WO2023038541A1 - Method of obtaining bromide salts - Google Patents

Abstract

The invention relates to obtaining metal bromide salts from bromine-containing multicomponent brines during the comprehensive treatment thereof and can be used to produce the saleable products NaBr, CaBr2Н2О, MgBr22H2O, SrBr22Н2О, LiBrН2О, Li2CO3, LiClH2O, LiOHН2О, MgO, MgCl2, Ca(OCl)2, SrCO3 from industrial calcium-magnesium chloride-type brines used in oil and gas production. The invention includes: technical solutions concerning the deep purification of industrial brine to remove petroleum products, iron and manganese; the obtaining of bromide solutions by absorbing bromine from bromine-air mixtures produced by the air desorption method, using alkaline solutions or slurries in the presence of reducing agents; and the extraction of lithium chloride from industrial brine that has been through the bromine extraction stage, using a granular LDH sorbent with lithium selectivity to obtain a primary lithium concentrate in the form of an aqueous solution of lithium chloride, from which Li2CO3, LiClН2О and LiOHH2O are obtained. A portion of the productive brine that has been through the bromine and lithium extraction stage is used to obtain Mg(OH)2, MgO, MgCl26H2O, neutral Са(OCl)2 and strontium concentrate. The invention also makes it possible to obtain from industrial brines solutions of NaOH and Na2CO3, Cl2, Н2 for use as reagents and energy carriers for obtaining Li2CO3, Mg(OH)2, Са(OCl)₂ and SrCO₃.

Description

METHOD FOR OBTAINING BROMIDE SALTS

Technical field

The present invention relates to the field of chemical technology and can be used in relation to the complex processing of polycomponent hydro-mineral raw materials and, in particular, natural bromine chloride brines containing bromide ions, lithium, magnesium, calcium, sodium and strontium ions, containing in addition, impurities of petroleum products, iron and manganese.

State of the art

The key solutions and techniques on which the industrial production of inorganic bromides is based, including modern production, were developed in the middle of the last century [Pozin M.E. Technology of mineral salts. Part 1, ed. 3rd revision and add. Moscow: "Chemistry", 1970, pp. 206 -236]. The fundamental process of all, without exception, technologies for obtaining inorganic bromides from bromine-bearing hydromineral raw materials is the separation of bromine from a raw material source. In this case, the primary technological operation is the oxidation of bromide ions to elemental bromine, which is a very volatile ingredient that is easily separated from brines by distillation.

Depending on the concentration level of elemental (oxidized) bromine, it is distilled off with a carrier gas flow, which is either superheated water vapor or air. The use of live steam is considered effective at concentrations of elemental bromine in brine of 1 kg/m ³ and above, provided that the primary product of production is elemental bromine.

All of the above technological methods and operations are basic in all, without exception, existing and proposed methods for obtaining commercial bromine products from bromine-bearing hydromineral raw materials. Otherwise, the existing and proposed methods differ in the choice of means for oxidizing bromide ions to elemental bromine, means for recovering elemental bromine from the carrier gas stream, and means for converting it into any commercial product. The traditional oxidizing agent contained in bromine brines of bromide ions into elemental bromine is gaseous chlorine, mechanically mixed with brines [Ksenzenko V.I., Stasinevich D.S. Chemistry and technology of bromine, iodine and their compounds. Moscow: "Chemistry"; 1979, p. 116 - 212]. In view of the fact that inorganic bromides can be produced from solutions obtained by absorbing bromine directly from bromine-air flows without the need to obtain elemental bromine as a reagent, modern trends in the production of inorganic bromide salts are based on the implementation of interactions of solutions or slurries of compounds of alkali, alkaline earth metals and magnesium , as well as compounds of other metals in the presence of reducing agents that exclude contamination of bromide solutions, with elemental bromine in the composition of bromine-air mixtures.

So the UK patent [UK Patent No. 285915] discloses the technological process for obtaining a concentrated solution of calcium bromide by reacting pulps based on calcium hydroxide or carbonate with bromine, which is part of the bromine-air mixture in the presence of reducing agents, for example, urea, cyanide, ammonium carbonate, formamide, formic acids, excluding contamination of the bromide solution with any foreign cations or anions. The main disadvantage of this method is the formation of by-products of hypobromite and bromate.

The method of obtaining metal bromides [US Patent No. 1863375, US Patent No. 2007758] using ammonia as a reducing agent reduces the risk of formation of hypobromites and bromates in bromide solutions. The disadvantage of this method is the risk of contamination of bromide solutions with chloride ions at the stage of oxidation by bromide ions with chlorine gas in violation of the ratio 2Br/Ch in favor of chlorine.

The application [Application US No. 20170283272 (CN 107999001A)] describes a method and equipment in relation to the production of high-purity calcium bromide from calcium hydroxide using an ammonium hydroxide solution as a reducing agent and as an absorbent of bromine. The method is multistage. At the first stage of interaction, during the absorption of bromine by the Ca(OH)2 pulp with an ammonia solution, predominantly HBr and N2 are formed according to the reaction:

ZVG2 + 2NH ₃ -> 6НВg + N2 (1).

The resulting hydrobromic acid then reacts with calcium hydroxide:

2HBr + Ca(OH) ₂ - CaBr ₂ + 2H ₂ O (2).

Along with CaBrg, by-products, for example, Ca(BrO3)r, can be formed at the first stage. To eliminate this undesirable phenomenon, the second stage of the process involves the introduction of a certain amount of hydrazine and is described by a chemical reaction:

Ca(BrO3) ₂ + 6N2H2 - CaBr ₂ + 6N2 + 6H ₂ O (3).

The disadvantage of this method is the limited range of products produced only by calcium bromide in the processing of polycomponent bromine brines containing, along with bromine, other valuable elements, such as lithium, calcium, magnesium, as well as the need to use imported commercial calcium hydroxide and a poisonous reagent - hydrazine as a reagent.

A method for the complex processing of bromine-bearing polycomponent hydro-mineral raw materials, implemented on an industrial scale in the USA using the polycomponent brine of the Great Salt Lake (BSO, Utah) as a raw material source [Yu.I. Ostroushko, L. V. Degtyarev. Hydromineral raw materials - an inexhaustible source of lithium / Analytical review, Moscow: TsNIIAtominform, p. 40 - 49] eliminates the disadvantages of the previous method by significantly expanding the range of commercial products produced. Along with bromine, sodium, potassium, magnesium sulfates, boric acid, bischofite are produced from this raw material source. The disadvantages of this method include the impossibility of implementing this method in a non-arid climate, since the method is based on the classical gallurgical scheme of staged evaporation of lake brine in artificial pools. Another disadvantage of this method is the lack of a real possibility of cost-effective production of lithium products from this raw material source, despite the rather high content of lithium in the one stripped off (final) brine.

In Russia in the 80s - 90s of the last century, technologies for the complex processing of bromine-bearing multicomponent brines were developed in relation to bromine-bearing formation brines of the sodium chloride type of Dagestan deposits [N.P. Kotsupalo, A.D. Ryabtsev. Chemistry and technology for obtaining lithium compounds from lithium-bearing hydromineral raw materials. Novosibirsk: academic publishing house "GEO", 2008. - 291 s - ISBN 978-5-9747-0114-6] and all, without exception, had low technical and economic indicators. The main reason for this was their focus mainly on the large-scale production of lithium products from these raw materials, as the main ones, in the absence of methods for the selective isolation of lithium from multicomponent brines at that time.

