Method of treating industrial effluents to remove cyanides and thiocyanates

FIELD: waste water treatment.

SUBSTANCE: cyanide effluents are treated with alkali or alkali-earth metal metabisulfite in presence of copper catalyst and residual cyanide and thiocyanate are subjected to bacterial destruction using strains Pseudomonas putida 21 and Pseudomonas stutzeri 18.

EFFECT: enabled detoxification of effluents within a wide cyanide and thiocyanate concentration range and therefore allowed use of the method for cleaning waste waters and slurries in gold mining, galvanic, pharmaceutical, and in a number of other industries.

 

The invention relates to the field of biotechnology, namely the protection of the environment, and for treatment of industrial wastewater and sludge from the free cyanides, thiocyanates and their complexes with metals and can be used in gold mining, electroplating, pharmaceutical and other industries.

Various methods of microbiological degradation of wastewater from the free cyanides, thiocyanates and their complexes with metals.

The known method bacterial treatment, tested for cyanide effluents gold plant about Eating, Nevada, USA. For the destruction of cyanide and its complexes used bacteria Pseudomonas pseudoalkaligenes, which were isolated from tail water (1).

The number of known strains of microorganisms isolated from industrial effluents and able to destructivity cyanides and thiocyanates in any form. In particular, cyanideseduxtion microorganisms include Pseudomonas fluorescens NCIMB 11764 (2), Pseudomonas paucimobilis ADS 39204 (3), Alcaligenes denitrificans (4), Fusarium oxysporum (5); to thiocyanatomethylthio microorganisms include Thiobacillus thioparas TN 115 (6), Thioalkalivibrio (ARH 1) and Thioalkalimicrobium (ALM 1) (7).

A known method of chemical decomposition of cyanide in the presence of copper catalyst gas containing oxygen and sulfur dioxide or sulfite or bisulfite or alkaline Molochnoe the additional metal (method INKO, which is similar to the proposed method of chemical treatment) (8). In the residual concentration of cyanide is above 0.1 mg/l, and the degree of degradation of thiocyanate no higher than 5-10%. As the prototype was selected bacterial-chemical method for the destruction of cyanide and thiocyanate in the wastewater, in which the cyanide chemical treatment translates into less toxic thiocyanate, and then when bacterial treatment they are oxidized in environmentally nitrates and sulfates (9). In the first stage, the process includes processing the polysulfides in the presence of low concentrations of metallic zinc at pH of 9.2. The weight ratio of polysulfide to CN-from 1:1 to 1.2:1. In the second stage, the thiocyanate is decomposed grammaticality chemolithotrophic bacteria (Thiobacillus), which form the ammonium and sulphate. Using nitrifying bacteria (Nitrosomonas, Nitrobacter)that are cultivated together with SCN-oxidizing,oxidized to. The optimum pH for bacterial degradation is in the range of 6.7 to 7.2. The residual content CN-when the original 1000 mg/l was less than 0.5 mg/l after chemical treatment. After bacterial treatment solutions containing 180 mg/l, 579 mg/l SCN-and less than 0.5 mg/l CN-were fully oxidized for lying is 28-40 hours in the reactor. The difference of the proposed method from the prototype is the following. For chemical treatment used metabisulfite sodium instead of polysulfide. The polysulfide used to translate CN-in SCN-. In the proposed method metabisulfite is used for neutralization CN-to a residual concentration acceptable for subsequent bacterial degradation. Residual cyanide and thiocyanate is used in bacterial processed by a consortium of bacteria Pseudomonas putida St and Pseudomonas stutzeri St for growth emitting CO2. Unlike the prototype of this method allows to carry out the neutralization in a wide range of concentrations of cyanide and thiocyanate (CN-- up to 30 mg/l SCN-up to 4000 mg/l). The proposed method allows cleaning not only wastewater and slurries.

The objective of the invention is to develop a method of purification of industrial effluents from cyanides and thiocyanates, which allows to reach the maximum permissible concentrations (MPC)established by the norms of SES (0.05 mg/l). This task is solved in that in front of microbiological processing, which reduces the concentration of cyanides and thiocyanates to MAC, it is proposed to carry out the chemical decomposition of the cyanide to acceptable for bacteria concentrations (no more than 30 mg/l).

