RU2666859C2 - Method for complex purification of mine waters - Google Patents

Method for complex purification of mine waters Download PDF

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Publication number
RU2666859C2
RU2666859C2 RU2016147246A RU2016147246A RU2666859C2 RU 2666859 C2 RU2666859 C2 RU 2666859C2 RU 2016147246 A RU2016147246 A RU 2016147246A RU 2016147246 A RU2016147246 A RU 2016147246A RU 2666859 C2 RU2666859 C2 RU 2666859C2
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Russia
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water
purification
mine water
copper
nickel
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RU2016147246A
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Russian (ru)
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RU2016147246A3 (en
RU2016147246A (en
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Алексей Анатольевич Королев
Александр Тимофеевич Крестьянинов
Сергей Александрович Краюхин
Константин Леонидович Тимофеев
Василий Анатольевич Кочин
Василий Романович Курдюмов
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Акционерное общество "Уралэлектромедь"
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents

Abstract

FIELD: purification technology.SUBSTANCE: invention can be used in the technology of purifying mine water from copper, nickel, manganese and hardness salts to produce water for domestic and drinking purposes, up to the standards set for drinking water. Such method is carried out by complex multi-stage water purification process. In the first stage, mine water is filtered through load of quartz sand with a particle size of 0.8–2.0 mm, in the second stage, copper, nickel and manganese are recovered in three or more sorption filters by aminodiacetate ion exchanger with a flow rate of 5–10 specific volumes per loading of one filter. Then, mine water is treated with 20 % solution of sodium carbonate to pH of 6.5–8.5. After that, the resulting calcium and magnesium carbonates are removed in an ultrafiltration step and the purified water is disinfected with ultraviolet radiation.EFFECT: method provides for a comprehensive purification of mine water from polluting elements with a high removal efficiency of impurities.1 cl, 2 ex, 1 tbl

