Method of sewage purification from cyanide-ions

FIELD: chemistry.

SUBSTANCE: method of sewage purification from cyanide-ions includes its processing with sulfate of bivalent iron in quantity 293 wt.p to 100 wt.p. CN-ions in presence in water of sorbent in form of fibrillated cellulose fibres, which contain in wt %: not less than 54% of fibres with length not more 0.63 mm and not less than 94% of fibres with length not more than 1.23 mm, with formation of reaction product in form of insoluble particles of iron cyanide. Reaction product is obtained in form of composite material, which consists of cellulose fibres with sorbed on them iron cyanide particles. Product of processing is discharged from water with application of pressured flotation.

EFFECT: invention makes it possible to simplify process of purification, reduce iron sulfate consumption, increase purification degree and provide possibility of carrying out purification in continuous mode.

2 cl, 3 ex

 

The invention relates to techniques for wastewater from cyanide and can be used at the enterprises of ferrous and nonferrous metallurgy, upon receipt of the gold cyanide way, in the chemical, machine-building industries.

The known method of wastewater treatment for cyanide ions by treatment with ferrous sulfate iron in its consumption of 10.5 parts by weight to 1 parts by weight of CN-ions in the presence of water, sodium carbonate, or potassium, or ammonium in an amount of 0.4 to 6.1 g/l (SU 1215307, C02F 1/58, publ. 29.02.88). After stirring the obtained suspension of the product of the reaction in the form of particles cyanide iron defend, the precipitate was separated. The residual content of CN-ions 0,06-0,40 mg/L.

The disadvantages of this method are the high consumption of ferrous sulfate, auxiliary substances, the long duration of the deposition product processing, noticeable residual concentration of CN-ion in water, the periodicity of the process.

There is also known a method of purification of waste water from cyanide ions by treatment of the mixture with a solution of sulphate ferrous iron in its consumption of 9.2 parts by weight to 1 parts by weight of ion CN with intensive mixing (SU 1380179, C02F 1/58, publ. 10.04.96). In the solution of iron sulphate is introduced into the flow of water parallel to the directional flow equal to the speed of the flow of waste water, followed by tightening the threads. The content of CN-ions in purified in the de after settling 0,08-of 2.86 mg/L.

The disadvantages of the method is the high complexity of the process, a high consumption of ferrous sulfate, noticeable residual content in the water CN-ions, the periodicity of the process.

New results from the use of the proposed method are simplifying the process, reducing consumption of iron sulfate, increasing the level of treatment, providing treatment in a continuous mode.

The above results are achieved by the fact that in the method of purification of waste water from cyanide ions, including its handling sulfate ferrous iron with the formation of the product of the reaction in the form of insoluble particles cyanide of iron, the removal of the product from water, according to the invention, the water treatment is carried out in the presence of water sorbent in the form of fibrillated cellulose fibers, containing in wt.% not less than 54% of fibres with a length of not more than 0,63 mm and not less than 94% of fibres with a length of not more than 1,23 mm, ferrous sulfate spend in the number of 293 parts by weight per 100 parts by weight of CN-ions, the reaction product is obtained as a composite material consisting of cellulose fibers with sorbed on them particles cyanide of iron, with the treatment product is removed from water by using pressure flotation. Cellulose fibers are served in water in an amount of 50-150 mg per 1 liter

Cellulose fibers (black) with these characteristics have a very high sorbl the authorized ability to chemically precipitated particles at the moment of their formation. In the composite material (KM), particulate cyanide iron (CI) may be more than 800 parts by weight per 100 parts by weight of fibers (CI:black>800:100). In practice, the sorption of particles, it is advisable to hold up to the value of the ratio CI:COL=300(±50):100. When increasing the length of the fibers of their activity and sorption capacity decreases, decreasing the length of the activity and capacity increase, however, at the same ratio CI:black increases the water retention KM and, consequently, difficulties arise when it is dehydration required for its disposal.

Fibrillated cellulose fibers have another important property. In the aquatic environment, they are even at a concentration of, for example, from 0.005% in water without stirring quickly form flocculi and cereals that are good at keeping air bubbles easily flatirons to the water surface and form a stable flotsam. When the use of such fibers in the process of pressure flotation there is no need to use auxiliary reagents, such as coagulants, flocculants and photoagency.

These properties fully possesses and KM.

Formed during flotation flotsam consisting of composite material, to be disposed of or cleaned. For this purpose it is first dewatered, for example, using a filter press or centrifuge, washed, again both voivat and dried. The dried material can be calcined at 500°C and to receive as a result of the decay scheme 3Fe(CN)2→3Fe3C+5C+3N2harmless products. You can also composite material treated with a solution of KCN and get the solution valuable product - yellow blood salt K4[Fe(CN)6]and regenerated silver.