The practical implementation of the complex processing of bromine-bearing polycomponent hydro-mineral raw materials containing lithium in its composition, including chloride brines of the calcium-magnesium type, began as a result of the development of technologies for obtaining commercial lithium products based on the selective reagent-free extraction of lithium using a granular sorbent, including a compound of a disordered structure , corresponding to the general chemical formula LiCl 2 A1(OH)3 pHgO and capable of selectively sorbing LiCl from multicomponent brines at room temperature and releasing sorbed LiCl upon contact of a saturated sorbent with fresh water [Patent RU No. 2284298].

On this basis, a method has been developed for obtaining granular calcium chloride in the complex processing of natural brines [Patent RU No. 2284298], including precipitation of CaCh H2O with an admixture of magnesium chloride from supersaturated brines of the calcium-magnesium chloride type, separation of the mother brine enriched by 1.3 - 1.4 times with lithium and bromine from the sediment, obtaining from the mother brine enriched with lithium and bromine a lithium concentrate using a granular sorbent based on LiCl 2A1(OH)3 pH2O, followed by precipitation of LiCl3 from the lithium concentrate with soda. After the extraction of lithium, the mother brine is used to produce bromine and magnesium oxide. At the same time, a part of the lithium concentrate, after purification from impurities and concentration, is subjected to membrane electrolysis, producing a solution of LiOH, which is processed into LiOH H2O, and anodic chlorine, which is used as an oxidizer of bromide ions into elemental bromine.

In terms of its technical essence and the achieved result, this method is the closest to the claimed one and was chosen by us as a prototype. However, along with the undoubted advantages, this method has disadvantages. The disadvantages of the method are:

- the absence in the technological cycle of operations that make it possible to purify brines from impurities of oil products, iron and manganese, which makes it difficult to use it directly for the complex processing of commercial brines of calcium-magnesium chloride type of oil and gas producing enterprises;

- the method is highly effective only in the processing of bromine-bearing brines supersaturated in salt content, in particular, in calcium content;

- obtaining inorganic bromides by this method only through the bromination of bases or carbonates of alkali, alkaline earth metals with elemental bromine, desorbed from the brine with live steam, followed by condensation into the liquid phase upon cooling;

- a limited range of manufactured commercial products.

The proposed method for the complex processing of bromine polycomponent hydro-mineral raw materials retains all the advantages of the prototype and eliminates the above disadvantages.

The essence of the invention

The technical result, which eliminates these shortcomings, is achieved using the following technical and technological solutions.

The technical result is achieved by the fact that the flow of the original commercial brine is alkalized, maintaining the pH in the commercial brine flow at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the flow of atmospheric air at the rate of 0.4 - 0.5 m ³ atmospheric air per 1 m ³ of commercial brine to transfer the soluble form of valence iron (+2) into the insoluble phase of iron with valency (+3), the resulting mixed air-brine flow is degassed by pouring it into a vessel having a blow-off into the atmosphere, with the output of the oil-enriched ascending part of the degassed flow of the commercial brine through the upper drain, followed by supply to the settling tank for separating oil and commercial brine and the output of the main descending part depleted in oil products degassed flow of commercial brine through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to transfer the soluble form of manganese with a valence (+2) into an insoluble form of manganese with a valence (+4), after sequential dosing into a commercial stream depleted in oil products, degassed and undergoing the stage of oxidation of manganese solution of the coagulant and flocculant, it is sent to the operation of flotation cleaning from suspended particles of impurities in a radial flotation machine with a flocculant and a saturation unit, a frothy drain of the flotation cell containing particles of impurities removed from the commercial brine flow after dosing flocculant is directed to the separation of solid and liquid phases in a press filter, the part separated from suspended particles is mixed with the flow of commercial brine entering the flotation.

The technical result is achieved by the fact that the commercial brine stream, which has passed the stages of flotation and control filtration, purified from impurities of oil products, iron and manganese, is sent to the operation of extracting lithium chloride on a granular sorbent DGAL-C1, the basis of which is the inorganic compound LiCl 2A1 (OH) 3 selective to LiCl pNgO, with the production of primary lithium chloride concentrate.

The technical result is achieved by the fact that the commercial brine that has passed the stage of extracting lithium chloride is sent to the operation of ejecting chlorine gas and oxidizing the bromide ions contained in the commercial brine into elemental bromine, while the desorption of elemental bromine from the commercial brine is carried out with a carrier gas flow returned to the operation desorption of elemental bromine after passage of a carrier gas stream saturated with bromine in succession of operations of absorption purification from active chlorine impurities in the form of an interhalogen compound BrCl, absorption purification from bromine and thus constantly circulating in a closed circuit: desorption of elemental bromine from a stream of commercial brine - purification from excess active chlorine in the form of the interhalogen compound BrCl - absorption of elemental bromine by alkaline and carbonate absorbents containing reducing agents to obtain aqueous solutions of bromide salts as bromine absorption products - desorption of elemental bromine from the field flow brine. The technical result is achieved by the fact that part of the stream of commercial brine that has undergone the extraction of lithium is used to extract magnesium in the form of magnesium hydroxide by introducing hydroxyl ions into the brine, extracting calcium in the form of calcium hydroxide, introducing hydroxide ions into the brine, extracting strontium in the form of carbonate strontium concentrate introduction of carbonate ions into the brine.

The technical result is achieved by the fact that in the case of the formation of carbon dioxide during the operation of absorption of bromine by alkaline carbonate absorbents in the presence of reducing agents, the flow of circulating carrier gas that has passed the operation of absorption of bromine is additionally subjected to purification from carbon dioxide by alkaline absorbents to obtain solutions or suspensions of carbonate salts as products absorption of carbon dioxide.

The technical result is achieved by the fact that the flow of bromine-containing carrier gas is purified from impurities of active chlorine in the composition of the interhalogen compound BgCl by absorption of BgCl by an aqueous solution of metal bromide, directing the spent absorbent to mixing with bromine-bearing commercial brine before its chlorination, the processes of absorption of bromine vapor from the gas stream - the carrier is carried out in two stages in the circulation-flow motion of the bromine absorbent in relation to the movement of the carrier gas stream being cleaned, while the output of the volume of the completely spent absorbent, which is a productive solution of the bromide salt, is carried out per unit time in a continuous mode from the first stage of absorption when the indicator is reached pH in the circulating absorbent is 5.0 - 5.5, compensating for the loss of absorbent by supplying an equivalent volume of absorbent to the first stage from the second absorption stage, in turn compensating the loss of absorbent in the second stage by supplying an equivalent volume to the second stage of absorption original absorbent.

The technical result is achieved by the fact that the purification of the carrier gas from carbon dioxide is carried out in two stages in the circulation-flow mode of movement of the absorbent containing sodium hydroxide in relation to the movement of the carrier gas stream purified from bromine, while the output of the volume of completely spent absorbent, which is with a productive sodium carbonate solution, is carried out in a continuous mode from the first absorption stage when the pH value in the circulating absorbent solution reaches 9.0 - 9.5, compensating for the volume loss by supplying an equivalent volume of absorbent to the first absorption stage from the second absorption stage, in turn, compensating loss of absorbent in the second stage of absorption by supplying to the second stage of absorption of an equivalent volume of the initial sodium hydroxide solution.

The technical result is achieved by the fact that the chlorine gas ejected by a stream purified from petroleum products, iron and manganese is produced by membrane electrolysis of a solution of sodium chloride obtained as a result of separation from a stream purified from oil products, iron and manganese commercial brine of bromine, lithium chloride, magnesium in the form of magnesium hydroxide, calcium in the form of calcium hydroxide, strontium in the form of carbonate strontium concentrate and purified from the remnants of impurities of calcium, magnesium, strontium and sulfate ions, first reagent alkaline carbonate method, then by ion exchange on the Lewatit TR-208 ion exchanger in the Na-form or on the ion exchanger analog in the Na-form, the NaOH solution produced as a by-product in the production of chlorine gas by membrane electrolysis is used as an alkaline reagent for the production of sodium bromide and soda solution, as well as a precipitating agent for the precipitation of manganese and calcium from the past stage of extraction of bromine, lithium chloride, magnesium, calcium and strontium for its reagent purification from the remainder of impurities, in addition, a soda solution produced from NaOH at the stage of obtaining a productive bromide solution metal is used as a reagent for the production of lithium carbonate and carbonate trontium concentrate.

