatment containing aromatic compounds with various functional groups, in particular halogen-containing phenols. Table 1

T and in l and “and

Continued table. 2

107.49-7.5944mic 13.6 .7.25107, 62-7.66ЗЗмин 187.69. Table

Table 4

Table

125 190 7.6635 min. 17 7.7117m 30s 34

Continued tabl, 5

Claims (2)

1. BIOCHEMICAL METHOD • PURIFICATION OF PHENOL-CONTAINING WASTE WATER, including the introduction of biogenic additives., Characterized in that, in order to reduce the commissioning period, simplify the process and increase the productivity of treatment facilities, biochemical treatment is carried out by microflora, including activated sludge, previously grown on organic compounds selected ( from a series including alcohols, acetone, sodium lactate, sucrose, or wastewater containing them, after the adaptation period, and adaptation is carried out by adding phenolic compounds in doses of 10-30 mg / l until completion is ok lized each dose. 2. The method according to π. 1, characterized in that the adaptation is carried out at 25-50 ° C and sodium acetate, pyrocatechol, organic compounds or wastewater, on which microflora are grown, are used as biogenic additives. SU., „1 s 00 00. with © ζ ©