The method consists in the following. First ASU is coming chemical treatment of cyanide wastewater (effluents) metabisulphite alkali or alkaline earth metal in the presence of a copper catalyst under stirring and aeration within 30-90 minutes The residual concentration of cyanide when it reaches 5.3-19.1 mg/l, pH of 10.5-9,4.

In order to bring the concentration of cyanides and thiocyanates to MAC, conduct subsequent microbiological processing. However, not all microorganisms, destructible cyanides and thiocyanates, able to grow in the environment resulting from chemical treatment. The consortium of bacteria Pseudomonas putida strain 21 and Pseudomonas stutzeri strain 18, highlighted by a long selection from the large number of strains (about 100) of different samples of anthropogenic pollution, was able to effectively decompose cyanides and thiocyanates after chemical treatment of industrial wastewater (effluents) within the concentration range specified above.

Microbiological processing obtained after chemical treatment carried out by a consortium of bacteria (10% by volume) in the presence of potassium phosphate and organic carbon source is required for activity of bacteria. The process is carried out in a reactor with stirring and aeration.

The technical result of the proposed method is the high degree of neutralization of cyanide industrial waste (sludge) from cyanides, thiocyanates and their complexes with metals. The proposed method due to the distinctive features of the prototype characteristics allows a high degree of destruction of cyanide and t is tiantou. Preliminary before bacterial treatment chemical decomposition CN-allows you to get a working pH range and optimum concentration of cyanides and thiocyanates used for a consortium of bacteria.

Description of used of a consortium of bacteria.

The consortium be stored in the laboratory of chemolithotrophic microorganisms inmi RAS.

The strain Pseudomonas putida No. 21 has the following characteristics :

Morphological features.

Cells are rod-shaped, motile, regular shape with rounded ends. The size of cells of 0.4-0.6×1,5-1,8 mm.

Monotech. Spores and capsules are not formed. Polymorphism is absent.

Propagated by division. Gram-negative.

Cultural characteristics.

On mesopatamia agar and synthetic environments forms a light grey fluorescent flat colonies with rough edges with a diameter of 3-5 mm

Physiological and biochemical properties.

Chemoorganotrophs, microaerophile, catalase and oxidase-positive. Gelatino not hydrolyses. As a source of carbon and energy uses glucose, sucrose, maltose, xylose, arabinose, glycerol, ethanol, succinate, lactate, acetate, arginine. Not using mannose, galactose, mannitol. As the nitrogen source uses mineral (,, CNS-and the organization is organic forms of nitrogen. Grows in the temperature range from 20 to 37C and pH 6.5-9,4. Optimal for growth are temperature 25-27C and pH 8.5 to 8.8. Content HZ (guanine/cytosine) bases 64,7 mol.%.

The strain has a high resistance to cyanide, breathing is not inhibited at concentrations CN-60 mg/L.

The strain Pseudomonas stutzeri No. 18 has the following characteristics :

Morphological features.

Cells are rod-shaped, motile, regular shape with rounded ends. The size of cells of 0.5-0.7×3,8-4,0 mm.

Monotech. The dispute is not formed. Has a capsule. Polymorphism is absent. Propagated by division. Gram-negative.

Cultural characteristics.

On mesopatamia agar and synthetic environments forms a dark yellow wrinkled colonies with a diameter of 5-8 mm

Fluorescent pigments are not formed. Forms yellow intracellular pigment unidentified nature.

Physiological and biochemical properties.

Chemoorganotrophs, microaerophile, catalase and oxidase-positive. Gelatino not hydrolyses. As a source of carbon and energy uses glucose, sucrose, trehalose, maltose, galactose, mannose, xylose, arabinose, mannitol, glycerol, ethanol, succinate, lactate, acetate, arginine. Does not use lactose, Inositol. As the nitrogen source uses mineral (,/img> CN-, SCN-) and organic forms of nitrogen.

Grows in the temperature range from 15 to 43C and a pH range of 6.8 to 9.4. The optimal growth temperature of 25-28C, pH of 8.7-8.9 in. Active (in.

Content HZ reason 64,4 mol.%.