The technical result is achieved by the fact that the Ca(OH)g, NaOH and Ch products produced from the components of the commercial brine are used as raw materials for the production of neutral calcium hypochlorite.

The technical result is achieved by the fact that to obtain productive solutions: sodium bromide, lithium bromide, magnesium bromide, calcium bromide, strontium bromide as absorbents of elemental bromine from the carrier gas flow, respectively, use: an aqueous solution of sodium hydroxide or an aqueous solution of sodium carbonate, an aqueous solution lithium hydroxide or an aqueous suspension of lithium carbonate, an aqueous suspension of magnesium hydroxide or an aqueous suspension of magnesium carbonate, an aqueous suspension of calcium hydroxide or an aqueous suspension of calcium carbonate, an aqueous suspension of strontium hydroxide or an aqueous suspension of strontium carbonate, and as a reducing agent ammonia, hydrazine, hydrazine hydrate, hydroxylamine , carbamide, formic acid or analogues of these reducing agents, the elemental composition of which excludes the risk of contamination of bromine absorbents by side ingredients.

The technical result is achieved by the fact that the resulting solutions of bromide salts are evaporated to obtain melts of bromide salts, the melts of bromide salts are cooled and either anhydrous solid-phase bromide salts, for example sodium bromide, or solid-phase crystalline hydrates of bromide salts, for example, calcium bromide dihydrate crystalline hydrate, are obtained.

The technical result is achieved by the fact that magnesium hydroxide isolated from the field solution is used to obtain magnesium oxide of the closing components of magnesia cements in the form of a solution of magnesium chloride and a solution of magnesium bicarbonate

NIA. The technical result is achieved by the fact that the solid phase of particles removed from the composition of the flotators, which is a mixture of FeO3 and MgCh with oil products, is used as a raw material additive at metallurgical enterprises.

The technical result is achieved by the fact that the primary lithium chloride concentrate obtained using the chloride-selective granular sorbent DGAL-C1 (based on the inorganic compound LiCl 2A1 (OH) 3 T1H2O of a disordered structure) after concentration by LiCl and purification from impurities is used to produce lithium carbonate, lithium chloride monohydrate, lithium hydroxide monohydrate, while anodic chlorine, formed during the production of lithium hydroxide monohydrate at the operation of membrane electrolysis of a solution of lithium chloride into a solution of lithium hydroxide, is used to oxidize bromide ions to elemental bromine in the technology for producing bromide salts from commercial brines of calcium chloride -magnesium type oil and gas producing enterprises.

The technical result is achieved by the fact that the flow of the original commercial brine is alkalized by mixing with an alkaline reagent, the pH in the commercial brine flow is maintained at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the atmospheric air flow at the rate of 0.4 - 0.5 m3 of atmospheric air per 1 m3 of commercial brine to transfer the soluble form of iron with valence (+2) into the insoluble form of iron with valence (+3), the resulting mixed air-brine flow is degassed by pouring it into a vessel having a blow-off into the atmosphere, with output of the ascending part of the degassed commercial brine stream enriched with oil products through the upper drain with subsequent supply to the source of the initial commercial brine and the withdrawal of the main descending part of the degassed commercial brine stream depleted in oil products through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to convert the soluble form of manganese with a valence (+ 2) in non-rac the created form of manganese with a valence (+4), is sequentially dosed into the coagulant and flocculant, depleted in oil products, degassed and undergoing the stage of oxidation of manganese, the flow of commercial brine, and it is sent to the operation of flotation purification from suspended particles of impurities in a radial flotator with a flocculator and a saturation unit, a frothy drain of the flotator , containing suspended particles of impurities removed from the flow of commercial brine after dosing the flocculant into it, is sent to the separation of solid and liquid phases in a press filter, the liquid phase separated from suspended particles of impurities is mixed with the flow of commercial brine entering the flotation, the flow that has passed the operations of flotation and control filtration purified commercial brine is first fed to the operation of ejecting chlorine gas and oxidizing the bromide ions contained in the commercial brine into elemental bromine, carried out desorption of elemental bromine from the commercial brine is carried out by a carrier gas stream, which is returned to the elemental bromine desorption operation after passing through the carrier gas stream saturated with bromine of successive operations, in which absorption purification from an admixture of active chlorine in the form of an interhalogen compound BrCl, absorption purification from bromine is carried out, and thus ensure constant circulation in a closed loop: desorption of elemental bromine from the flow of commercial brine - purification from excess active chlorine in the form of interhalogen compound BrCl - absorption of elemental bromine by alkaline and carbonate absorbents containing reducing agents to obtain aqueous solutions of bromide salts as products bromine absorption - desorption of elemental bromine from the flow of commercial brine, and the flow of the commercial solution, which has passed the stage of extraction of bromine, is directed to the extraction of lithium chloride on a granular sorbent, which is used as LiC1.2Al (OH )3.nH2O of a disordered structure, with the production of a lithium chloride concentrate, while using a part of the stream of commercial brine that has undergone the extraction of lithium and bromine for the sequential extraction of magnesium in the form of magnesium hydroxide by introducing hydroxyl ions into the brine, the extraction of calcium in the form of calcium hydroxide by introducing hydroxyl into the brine -ions, extraction of strontium in the form of a carbonate strontium concentrate by introducing carbonate ions into the brine.

The advantage of the proposed method in comparison with the method of the prototype is:

1. In expanding the range of hydromineral bromine raw materials suitable for obtaining bromide salts by bringing to the use of multicomponent commercial brines of oil and gas producing enterprises for these purposes;

2. In expanding the range of commercial products produced from the same raw material source;

3. In reducing the cost of production by expanding the range of manufactured products;

4. In the possibility of commissioning any of the technological stages as soon as it is ready, regardless of the readiness and operation of other technological stages;

5. In the possibility of implementing the production of bromides of any metals without the need to restructure the hardware design.

The reality of achieving the technical result is confirmed by the description of the technological scheme for the complex processing of bromine-bearing polycomponent commercial brines of calcium-magnesium chloride type.

List of drawings Fig. 1. Principal process flow diagram for the production of metal bromides from field polycomponent bromine-bearing brines of calcium-magnesium chloride type.

In accordance with the process flow diagram (Fig. 1), the flow of the original bromine-bearing multicomponent brine with pH = 4.5 - 5.0, containing oil products, iron (+2) and manganese (+2) in the form of impurities, is alkalized with a NaOH solution to pH \u003d 6.5 - 7.0 and subjected to aeration by mixing with a given volumetric flow of atmospheric air for the oxidation of Fe ²⁺ to Fe ³⁺ according to the mechanism described by the following chemical reactions:

The mixed brine-air flow of the brine is degassed in the process of its downward movement through a container having a blow-off into the atmosphere. In the process of degassing, the oil is partially floated by air and coagulated. The upper layer of brine enriched with oil in the process of degassing is constantly withdrawn from the process with a small flow through the upper drain and returned to the oil and brine separation stage. The main flow of degassed and partially depleted in oil products and containing suspended particles of Fe ₂ O ₃ is removed through the bottom drain and mixed with an oxidizing agent solution in the form of a compound containing hypochlorite ions (NaOCl or Ca(OC1)g) to oxidize soluble Mn ²⁺ to insoluble Mn ⁴⁺ by reaction:

MnCh + OCF + H ₂ O - * MnO ₂ ; + ZSG + 2Н ⁺ (5)

After dosing coagulant and flocculant into the brine flow, it enters the operation of flotation of the suspended particles of Fe ₂ O ₃ contained in it, MnOg and residual oil. During the flotation process, suspended solids are removed from the main brine stream in the top froth overflow. A flocculant is dosed into the foam overflow stream and subjected to phase separation on a press filter. The cake obtained after separation of the phases, containing Fe ₂ O ₃ , MnOg and the remains of oil products is stored and sent to metallurgical plants, and the liquid phase is mixed with the brine flow entering the flotation.