The method is as follows. Preparing a suspension of the sorbent with the above characteristics of the fibers with their concentration, for example, 3 wt.%. Prepare a solution of sulphate ferrous iron to its concentration, for example, 10%.

Water cleaned in the unit of continuous action, including the mixer, reactor, saturator, the flotation machine and the filter press.

In the mixer serves the waste water and the specified number of color from obtaining a dispersion containing fibers 50-150 mg/l of water. The dispersion is sent to the reactor, which also serves sulfate solution of ferrous iron calculated 293 parts by weight per 100 parts by weight of water contained in the CN-ions. As a result of reactions forms a water-insoluble product in the form of particles cyanide iron (II) Fe2[Fe(CN)6]that are sorbed on black with the formation of KM. The resulting dispersion is sent to the saturator, saturate it with air at a pressure of 2-3 ATM and served in the flotation cell. In the flotation cell composite material completely oated with the formation of flotsam. His conclusion is drawn from the flotation cell, direct to dehydration and further processing.

The following examples illustrate the possibilities of the proposed method.

Example 1. Purify water with the content of CN-ions in the composition of NaCN or KCN 10 mg/liter mixer to water add black at the rate of 50 mg/L. the resulting dispersion is sent to the reactor and serves in her solution of FeSO4from the calculation of 29.3 mg per 1 liter of dispersion. As a result of reactions are formed 20,75 mg CG in 1 l of water and, accordingly, 70,75 mg KM with a value in it in parts by weight CG:COL=41,5:100. The dispersion is sent to the saturator, then in the flotation cell, where KM is oated. In the starting period of operation of the plant since the beginning of the breeding flotsam from the flotation cell completely fed into the mixer and from that moment it was fresh sorbent stop. When you reach a ratio CI:black KM, equal to 300:100, part of MILES removed from the process, and in the mixer start fresh sorbent in the number equal to the number of color output from a process within KM.

Output KM dehydrated, washed, dried, treated with a solution of KCN and get 236,6 mg yellow blood salt out of every 100 mg CN-ions from waste water during its treatment.

Purified water contains sulphate of sodium or potassium in an amount equivalent to equal content in wastewater CN-ions, i.e. 9,105 mg Na2SO4or 11,17 mg K2SO4 in 1 l of treated water. CN-ions in the water are not detected.

Example 2. Unlike example 1, the waste water contains 278 mg/l CN-ions in water color is supplied from the calculation of 150 mg/l, the solution of FeSO4dispense in dispersion in the reactor based 814,54 mg per 1 l of water. As a result of reactions in 1 l of water are formed 576,57 mg CG and, accordingly, 726, 57 mg km, with the balance of CG:COL=384:100. From the process shows all KM. It is washed, dewatered, dried and calcined at 520°C with the formation of iron carbide FeC, carbon and gaseous N2. Purified water contains 253,12 mg PA2SO4or 310.5 mg K2SO4,CN-ions in the water are not detected.

Example 3. Purify water with the content of CN-ions in the form of Na2[Zn(CN)4] in the amount of 120 mg/L. gray served in the water in the mixer at the rate of 100 mg/L. Solution of FeSO4dispense in a dispersion solution in the amount of 351,6 mg/l In the reaction are formed 163,88 mg/l Na2SO4,186,26 mg/l ZnSO4and 248,95 mg/l particles CJ, adsorbed on 100 mg black with education 348,46 mg/l KM. KM can be processed as described in examples 1 and/or 2. Purified water can be used to obtain a composite sorbent in the form of silver adsorbed on them particles of zinc hydroxide. This sorbent can be used to obtain gold cyanide way. In this method, after the separation of the gold in the waste water in RA is solved form contains Na 2[Zn(CN)4].

1. The method of purification of waste water from cyanide ions, including its handling sulfate ferrous iron with the formation of the product of the reaction in the form of insoluble particles cyanide of iron, the removal of the product from water, wherein the water treatment is carried out in the presence of water sorbent in the form of fibrillated cellulose fibers, containing in wt.% not less than 54% of fibres with a length of not more than 0,63 mm and not less than 94% of fibres with a length of not more than 1,23 mm, ferrous sulfate spend in the number of 293 parts by weight per 100 parts by weight of CN-ions, the reaction product is obtained as a composite material consisting of cellulose fibers with sorbed on them particles cyanide of iron, with the treatment product is removed from water by using pressure flotation.

2. The method according to claim 1, characterized in that the cellulose fibres are served in water in an amount of 50-150 mg per 1 liter



 

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