Description

The invention relates to methods for purification of mine water from heavy metals, mainly from copper, nickel and manganese, as well as from hardness salts (calcium and magnesium), and can be used to obtain household water due to the high efficiency of removing designated impurities.
A known method of purification of mine water from calcium and magnesium by filtration through an inorganic sorbent is a calcined flask obtained by firing alumina flask fractions <0.5 mm and 0.5-1.0 mm in a mass ratio of 5 to 2, respectively, to a temperature of 1000- 1100 ° C [1]. The disadvantages of this method include the low degree of extraction of the flask of copper, nickel and manganese ions from mine water, as well as the inability to regenerate the sorbent due to the peculiarities of its composition, which leads to the need for disposal of the spent material and its constant replacement.
A known method of purification of mine water from contaminants, including copper, nickel, manganese, and hardness salts, using reverse osmosis, in which there is a separation of the water stream under pressure of 2.0-2.5 MPa into a highly demineralized permeate and concentrate [2]. The disadvantages of this method include the need for special reagent preparation of mine water, which includes the addition of a coagulant to precipitate suspended solids, sodium metabisulfate to bind free chlorine, which destroys the membranes of the reverse osmosis unit, antiscale and sulfuric acid to prevent the deposition of hardness salts and salts of iron and manganese respectively on the installation membranes. This requires the installation of additional equipment and means for controlling the dosage of reagents, leading to additional economic costs. A common drawback of reverse osmosis schemes is the need to utilize concentrates from a reverse osmosis unit, which can be neutralized only by evaporation to obtain dry salts.
A known method of purification of groundwater from manganese and hardness salts by oxidation of the first compounds with oxygen and filtration on an inert load, followed by softening with a 4% sodium hydroxide solution [3]. The disadvantages of this method include the impossibility of purifying water from copper and nickel, as well as the high cost of alkali used to soften it.
There is a method of purifying water from manganese by filtration through loading of carbonate-type manganese ore thermally modified at 400-600 ° C, which is also a catalyst for the oxidation of manganese to a sparingly soluble compound [4]. However, this method does not involve the purification of mine water from copper, nickel and hardness salts. In addition, the catalytic charge is sensitive to the pH level of the source water: at pH <6.0, it may dissolve with the removal of manganese ions into the filtered water.
Closest to the claimed technology for purification of mine water is a method of extracting copper and iron from them using sorption on aminodiacetate ion exchange resin (ion exchange resin) ANKB-35 in the H + form, followed by desorption of the resin with sulfuric acid to obtain concentrated eluates [5]. In this method, copper ions are concentrated from 0.15 g / dm 3 in the original mine water to 4.60 g / dm 3 in the eluate, iron from 0.88 to 5.28 g / dm 3 . It also proposed a method for increasing the selectivity of copper extraction in order to obtain cleaner copper-containing eluates, which is achieved by hydrolytic precipitation of iron at pH = 3.5 before the sorption purification step. The disadvantages of this method include the lack of information on the comprehensive purification of nickel and manganese on the specified ion exchange resin, despite the mechanism of extraction of these metals similar to copper and iron.
The objective of the invention is the purification of mine water from copper, nickel and manganese ions with their subsequent softening, which can be used in a comprehensive purification of mine water from any impurities.
The problem is solved in that in the proposed method, mine water passes through several stages of purification. At the first stage, filtration through the loading of quartz sand with a particle size of 0.8-2.0 mm, the capture of mechanical impurities occurs. At the second stage, copper, nickel and manganese are extracted in sorption filters with aminodiacetate ion exchanger with a flow rate of 5-10 specific volumes for loading one filter. To obtain pure nickel eluates, which can be used in the production of nickel sulfate, treatment of mine water through three or more stages of filters loaded with ion exchanger is provided. Selective extraction of nickel ions occurs on the filter of the second stage. After sorption treatment, mine water is treated with a 20% solution of sodium carbonate, which allows you to adjust the pH of the water to 6.5-8.5, as well as reduce the content of hardness salts after the start of their removal from the ion-exchange resin. The resulting calcium and magnesium carbonates are removed in the ultrafiltration step. The purified water is disinfected with ultraviolet radiation.
The essence of the invention is illustrated by examples.
Example 1
Mine water was subjected to purification, including the following stages:
1) purification from mechanical impurities on a filter loaded with quartz sand;
2) sorption purification of copper, nickel and manganese on filters loaded with aminodiacetate ion exchanger;
3) adjustment of the pH level of water and its softening with a 20% sodium carbonate solution;
4) ultrafiltration of water to remove suspended calcium and magnesium carbonates;
5) disinfection of water by ultraviolet radiation;
6) resin regeneration with a 5% hydrochloric acid solution to obtain a nickel-containing eluate.
The extraction of copper in this case reached 98%, nickel - 95%, manganese - 99%. As a result of softening, it was possible to remove up to 95% calcium and up to 40% magnesium. The compositions of the source and treated mine water in comparison with the requirements of sanitary norms and rules are shown in table 1.
Figure 00000001
Example 2
Mine water was subjected to purification, including stages similar to example 1, except:
6) resin regeneration with 10% sulfuric acid solution to obtain a nickel-containing eluate.
The impurity extraction indices are similar to Example 1. After resin regeneration, eluates with a high nickel content of 10% and lower manganese content by 6% were obtained than after regeneration with hydrochloric acid, which makes it more preferable to use sulfuric acid. Nickel can be extracted from the resulting solution by evaporation to obtain nickel sulfate heptahydrate according to GOST 4465-74.
Example 3
Mine water was subjected to purification, including stages similar to example 1, but additionally was carried out:
7) chemical disinfection of water with 34% sodium hypochlorite solution. The indicators of the extraction of impurities and the quality of purified water are similar to example 1.
Information sources
1. Shuvalov Yu.V., Kuzmin D.N., Grishchenko A.E., Volkovskaya S.G. The method of purification of mine water // RF Patent No. 2260565 from 10.21.04. Publ. in bull. No. 26, 09/20/2005.
2. Yankovsky N.A., Stepanov V.A. The method of obtaining deeply demineralized water // RF patent №2281257 from 09/07/2004, Publ. in bulletin No. 6, 08/10/2006.
3. Zhurba MG, Govorova Zh.M., Govorov OB, Amosova EG, Dolgopolov PI, Rogovoy VA, Zhuravlev SP The method of purification of groundwater from iron, manganese and hardness salts // RF Patent No. 2285669 from 05/14/2005. Publ. in bull. No. 29, 10.20.2006.
4. Bochkarev G.R., Beloborodoe A.V., Pushkareva G.I., Skiter N.A. A method of purifying water from manganese // RF Patent No. 2184708 of 01/15/2001. Publ. in bull. No. 19 July 10, 2002.
5. Black M.L. Sorption extraction of rare-earth and non-ferrous metals from mine waters and pulps: dis. ... cand. tech. Sciences: 05.17.02 / M.L. The black; Ural State Technical University. - Yekaterinburg: USTU-UPI, 2005 .-- 142 p.: Ill. (As a manuscript).
6. Drinking water. Hygienic requirements for water quality of centralized drinking water supply systems. Quality control. SanPiN 2.1.4.1074-01. - M., 2002 .-- 62 p.