The proposed technology for the complex processing of commercial polycomponent bromine brines also allows you to change the sequence of input of bromine and lithium technological stages without changing the main indicators of these industries. On the basic technological scheme, the implementation option for the advanced introduction into production of lithium processing unit in relation to bromine is shown by a dash-dotted line. If the technological scheme for the production of complex processing of commercial bromine-bearing multicomponent brines is implemented according to the option involving the extraction of bromine from the purified brine before the extraction of lithium chloride (on the basic technological scheme, the implementation option for the advanced introduction of bromine redistribution into production in relation to lithium is shown by a solid line), then the past operations flotation and control filtration, the brine is sent to the operation of chlorine gas ejection. The ejection operation provides, firstly, uniform dissolution of chlorine gas in the volume of the commercial brine flow, and secondly, optimal conditions for the oxidation of bromide ions contained in the commercial brine into elemental bromine, which is described by the following chemical reaction equation:

С1 ₂ + 2ВГ -> Вг ₂ + 2СГ (6)

In view of the fact that the achievement of a high degree of oxidation (not lower than 95%) of bromide ions can be ensured only by an excess of chlorine dissolved in the commercial brine, the formation of a certain amount of the interhalogen compound BrCl is inevitable in the brine according to the reaction:

Br ₂ + C1 ₂ -> 2BrC1 (7)

Further, the commercial brine, containing in its composition dissolved Br with an admixture of BrCl, enters the operation of desorption of bromine from the commercial brine into the gas phase. For the desorption of bromine from the commercial brine, a process is used based on countercurrent contact of the carrier gas flow with the commercial brine flow in apparatuses that provide a highly developed contact surface of the interacting phases. The process of bromine desorption is carried out in a circulation-countercurrent mode of movement of the commercial brine with respect to the movement of the carrier gas flow saturated with Br and BrCl vapors, which allows changing the depth of bromine desorption during operation with a change in the bromine concentration in the commercial brine. Having passed the desorption stage and saturated with Br and BrCl vapors, the carrier gas is first purified from chlorine bromide by countercurrent absorption from the carrier gas flow by an absorbent containing bromide ions in its composition. As an absorbent, BrCl can act as a part of the commercial brine that has passed the stage of purification from iron, manganese and oil products, and a part of the productive solution of metal bromide, which is the final product of the bromine absorption operation. The process of BrCl absorption by bromide absorbents is described by the following chemical reaction equation:

BrC1 + VG -> _Br2 + C? (8)

В случае использования щелочных растворов и пульп в присутствии аммиака процесс абсорбции описывается следующими уравнениями химических реакций: Thus, the carrier gas flow is enriched with elemental bromine, and the active chlorine, which is in the composition of BrCl, passes into the absorbent, being reduced to chlorine ions. Purified from active chlorine and enriched with bromine, the carrier gas enters the bromine absorption operation. The operation of absorbing elemental bromine from a carrier gas stream to obtain a productive bromide solution as the end product of this operation is carried out with alkaline solutions or carbonate solutions (NaOH, arCO3, LiOH, KOH, K2CO3), alkaline (Ca(OH)g, Mg(OH) 2, 8g (OH)g) or carbonate (CaCO3, MgCOs, ZrCO3. N2CO3) pulps in the presence of reducing agents such as NH3, N2H2, (NH2)2CO, which exclude contamination of bromide solutions with foreign cations or anions. In the case of using alkaline solutions and pulps in the presence of carbamide, the absorption process is described by the following equations of chemical reactions:

In the case of using alkaline solutions and pulps in the presence of ammonia, the absorption process is described by the following equations of chemical reactions:

2NH3(r) + 6OH(p) + 3Br2( _G ) — ► N2(r)T + 6Br'(p) + 6H2O (13)

NH _{3 (} r) + H ₂ O (p) -\u003e NH ₄ OH (p) (14)

SVg ₂ (g) + 2NH ₄ OH _(P ) N2 ₍ r)? + 6НВг( _Р ) + 2Н ₂ О ₍ р) (15)

OH'(p) + HBr(p) - Br'(p) + HgO(p) (16)

In the case of using carbonate solutions and pulps in the presence of ammonia, the absorption process is described by the following equations of chemical reactions:

The process of alkali-carbonate absorption is carried out in the mode of countercurrent movement of the carrier gas flow and the absorbent flow in two stages with the flow-circulation movement of the absorbent in stages.

The first absorption stage mainly performs the function of finishing the absorbent coming from the second stage to a productive bromide solution (NaBr, CaBr, MgBr ₂ , LiBr, SrBn) with a concentration close to 300 g/dm ³ with a pH value of 5.0 - 5.5. At this stage, the degree of absorption does not exceed 65%. The second stage of absorption performs the functions of deep purification of the carrier gas from bromine vapor by maintaining a sufficient precisely high alkalinity in the circulation tank of the second absorption stage. The absorbent of the second stage of bromine absorption, transferred to the first stage, has a pH value of 8.5 - 9.0. The proposed scheme for the absorption of bromine from a carrier gas makes it possible to simplify the process control by outputting a given volume of a productive bromide solution per unit of time equivalent to the volume of the initial absorbent supplied for absorption.

The carrier gas purified from bromine vapors, if it contains carbon dioxide resulting from the absorption of bromine by carbonate solutions or pulps, as well as from the absorption of bromine by alkaline solutions using urea as a reducing agent, is subjected to purification from carbon dioxide by its absorption with NaOH solution , described by the following chemical reaction equation:

CO2(g) + NaOH(p) —> NagCO3(p) + HgO(p) (24)

The organization scheme of the carbon dioxide absorption process is similar to the organization scheme of bromine absorption with the complete identity of the equipment used. At the same time, the first stage of CO2 absorption performs mainly the function of finishing the absorbent coming from the second stage of absorption to a productive soda solution, composition: MagSOz - 225 - 230 g/dm ³ , d=l 157 g/dm ³ , pH=9.5. At the second stage of absorption, a deep removal of CO2 from the carrier gas stream is ensured by maintaining the pH value in the absorbent at a level of 11.0 - 11.5. The productive NaOH solution is withdrawn from the first stage, compensating the withdrawn volume by supplying the NaOH solution to the second stage of absorption, the concentration determined by the calculation of the material balance.

Produced productive bromide solution is used for the production of anhydrous bromides or for the production of their crystalline hydrates by deep evaporation and crystallization upon cooling. For example, the production of anhydrous NaBr from a productive solution of sodium bromide is carried out in two steps. At the first stage, the solution is evaporated until the density of the evaporated medium reaches 1400 - 1420 g / dm ³ , that is, until a melt is obtained

NaBr. Evaporation of the melt is carried out until the crystallization of anhydrous NaBr and the achievement of T : W = 4.75 - 5.0 : 1, which corresponds to a temperature of 142 - 145°C.

In turn, the evaporation of the productive CaBrg solution is carried out until a melt corresponding to the composition CaBr 2HgO is obtained. Next, the melt is converted into a solid phase by pouring onto the cooled surface of a rotating drum. The layer “freezing” on the surface of the drum is cut off with toothed scrapers, obtaining a flaky calcium bromide crystalline hydrate corresponding to the general formula CaBr 2HrO.

