WO2023038541A1 - Procédé de production de sels de bromure - Google Patents

Procédé de production de sels de bromure Download PDF

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WO2023038541A1
WO2023038541A1 PCT/RU2022/000265 RU2022000265W WO2023038541A1 WO 2023038541 A1 WO2023038541 A1 WO 2023038541A1 RU 2022000265 W RU2022000265 W RU 2022000265W WO 2023038541 A1 WO2023038541 A1 WO 2023038541A1
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Prior art keywords
bromine
brine
commercial
flow
absorption
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PCT/RU2022/000265
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English (en)
Russian (ru)
Inventor
Александр Дмитриевич Рябцев
Сергей Александрович Антонов
Елизавета Петровна Гущина
Виктор Александрович БЕЗБОРОДОВ
Андрей Александрович Кураков
Николай Михайлович Немков
Алексей Олегович ПИВОВАРЧУК
Евгений Олегович ЧЕРТОВСКИХ
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Общество с ограниченной ответственностью "Экостар-Наутех"
Общество с ограниченной ответственностью "ИРКУТСКАЯ НЕФТЯНАЯ КОМПАНИЯ"
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Priority claimed from RU2021126423A external-priority patent/RU2780216C2/ru
Application filed by Общество с ограниченной ответственностью "Экостар-Наутех", Общество с ограниченной ответственностью "ИРКУТСКАЯ НЕФТЯНАЯ КОМПАНИЯ" filed Critical Общество с ограниченной ответственностью "Экостар-Наутех"
Publication of WO2023038541A1 publication Critical patent/WO2023038541A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C01F5/10—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium chloride with water vapour
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins

Definitions

  • 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.
  • elemental (oxidized) bromine 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.
  • a carrier gas flow which is either superheated water vapor or air.
  • 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.
  • 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.
  • 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.
  • 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 second stage of the process involves the introduction of a certain amount of hydrazine and is described by a chemical reaction:
  • 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.
  • 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.
  • 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.
  • this method is the closest to the claimed one and was chosen by us as a prototype.
  • this method has disadvantages.
  • the disadvantages of the method are:
  • the method is highly effective only in the processing of bromine-bearing brines supersaturated in salt content, in particular, in calcium content;
  • 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;
  • 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
  • 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
  • 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
  • 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.
  • anhydrous solid-phase bromide salts for example sodium bromide
  • solid-phase crystalline hydrates of bromide salts for example, calcium bromide dihydrate crystalline hydrate
  • 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 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.
  • the oil 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:
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • an absorbent containing bromide ions in its composition.
  • 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:
  • 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.
  • 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.
  • reducing agents such as NH3, N2H2, (NH2)2CO, which exclude contamination of bromide solutions with foreign cations or anions.
  • 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:
  • 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.
  • 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.
  • 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
  • the evaporation of the productive CaBrg solution is carried out until a melt corresponding to the composition CaBr 2HgO is obtained.
  • 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.
  • DGAL-C1 granular selective sorbent
  • this compound 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.
  • 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.
  • precipitants concentrated solutions of Na 2 CC> 3 or (MH ⁇ gCO3) are used in accordance with the reactions taking place:
  • 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:
  • 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.
  • 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
  • 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.
  • 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:
  • 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.
  • 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:
  • 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).
  • 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 .
  • Table 2 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
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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Abstract

L'invention se rapporte à la production de sels de bromure de métaux à partir de solutions salines bromifères à plusieurs composants lors de leur traitement complexe, et peut être utilisée pour produire des produits commerciaux NaBr, CaBr2Н2О, MgBr22H2O, SrBr22Н2О, LiBrН2О, Li2CO3, LiClH2O, LiOHН2О, MgO, MgCl2, Ca(OCl)2, SrCO3 à partir de solutions salines industrielles de type calcium-magnésium issues d'entreprises d'extraction de gaz et de pétrole. L'invention comprend des mesures consistant à purifier en profondeur une solution saline industrielle pour éliminer les produits pétroliers, le fer et le manganèse, obtenir des solutions de bromure par absorption du brome à partir de produits secondaires selon un procédé de désorption aérienne de mélanges brome-air avec des solutions alcalines ou des pulpes en présence d'agents réducteurs, extraire le chlorure de lithium de la solution saline industrielle ayant subi l'étape d'extraction de brome sur un sorbant granulé sélectif envers le lithium DHAL-C1 afin de produire un concentré de lithium primaire sous forme d'une solution aqueuse de chlorure de lithium à partir de laquelle on produit Li2CO3, LiClН2О et LiOHH2O. Une partie de la solution saline ayant subi l'étape d'extraction de brome et de lithium est utilisée pour la production de Mg(OH)2, MgO, MgCl26H2O, Са(OCl)2 neutre et de concentrée de strontium. L'invention permet également de produire à partie de solutions salines industrielles de solutions de NaOH et Na2CO3, Cl2, Н2, que l'on utilise comme réactifs et fluides énergétiques pour la production de Li2CO3, Mg(OH)2, Са(OCl)2 et SrCO3.
PCT/RU2022/000265 2021-09-08 2022-08-31 Procédé de production de sels de bromure WO2023038541A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2157339C2 (ru) * 1998-09-15 2000-10-10 Закрытое акционерное общество "Экостар-Наутех" Способ получения бромистого лития из рассолов
RU2189362C2 (ru) * 2000-06-19 2002-09-20 Общество с ограниченной ответственностью "ЛУКОЙЛ-Коми" Способ комплексной переработки попутных вод нефтяных месторождений
RU2190700C1 (ru) * 2001-01-09 2002-10-10 Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" Способ извлечения иода и брома из природных вод
RU2724779C1 (ru) * 2020-01-14 2020-06-25 Публичное акционерное общество «Татнефть» имени В.Д. Шашина Способ комплексной переработки попутных вод нефтяных месторождений
US20210087697A1 (en) * 2019-09-25 2021-03-25 Ecostar-Nautech Co., Ltd. Method for producing lithium hydroxide monohydrate from brines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2157339C2 (ru) * 1998-09-15 2000-10-10 Закрытое акционерное общество "Экостар-Наутех" Способ получения бромистого лития из рассолов
RU2189362C2 (ru) * 2000-06-19 2002-09-20 Общество с ограниченной ответственностью "ЛУКОЙЛ-Коми" Способ комплексной переработки попутных вод нефтяных месторождений
RU2190700C1 (ru) * 2001-01-09 2002-10-10 Государственное унитарное предприятие "Всероссийский научно-исследовательский институт химической технологии" Способ извлечения иода и брома из природных вод
US20210087697A1 (en) * 2019-09-25 2021-03-25 Ecostar-Nautech Co., Ltd. Method for producing lithium hydroxide monohydrate from brines
RU2724779C1 (ru) * 2020-01-14 2020-06-25 Публичное акционерное общество «Татнефть» имени В.Д. Шашина Способ комплексной переработки попутных вод нефтяных месторождений

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