The sequence of the 16 S RNK closest to a standard strain of P. stutzerii ATCC 17588, however, differs significantly speed the destruction of the SCN-. The strain is resistant to concentrations in the environment thiocyanate to 6 g/L.

An example of the method.

Used industrial wastes (slurry) after cyanidation of gold-bearing material. The solids content amounted to 20-30%. In the liquid phase contained (mg/l): Mg - 0,4, SO4- 700, CN-total - 200, SCN-- 4200, C - 13, Zn - 3, Fe - 500, Ni is 2.5, As - 1,2, Sb - 5. Chemical treatment was carried out with sodium metabisulfite (consumption, Na2S2O5/CN-5 g/g) in the presence of a catalyst CuSO4at pH of 10.5-to 9.4. When handling cyanide effluent content of the cyanide ion was reduced to 5.8 mg/l, and thiocyanate to 4000 mg/L.

Pulp after chemical treatment was used for microbiological degradation of residual concentrations CN-and SCN-.

Bacterial degradation was carried out in 3 reactors with mechanical stirring and aeration at a temperature of 25-30C With the help of a consortium of bacteria Pseudomonas putida strain 21 and Pseudomonas stutzeri strain 18, which is carried in the slurry in equal shares (5% by volume). The concentration of the cyanide ion was 5.8 mg/l and thiocynate-ion 4000 mg/L. the Working pH value was from 9.0 to 9.4, which was supported by solutions of NaOH and H2SO4. Full oxidation of 5.8 mg/l CN-occurred for 60 minutes Then the destruction of the SCN-24 hours. The final concentration of SCN-was below 0.05 mg/L. the Final products of the decomposition of carbonates were.

The concentration of bacterial cells reached a value of 2.7·1010in 1 ml.

Literature.

1. S.K.Dubey and D.S.Holmes. Biological cyanide destruction mediated by microorganisms. World Journal of Microbiology & Biotechnology. 1995. vol.11. pp.257-265.

2. D.A.Kunz, O.Nagappan, J.Silva-Avalos a. G.T.Delong. Utilization of cyanide as a nitrogenous substrate by Pseudomonas fluorescens NCIMB 11764: evidens for multiple pathways of metabolic conversion. Applied and Environmental microbiology. 1992. p.2022-2029.

3. J.L.Whitlock. Biological detoxification of precious metal processing wastewaters. Geomicrobiology Journal. 1990. v.8. pp.241-249.

4. S.Basheer, O.M.Kut, J.E.Prenosil, and J.R.Bourne. Kinetics of enzimatic degradation of cyanide. Biotechnology and Bioengineering, 1992. vol.39. pp.629-634.

5. P.T.Pereira, J.D.Arrabaca a. M.T.Amaral-Collaco. Isolation, selection and characterization of a cyanide-degrading fungus from an industrial effluent. Interational Biodeterioratoin a. Biodegradation. 1996. pp.45-52.

6. Y.Katayama, T.Kanagawa a. H.Kuraishi. Emission of carbonyl sulfide by Thiobacillus thioparus grown with thiocyanate in pure and mixed cultures. FEMS Microbiolgy Letters. 1993. v.114. pp.223-228.

7. D.Y.Sorokin, .P.Tourova, ..Lysenko, a, J.G.Kuenen. Microbial tiocyanate utilization under highly alkaline conditions. Applied a. Environmental Microbiology. Feb. 2001. pp.528-538.

8. E.Devayst, G.Robbins, R.Vergunst. Ynco SO2/Air. Ynco's cyanide removal technology. Mining Eng. (USA). 1991. 43. No. 2. pp.205-207.

9. US Patent No. 4737289, Apr.2, 1988. F.J.Castaldi, T.W.Trofe, G.C.Page, K.M.Adams. Process fore waste water treatment.

The method of purification of industrial effluents from cyanides and thiocyanates, including chemical treatment and bacterial degradation of cyanides and thiocyanates, characterized in that the chemical treatment is carried out by metabisulphite alkali or alkaline earth metal, and bacterial degradation of residual cyanide and thiocyanate carried out with the help of a consortium of bacteria Pseudomonas putida strain 21 and Pseudomonas stutzeri strain 18.



 

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