Bromides of other metals are produced in a similar way, using hydroxides or carbonates of the corresponding metals (Li, Mg, Sr, Zn, Fe, etc.). Technological processes in this case will differ only in the values of the concentrations of the corresponding bromides in the produced productive solutions and the temperature conditions for dehydration of the productive solutions of bromides.

The commercial brine, which has passed the bromine extraction stage, is directed to the extraction of lithium chloride. The extraction of lithium chloride is carried out on a granular selective sorbent DGAL-C1, the basis of which is a compound of lithium and aluminum, corresponding to the general formula NCH2A1(OH)3 pH ₂ O and having a disordered structure. Upon contact with a highly mineralized lithium-bearing chloride brine, this compound is able to selectively sorb (intercalate) LiCl from the brine until it is completely saturated with lithium, while giving an equivalent amount of water to the brine. In turn, when the sorbent saturated with lithium chloride comes into contact with fresh water, desorption (deintercalation) of lithium chloride from the saturated sorbent into fresh water occurs, thus forming the primary lithium concentrate in the form of a dilute aqueous solution of lithium chloride with an admixture of brine microcomponents and returning to the sorbent the ability to sorb LiCl again. from brine. In this case, the LiCl desorption process is accompanied by the intercalation by the sorbent of water molecules lost during the operation of LiCl sorption from the brine. The process of production of primary lithium concentrate can be described by the following equations: stage of sorption (intercalation) of LiCl from brine

LiCl [LPR] + [LiCl 2A1 (OH) z.pN ₂ O] - (1 - m) LiCl [LPR] +

где: [ЛПР] - литиеносный промысловый рассол. + [(1 + m)LiC12Al(OH) ₃ (nm)H ₂ 0] (25) stage of desorption (deintercalation) of LiCl from saturated sorbent

where: [LPR] - lithium-bearing commercial brine.

The primary lithium concentrate obtained without reagents after purification from impurities and concentration in the form of a productive solution of LiCl is used for the production of lithium products Li ₂ CC> 3 and LiOH H ₂ O.

Lithium carbonate is obtained from the productive solution by precipitation. As precipitants, concentrated solutions of Na ₂ CC> 3 or (MH^gCO3) are used in accordance with the reactions taking place:

2LiCl _(P ) + Na ₂ CO ₃ ( _P) - Li ₂ CO _{3 (T} )i + 2NaCl _(p) (27)

2LiCl _(p ) + (NH ₄ )2CO3( _P ) Li ₂ CO _3(T )i + 2NH4Cl _(p) (28)

The Na ₂ COs solution obtained during the production of bromides can be used to precipitate lithium carbonate. Lithium hydroxide monohydrate is produced by obtaining a productive solution of LiCl by membrane electrolysis to obtain a solution of LiOH, cathodic hydrogen and anodic chlorine. The process is described by the following overall reaction:

Membrane electrolysis

2LiCl( _P ) + HgO(p) — > LiOH( _P ) + H2(g) + C1 ₂ (g) (29)

The LiOH solution obtained by membrane electrolysis is evaporated, LiOH H2O crystallizes. Anode chlorine is used as an oxidizing agent for bromide ions at the technological stage for the production of bromide salts from commercial brine. Cathodic hydrogen is used as a heat carrier in the production of heating steam.

Commercial brine, past the stage of extraction of bromine and lithium chloride, is divided into two streams. One of the streams (main) is used in hydrocarbon production technology. Another stream of commercial brine (smaller) is first sent to extract magnesium by precipitating it in the form of hydroxide using NaOH solution or Ca(OH) ₂ suspension for precipitation according to the reactions:

MgCl ₂ ( _P ) + 2NaOH _(P ) Mg(OH) ₂ (T)l + 2NaCl _(p) (30)

MgCl ₂ (p) + Ca(OH) ₂ (p) Mg(OH)2 ₍ T)l + CaC12 _(P ) (31)

Precipitation of magnesium with a suspension of Ca(OH) ₂ is preferred because it eliminates the risk of formation of colloidal solutions that make it difficult to separate the solid phase of Mg(OH) ₂ from the mother field solution. The resulting precipitate Mg(OH) ₂ is used either to obtain magnesia by drying and calcining according to the reaction: t>450°C

Mg(OH) ₂₍ T) MgO _(T ) + H ₂ O(«) (32) or to obtain various modifications of Sorel cement. To this end, only a portion of the magnesium hydroxide produced is used to produce MgO. Another part of Mg(OH) ₂ is used to obtain mixing solutions according to the reactions:

Mixing MgO with a mixing solution makes it possible to obtain high-quality magnesium cements (Sorel cement), which have high strength and chemical resistance in multicomponent brine environments.

After removal of magnesium, the flow of commercial brine enriched with NaCl or CaCh is directed to the precipitation of Ca(OH)g, carried out with a solution of NaOH according to the reaction:

CaCh(p) + 2NaOH( _P ) — * Ca(OH) ₂ (t) + 2NaCl( _P ) (35) After separation from the brine, the Ca(OH) ₂ precipitate produced is used as an absorbent for the production of CaBr ₂ 2H ₂ O, as a magnesium precipitant, and also as a reagent for the production of neutral calcium hypochlorite.

After the precipitation of calcium, the flow of commercial brine enriched with NaCl is used to obtain a carbonate strontium concentrate by using a solution of Na ₂ CO3 as a precipitant. The process is described by the following chemical reaction equation:

SrCl ₂ ( _P ) + Ma ₂ CO3( _P ) — > 8rCO3(t)1 + 2NaCl( _P ) (36)

Since the commercial brine entering the precipitation of strontium inevitably contains a residual amount of calcium (the solubility of Ca(OH) ₂ in the commercial brine is not lower than 2.5 g/dm ³ ), the precipitated strontium carbonate will be contaminated with CaCO3.

After the precipitation of strontium, the commercial brine, which is transformed into NaCl brine during the extraction of lithium, bromine, magnesium, calcium and strontium after reagent purification from sulfate ions and the remainder of calcium, magnesium and strontium, is sent for ion-exchange purification using Lewatit 208TP polyampholyte in Na as a sorbent -form or analogues of this ion exchange resin. The ion-exchange purification process is described by the following equations:

Na ⁺

[Lewf

\Na ⁺ _(T)

Regeneration of the spent ion exchanger is carried out in two stages: first, with a solution of hydrochloric acid to obtain an “acidic” solution of MgCh and CaCl ₂ as the spent regenerate and transfer the ion exchanger to the H-form, then with a NaOH solution to transfer the ion exchanger to the Na-form. The regeneration process is described by the following equations:

The spent regenerates are sent for mixing with the industrial brine (NaCl solution) that has passed the strontium precipitation stage and is supplied to the reagent cleaning operation. After reagent purification, the NaCl solution is used as a raw material for the production of NaOH solution and chlorine gas by membrane electrolysis. The process is described by the following overall reaction:

Membrane electrolysis

2NaCl _(p ) + 2H ₂ O (p) 2NaOH _(p) + H _{2 (g)} T + C1 _{2 (g} ) T (40)

The produced chlorine gas is used as the main reagent in the production of bromides. The NaOH solution, which is the catholyte of membrane electrolysis, is used as a reagent for the production of productive sodium bromide and sodium carbonate solutions, as well as a reagent for the precipitation of Mg(OH) ₂ and the production of neutral calcium hypochlorite. Cathodic hydrogen is used as an energy carrier in the production of heating steam used in the evaporation of productive bromide solutions.