Claims (1)

  1. A method for comprehensive purification of mine water, including the stages of mechanical purification and sorption of copper on aminodiacetate ion exchange resin, characterized in that at the first stage, mine water is filtered through a load of silica sand with a particle size of 0.8-2.0 mm, in the second stage, copper, nickel and manganese are recovered in three or more sorption filters with aminodiacetate ion exchange resin with a flow rate of 5-10 specific volumes for loading one filter, then mine water is treated with a 20% sodium carbonate solution to a pH of 6.5-8.5, the resulting calcium and magnesium carbonates are removed in stages ultrafiltration and purified water is disinfected with UV radiation.
RU2016147246A 2016-12-01 2016-12-01 Method for complex purification of mine waters RU2666859C2 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2130477A1 (en) * 1971-06-19 1972-12-21 Bayer Ag Process for separating copper from the metals iron, cobalt, nickel and / or manganese
US4502645A (en) * 1981-07-28 1985-03-05 Ryobi Limited Fishing spinning reels
RU2033440C1 (en) * 1992-11-19 1995-04-20 Шуленина Зинаида Макаровна Method of extraction of copper from solution
RU2125105C1 (en) * 1996-12-06 1999-01-20 Внедренческий научно-экспериментальный центр "Экотур"(ИП ВНЭЦ) Method of nickel recovery from sheet solutions of electroplating
RU2213154C2 (en) * 2001-11-01 2003-09-27 Рычков Владимир Николаевич Method of recovering copper from mine water and pulps
CN101628761A (en) * 2009-08-18 2010-01-20 湖南邦普循环科技有限公司 Treatment method of nickel-cobalt-manganese wastewater generated in waste and old battery treatment process
RU2430981C1 (en) * 2010-03-30 2011-10-10 Владимир Алексеевич Гуров Procedure for extraction of nickel from solutions and for purification from impurities

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2130477A1 (en) * 1971-06-19 1972-12-21 Bayer Ag Process for separating copper from the metals iron, cobalt, nickel and / or manganese
US4502645A (en) * 1981-07-28 1985-03-05 Ryobi Limited Fishing spinning reels
RU2033440C1 (en) * 1992-11-19 1995-04-20 Шуленина Зинаида Макаровна Method of extraction of copper from solution
RU2125105C1 (en) * 1996-12-06 1999-01-20 Внедренческий научно-экспериментальный центр "Экотур"(ИП ВНЭЦ) Method of nickel recovery from sheet solutions of electroplating
RU2213154C2 (en) * 2001-11-01 2003-09-27 Рычков Владимир Николаевич Method of recovering copper from mine water and pulps
CN101628761A (en) * 2009-08-18 2010-01-20 湖南邦普循环科技有限公司 Treatment method of nickel-cobalt-manganese wastewater generated in waste and old battery treatment process
RU2430981C1 (en) * 2010-03-30 2011-10-10 Владимир Алексеевич Гуров Procedure for extraction of nickel from solutions and for purification from impurities

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DE 2130477 A1, 19/01.1971. *
ФРОГ Б.Н., ЛЕВЧЕНКО А.П. Водоподготовка. Москва, изд. "Ассоциация строительных вузов", 2007, с. 452. *
ЧЕРНЫЙ М.Л. Сорбционное извлечение редкоземельных и цветных металлов из шахтных вод и пульп. Авто диссертации на соискание ученой степени кандитата технических наук. Екатеринбург, 2005 г. *
ЧЕРНЫЙ М.Л. Сорбционное извлечение редкоземельных и цветных металлов из шахтных вод и пульп. Автореферат диссертации на соискание ученой степени кандитата технических наук. Екатеринбург, 2005 г. *

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