Neutral calcium hypochlorite is obtained by precipitation of the Ca(OC1) ₂ phase, from the resulting exchange reaction when mixing saturated aqueous solutions of sodium hypochlorite and calcium hypochlorite, produced by chlorination of a NaOH solution and a suspension of Ca(OH) ₂ according to the reactions:

The Ca(OS1) ₂ precipitate is separated from the mother liquor and dried to obtain commercial calcium hypochlorite with an active chlorine content of at least 60% w/w. and containing in its composition water-insoluble impurities in an amount of not more than 6.0% wt.

The active chlorine mother liquor of the neutral calcium hypochlorite precipitation operation is divided into two streams and, after dosing the appropriate amounts of NaOH and Ca(OH) _{2 ,} is returned to the operations for obtaining hypochlorite solutions (reactions 41, 42).

The possibility of implementing the proposed method for the complex processing of bromine-bearing polycomponent hydro-mineral raw materials in the form of commercial brines of calcium-magnesium chloride oil-producing enterprises in practice is confirmed by the following examples.

Example 1

Commercial polycomponent bromine brine, the elemental composition of which is presented in table 1, was used as a feedstock for the production of anhydrous sodium bromide and calcium bromide crystalline hydrate in a pilot plant for the production of bromides, designed and assembled in accordance with the scheme of bromide the division shown in Fig. 1. The productivity of the pilot plant for the processing of commercial brine was 1224 dm ³ /h. NaOH solution (bromine absorbent) and (NHg^CO (reducing agent) were used as reagents for obtaining NaBr. To obtain samples of calcium bromides, in one case, an aqueous suspension of Ca(OH)g (absorbent) and CMHg)gCO (reducing agent) were used. In the case of an aqueous suspension of CaCO3 (absorbent) and KHN3 (reductant). The specific consumption of regents for cleaning 1 dm ³ of the original commercial brine from oil products, iron and manganese was: NaOH (neutralizing agent, flocculant) - 17.6 mg; atmospheric air - 0.5 dm ³ ; polyacrylamide (coagulant) - 7.3 mg; calcium hypochlorite - 39.4 mg. The return flow of commercial brine enriched with oil products in the degassing process was 9.75 dm ³ /h with an oil content of 14.71 g/dm ³ , iron 0.3 g/dm ³ , manganese 0.1 g/dm ³ .

Поток очищенного от примесей промыслового рассола, поступающего на переработку, составлял 1214,25 дм³/ч. Остаточное содержание примесей в промысловом рассоле, используемом для получения образцов бромидных солей, составляло: нефтепродукты < 5 мг/дм³; Fe < 1 мг/дм³; Мп < 1 мг/дм³. Массовый выход, высушенного до отсутствия потери веса кека, образующегося при переработке пенного слива флотатора составил 579,3 г/ч при вещественном составе (% мае.): нефтепродукты - 16,03; РегОз - 54,21 ; МпОг - 21,80; НгО - 7,96. Основные показатели технологических процессов получения бромидов из очищенного продуктивного бромоносного поликомпонентного рассола представлены в таблице 2. Таблица 2 - Основные показатели процессов получения образцов бромидов из очищенного от примесей рассола

Table 1 - Composition of the original commercial brine

The flow of commercial brine purified from impurities entering the processing was 1214.25 dm ³ /h. The residual content of impurities in the commercial brine used to obtain samples of bromide salts was: oil products <5 mg/dm ³ ; Fe < 1 mg/ ^dm3 ; Mp < 1 mg/dm ³ . The mass yield of the cake dried to the absence of weight loss, formed during the processing of the frothy drain of the flotator, was 579.3 g/h with a material composition (% wt.): oil products - 16.03; PerOs - 54.21; MnOg - 21.80; HgO - 7.96. The main indicators of technological processes for obtaining bromides from a purified productive bromine-bearing polycomponent brine are presented in Table 2. Table 2 - The main indicators of the processes for obtaining samples of bromides from a brine purified from impurities

Produced productive bromide solutions were subjected to dehydration. The productive NaBr solution was first evaporated to reach a density of 1412 g/dm ³ , then the evaporated solution was dehydrated under vacuum with stirring to T : W = 4.8 : 1, cooled, the resulting product after grinding weighed 6.508 kg. The results of the analysis of the obtained sample for the content of the main substance and impurities are presented in table 3. Productive solutions of calcium bromide No. 1 and No. 2 were evaporated to obtain a melt (t=147°C), which was dehydrated under vacuum until the melt reached a temperature of 198°C, which corresponds to residual water content in the melt corresponding to the chemical formula CaBr2HgO (hydrated calcium bromide). The obtained melts were poured onto a rotating cooled drum equipped with scrapers, the shell of which was made of titanium. The resulting flake products were weighed. The weight of the sample from the productive solution No. 1 was 8.251 kg, and the weight of the sample from the productive solution No. 2 was 7.887 kg. The results of the analysis for the content of the main substance and impurities are presented in table 4.

Table 3 - Indicators of the obtained sample of sodium bromide in comparison with the product corresponding to TU 20.13.31-003-55547777, grade 1

Table 4 - Indicators of the obtained samples of hydrated calcium bromide

The results obtained confirm the possibility of obtaining high-quality bromide salts by the proposed method from commercial waters of oil and gas processing enterprises by the proposed method. At the same time, the yield of bromine from the bromine-bearing commercial brine into commercial bromides is at least 93.5% while maintaining the material composition of the brine. The experiments also confirm the possibility of obtaining a wide range of bromide salts by the proposed method.

Example 2

The commercial brine that passed the stage of bromine extraction (residual bromine content 0.26 g/dm ³ and pH=2) after adjusting the pH of the brine to 6.5-7.0 was used as a raw material for the production of lithium products in a pilot plant. A pilot plant for the production of lithium products, including a sorption-desorption module (SDM) for separating the primary lithium concentrate from the commercial brine, which passed the stage of bromine extraction, which was based on four sorption-desorption columns containing a granular sorbent DGAL-S1 (granule size 0.30 - 3.2 mm) in volume

29 dm ³ in each column. The device of the sorption-desorption module of four columns made it possible to conduct the process of obtaining primary lithium concentrate in a continuous mode with minimal downtime of the columns at the stages of the technological operation obtaining a primary lithium concentrate, which included: a stepwise stage of displacement of the brine from the column, which passed the stage of sorption and saturation of the sorbent with lithium chloride, a staged stage of water desorption of lithium from the sorbent, which passed the stage of removal of the brine.

The resulting primary lithium concentrate was divided into three equal parts, each of which, after purification from impurities and concentration (reverse osmosis concentration in combination with thermal concentration), was brought to productive lithium concentrates from which samples of LigCO3, NCHH2O and LONH2O were produced, the weight of which was respectively 1.387 kg, 2.185 kg and 1.425 kg. The main indicators of the technological production of primary lithium concentrate are presented in Table 5. The compositions of Li2CO3, LiCl H2O and NOH H2O samples obtained from primary lithium concentrate are presented in Table 6.

Table 5 - Main indicators of the technology for obtaining primary lithium concentrate from commercial brine that has passed the stage of bromine extraction

Table 6 - Chemical composition of commercial lithium products produced from primary lithium concentrate

The experiments performed confirm the possibility of separating LiCl from brine in the form of primary lithium concentrate from polycomponent commercial brines of oil and gas producing enterprises and producing high-quality lithium products from it. The macro-base of commercial brine after passing through the lithium stage remains unchanged with a decrease in the total salt content by no more than 2% due to dilution of the brine with spent washing brine.

Example 3

According to the method described in example 2, the primary lithium concentrate was obtained from a multicomponent commercial brine purified from petroleum products, iron and manganese, which was not subjected to bromine extraction. The composition of the resulting primary lithium concentrate (g/DM ³ ): Li - 0.529; Ca - 1.33; K ⁺ -0.15; Mg ²⁺ - 0.10; Na - 0.08; Cl - 6.34; Br - 0.08; SO' - 0.01; HCO3 - 0.04; B <0.01; pH - 7.0 differed significantly from the composition of the primary lithium concentrate produced in example 2, only the content of bromine (0.08 g/DM ³ in relation to 0.005 g/DM ³ ). However, this did not lead to a significant increase in the bromine content in the lithium carbonate sample produced from the primary lithium concentrate, in which the bromine content did not exceed 0.001% wt.

Example 4

Part of the flow of commercial brine that passed the stage of extraction of bromine and lithium chloride was used to sequentially obtain samples of Mg(OH)2, Ca(OH)2 and a sample that had been concentrated. The commercial brine stream obtained at the final stage was processed into NaCl brine, which, after reagent and ion-exchange purification from Mg and Ca, was used to produce a concentrated NaOH solution (catholyte) and chlorine gas by membrane electrolysis of NaCl brine. Gaseous SI produced by membrane electrolysis and NaOH solution (30 - 32 wt %) were used as reagents in the production of bromides, in the production of precipitated Mg(OH)2, Ca(OH)2 and neutral calcium hypochlorite. The concentration of NaCl in the anolyte at the entrance to the cell maintained at the level of 270 - 280 g/DM ³ when the content of HC1 1 - 2 g/DM ³ . The composition of NaCl make-up brine in the anolyte was (g/dm ³ ): NaCl - 300 - 310; C103 <15; SO4 ² '<4.0; Ca + Mg + Sr < 0.5 10' ³ . The temperature of the electrolysis was maintained at 70 - 80°C. The current efficiency of chlorine was 94 - 96%, the current efficiency of alkali was 75 - 85%.

Precipitation of Mg(OH)2 from the field solution was carried out in two stages: at the first stage, achieving the maximum degree of Mg(OH)2 content in the sediment, precipitation was carried out with a mixed suspension of Ca(OH)g and Mg(OH)2, removing the formed precipitate by thickening and thick phase filtration. Next, the phase of the commercial brine with a residual content of MgCh was brought into contact with the NaOH solution, achieving the introduction of a stoichiometric amount of NaOH in relation to the mass amount of MgCh in the volume of the initial processed commercial solution. The precipitate was washed and divided into two unequal parts. Most of the washed cake after drying contained 99.3% Mg(OH)2. The obtained products: solid-phase MgO (binder) and Mg(HCOa)2 solution (closing agent) were further used in the preparation of various Sorel cement samples.

Precipitation of Ca(OH)g from the commercial brine, which passed the stage of magnesium extraction, was carried out with a NaOH solution based on the input of 90% of the stoichiometric amount of CaCh in the processed solution. The precipitation was carried out in one stage. The Ca(OH)g precipitate was separated from the mother liquor by centrifugation. After washing, the wet precipitate of Ca(OH)g contained up to 0.4% wt. strontium and up to 0.2% sodium. The resulting wet precipitate of Ca(OH)g was used as a reagent to obtain a saturated solution of Ca(OC1)g + CaCh by chlorination of an aqueous pulp of Ca(OH)g. The solution extremely saturated in NaOCl, necessary for obtaining neutral calcium hypochlorite by the exchange reaction, was produced by direct chlorination of the catholyte (NaOH solution) with anodic chlorine produced by membrane electrolysis of the NaCl solution. Samples of neutral calcium hypochlorite produced from reagents obtained from multicomponent commercial brine after drying and grinding had the form of a white powder and had the following composition (% wt.): active chlorine - 62 - 63; HgO - 1.8 - 2.0; sediment insoluble in water - 4.0 - 4.1, with a thermal stability coefficient of at least 90%. All samples of the resulting product met the requirements of GOST 25263-82, grade 1.

Claims

28 Claims 1. The method of complex processing of bromine-bearing polycomponent hydromineral raw materials, including the production of a lithium chloride concentrate from bromine-bearing polycomponent hydromineral raw materials by a sorption method using a granular sorbent DGAL-C1, the basis of which is an inorganic compound LiCl 2A1 (OH)3 pNgO selective to LiCl, followed by direct contact of the bromine-bearing polycomponent hydromineral raw materials with a given mass amount of gaseous chlorine, accompanied by the oxidation of bromide ions into elemental bromine, desorption of elemental bromine from the flow of bromine-bearing polycomponent hydromineral raw materials and the production of magnesium oxide from magnesium hydroxide isolated from bromine-bearing polycomponent hydromineral raw materials, otl and h and with the fact that commercial brines of calcium-magnesium chloride type of oil and gas producing enterprises are used as bromine-bearing polycomponent hydromineral raw materials, while the flow of the initial about the commercial brine is alkalized by mixing with an alkaline reagent, the pH in the commercial brine flow is maintained at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the atmospheric air flow at the rate of 0.4 - 0.5 m ³ of atmospheric air per 1 m ³ of commercial brine to transfer the soluble form of iron with a valence (+2) into an insoluble form of iron with a valence (+3), the resulting mixed air-brine flow is degassed by pouring it into a vessel having a blow-off into the atmosphere, with the withdrawal of the ascending part enriched with oil products degassed flow of commercial brine through the upper drain, followed by supply to the source of the original commercial brine and the withdrawal of the main descending part of the degassed commercial brine depleted in oil products through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to convert the soluble form of manganese with valence (+2) into an insoluble form manganese valency (+4), successor coagulant and flocculant are dosed into the oil-depleted degassed and manganese-oxidized flow of commercial brine, and it is sent to the operation of flotation purification from suspended particles of impurities in a radial flotator with a flocculator and a saturation unit, a frothy drain of the flotator containing suspended particles removed from the commercial brine flow After the flocculant is dosed into it, the impurities are sent to the separation of the solid and liquid phases in a press filter, the liquid phase separated from the suspended particles of impurities is mixed with the commercial brine flow entering the flotation, the purified commercial brine flow, which has passed the flotation and control filtration operations, is fed to the lithium chloride extraction operation on granular sorbent, which is used as 1lSG2A1(OH)3 pNgO of a disordered structure, with the production of lithium chloride concentrate, then the commercial brine freed from lithium chloride is fed to the operation of ejecting chlorine gas and oxidizing the bromide ions contained in the commercial brine into elemental bromine, desorption of elemental bromine from of commercial brine with a carrier gas stream, which is returned to the elemental bromine desorption operation after passing through the carrier gas stream saturated with bromine of successive operations, in which absorption purification is carried out from an admixture of active chlorine in the form of an interhalogen compound BrCl, absorption purification from bromine, and thus provide , constant circulation in a closed circuit: desorption of elemental bromine from the stream of commercial brine - purification from excess active chlorine in the form of interhalogen compound BrCl - absorption of elemental bromine by alkaline and carbonate absorbents containing reducing agents to obtain aqueous solutions of bromide salts as products of absorption of bromine - desorption of elemental bromine from the stream of commercial brine, while using a part of the stream of commercial brine that has undergone extraction of lithium and bromine for the sequential extraction of magnesium in the form of magnesium hydroxide by introducing hydroxyl ions into the brine, extraction of calcium in the form of hydroxide calcium by introducing hydroxyl ions into the brine, extracting strontium in the form of carbonate strontium concentrate by introducing carbonate ions into the brine. 2. The method according to claim 1, characterized in that in the case of the formation of carbon dioxide in the operation of absorption of bromine by alkaline and carbonate absorbents in the presence of reducing agents, the flow of circulating carrier gas, which has undergone the operation of absorption of bromine, additionally subjected to absorption purification from carbon dioxide with a NaOH solution to obtain a Na2COs solution. 3. The method according to p. mixing with bromine-bearing commercial brine before its chlorination, the processes of absorption of bromine vapor from the carrier gas stream are carried out in two stages in the circulation-flow movement of the bromine absorbent relative to the movement of the carrier gas stream being cleaned, while removing the volume of completely spent absorbent, which is a solution of bromide salt , per unit time is carried out in continuous mode from the first stage of absorption when the pH value in the circulating absorbent reaches 5.0 - 5.5, compensating for the loss of the absorbent by supplying an equivalent volume of absorbent from the second stage of absorption to the first stage of absorption, in turn compensating for the loss of the absorbent in the second stage by supplying to the second absorption stage an equivalent the volume of the original absorbent. 4. The method according to p. of the carrier gas stream purified from bromine, while the volume of the completely exhausted absorbent, which is a solution of sodium carbonate, is removed continuously from the first stage of absorption when the pH value in the circulating absorbent solution reaches 9.0 - 9.5, compensating for the decrease in volume by supplying to the first absorption stage of an equivalent volume of absorbent from the second absorption stage, in turn, compensating for the loss of absorbent in the second absorption stage by supplying an equivalent volume of the initial sodium hydroxide solution to the second absorption stage. 5. The method according to p. obtained as a result of the separation from the flow of commercial brine of lithium chloride, bromine, magnesium in the form of magnesium hydroxide, calcium in the form of calcium hydroxide, strontium in the form of carbonate strontium concentrate and purified from residues of impurities of calcium, magnesium, strontium and sulfate ions, first with a reagent alkali-carbonate method, then by ion exchange on the Lewatit TR 208 ion exchanger in the Na-form or on the ion exchanger - analogue in the Na-form, the NaOH solution obtained in the production of chlorine gas by membrane electrolysis is used as an alkaline reagent for the production of sodium bromide and soda solution, as well as in as a precipitating agent for the precipitation of magnesium and calcium from the past stage of extraction of lithium chloride and bromine of the field solution at the stage and its reagent purification from the remainder of impurities, in addition, a soda solution produced from NaOH in the operation of obtaining a metal bromide solution is used as a reagent for obtaining lithium carbonate and strontium carbonate concentrate. 6. The method according to paragraphs. 1, 5, differing in that the Ca(OH)2, NaOH, and Ch products produced from the components of the commercial brine are used as raw materials for the production of neutral calcium hypochlorite. 7. The method according to p. carrier, respectively, using an aqueous solution of sodium hydroxide or an aqueous solution of sodium carbonate, an aqueous solution of lithium hydroxide or an aqueous suspension of lithium carbonate, an aqueous suspension of magnesium hydroxide or an aqueous suspension of magnesium carbonate, an aqueous suspension of calcium hydroxide or an aqueous suspension of calcium carbonate, an aqueous suspension of strontium hydroxide or an aqueous suspension of strontium carbonate, and as reducing agents ammonia, hydrazine, hydrazine hydrate, hydroxylamine, urea, formic acid. 8. The method according to p. salts. 9. The method according to claim 1, characterized in that magnesium hydroxide isolated from the commercial brine is used to produce magnesium oxide and closing components of magnesia cements in the form of a solution of magnesium chloride and a solution of magnesium bicarbonate. 10. The method according to claim 1, characterized in that the solid phase of particles removed from the composition of the foamy drain of the flotator, which is a mixture of FeO3 and MnCh with petroleum products, is used as a raw material additive at metallurgical enterprises. 11. The method according to claim 1 differs in that the obtained lithium chloride concentrate after concentration by LiCl and purification from impurities is used for the production of lithium carbonate and / or lithium chloride monohydrate and / or lithium hydroxide monohydrate , while anodic chlorine, formed during the production of lithium hydroxide monohydrate at the operation of membrane electrolysis of a solution of lithium chloride into a solution of lithium hydroxide, is used for the oxidation of bromide ions to elemental bromine in the technology for producing bromide salts from field brines of calcium-magnesium chloride type of oil and gas producing enterprises. 12. A method for the complex processing of bromine-bearing polycomponent hydromineral raw materials, including direct contact of a stream of bromine-bearing polycomponent hydromineral raw materials with a given mass amount of gaseous chlorine, accompanied by the oxidation of bromide ions into elemental bromine, desorption of elemental bromine from a stream of bromine-bearing polycomponent hydromineral raw materials, subsequent production from bromine-bearing polycomponent hydromineral raw materials raw materials of lithium chloride concentrate by the sorption method using granular sorbent DGAL-C1, which is based on the LiCl-selective inorganic compound LiCl2A1(OH)3 pH2O and obtaining magnesium oxide from magnesium hydroxide isolated from bromine-bearing polycomponent hydromineral raw materials, and with the fact that commercial brines of calcium-magnesium chloride type of oil and gas producing enterprises are used as bromine-bearing polycomponent hydromineral raw materials, while the flow of the initial the commercial brine is alkalized by mixing with an alkaline reagent, the pH value in the commercial brine flow is maintained at the level of 6.5 - 7.0, then the commercial brine flow is mixed with the atmospheric air flow at the rate of 0.4 - 0.5 m ³ of atmospheric air per 1 m ³ of commercial brine to transfer the soluble form of iron with valence (+2) into the insoluble form of iron with valence (+3), the resulting mixed air-brine stream is degassed 32 by pouring it into a vessel having a blow-off into the atmosphere, with the output of the ascending part of the degassed flow of commercial brine enriched with oil products through the upper drain, followed by supply to the source of the original commercial brine and the withdrawal of the main descending part of the degassed flow of commercial brine depleted in oil products through the lower drain for mixing with an oxidizing agent containing hypochlorite ions to convert the soluble form of manganese with valence (+2) into the insoluble form of manganese with valence (+4), the coagulant and flocculant are sequentially dosed into the degassed and manganese-oxidized stream of commercial brine depleted in oil products and sent to the flotation cleaning operation from suspended particles of impurities into a radial flotator with a flocculator and a saturation unit, the foamy drain of the flotator, containing suspended particles of impurities removed from the flow of commercial brine, after dosing the flocculant into it, is directed to the separation of solid and liquid phases into the press filter, the liquid phase separated from suspended particles of impurities is mixed with the flow of commercial brine entering the flotation, the stream of purified commercial brine that has passed the operations of flotation and control filtration is fed to the operation of ejecting chlorine gas and oxidizing the bromide ions contained in the commercial brine into elemental bromine , carry out the desorption of elemental bromine from the commercial brine with a carrier gas stream, which is returned to the elemental bromine desorption operation after passing through the carrier gas stream saturated with bromine of successive operations, in which absorption purification from an admixture of active chlorine in the form of an interhalogen compound BrCl, absorption purification from bromine , and thus provide constant circulation in a closed circuit: desorption of elemental bromine from the flow of commercial brine - purification from excess active chlorine in the form of interhalogen compound BrCl - absorption of elemental bromine by alkaline and carbonate a bsorbents containing reducing agents to obtain aqueous solutions of bromide salts as bromine absorption products - desorption of elemental bromine from the flow of commercial brine, and direct the flow of commercial solution, which has passed the stage of bromine extraction, to extract lithium chloride on a granular sorbent, which is used as LiCl 2A1( OH)z pN3O of a disordered structure, with the production of lithium chloride concentrate, while using a part of the flow of commercial brine that has undergone the extraction of lithium and bromine for the sequential extraction of magnesium in the form of magnesium hydroxide by introducing hydroxyl ions into the brine, the extraction of calcium in the form of calcium hydroxide by introducing hydroxyl into the brine -ions, extraction of strontium in the form of a carbonate strontium concentrate by introducing carbonate ions into the brine.