WO2010092117A1 - Preparation of purified calcium chloride - Google Patents

Preparation of purified calcium chloride Download PDF

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Publication number
WO2010092117A1
WO2010092117A1 PCT/EP2010/051723 EP2010051723W WO2010092117A1 WO 2010092117 A1 WO2010092117 A1 WO 2010092117A1 EP 2010051723 W EP2010051723 W EP 2010051723W WO 2010092117 A1 WO2010092117 A1 WO 2010092117A1
Authority
WO
WIPO (PCT)
Prior art keywords
calcium chloride
chloride solution
purified
preparing
magnesium
Prior art date
Application number
PCT/EP2010/051723
Other languages
English (en)
French (fr)
Inventor
Claude Breton
Michel Hanse
Laurent Bessenay
David Savary
Original Assignee
Solvay Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Sa filed Critical Solvay Sa
Priority to RU2011137433/05A priority Critical patent/RU2011137433A/ru
Priority to CN2010800074965A priority patent/CN102317212A/zh
Priority to EP10703471A priority patent/EP2396278A1/en
Publication of WO2010092117A1 publication Critical patent/WO2010092117A1/en

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Classifications

    • 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
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C01F11/32—Purification
    • 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
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides

Definitions

  • the magnesium must be removed in order to meet the specifications for the end product. It is known that this step can be carried out by adding an alkaline agent to the medium to be purified, which agent results in the magnesium precipitating in the form of its hydroxide Mg(OH) 2 . Nevertheless, if the precipitation OfMg(OH) 2 is poorly controlled (from the point of view of the chemistry of the reaction and/or its implementation), the liquid/solid separation which follows will be very difficult to achieve.
  • the present invention proposes a process for preparing a purified calcium chloride solution comprising a step (d) of precipitating magnesium and other impurities from a calcium chloride solution containing magnesium and other impurities in solubilized form via alkalinization of this solution by addition of calcium hydroxide, preferably in the form of milk of lime, followed by a step (e) of separating the precipitate from the calcium chloride solution, preferably by settling and/or by filtration, so as to obtain a purified calcium chloride solution.
  • the liquid/solid separation may be carried out by any other suitable liquid/solid separation method such as, for example, a simple settling, or a centrifugation, or a filtration, or else by combining various known methods.
  • the precipitation in step (d) of magnesium and other impurities from a calcium chloride solution containing magnesium and other impurities in solubilized form via alkalinization of this solution by addition of calcium hydroxide, preferably in the form of milk of lime, is carried out in a continuous mode.
  • the step (d) is carried out in a batch or semi-batch mode.
  • the expression continuous mode is understood to mean a mode of realization of the precipitation step (d), according to which a reaction device is used, into which the calcium chloride solution and the calcium hydroxide are continuously or quasi-continuously introduced, and from which the solution and products of the reaction are continuously or quasi-continuously withdrawn.
  • the reaction device comprises advantageously one or more reactors sufficiently mixed to avoid the settling of the calcium hydroxide, when in solid form, and the settling of precipitate.
  • the continuous or quasi-continuous introduction of the calcium chloride solution and the calcium hydroxide can be realized with any suitable means such as for instance with centrifugal pumps or peristaltic pumps.
  • the introduction of calcium hydroxide, when in solid or powder form, in the reaction device can be carried out with any suitable means such as, for instance, with screw feeding systems, vibrating feeders, or loss-in weight feeding systems.
  • the continuous or quasi-continuous withdrawal of the solution and products of the reaction from the reaction device can be carried out with any suitable means such as, for instance, with centrifugal pumps or peristaltic pumps for a continuous withdrawal or with gravitational draining controlled sequentially by means of electric or pneumatic valves for a quasi-continuous withdrawal.
  • quasi-continuous introduction or withdrawal is understood to mean an introduction or withdrawal of solution, reactants, or products of reaction that, although non continuous in a strict sense, enable the same function, as for instance sequential introductions or sequential withdrawals in which the quantities of solution, reactants, or reaction products, are small compared to the total quantity contained in the reaction device.
  • the present description of the invention uses the term of precipitation of magnesium and other impurities in semi-batch mode.
  • the mean residence time of the calcium chloride solution in the device of reaction is advantageously equal to or greater than 15 minutes, preferably equal to or greater than 30 minutes. It is in general less than or equal to 5 hours, preferably less than or equal to 2 hours.
  • the concentration of the aqueous calcium chloride solution is generally equal to or greater than 10 weight % of calcium chloride, preferably equal to or greater than 30 weight %, more preferably equal to or greater than 32 weight %, and most preferably equal to or greater than 35 weight % of calcium chloride.
  • the concentration of the aqueous calcium chloride solution is generally less than or equal to 60 weight %, preferably less than or equal to 50 weight %, more preferably at less than or equal to 40 weight %, and most preferably less than or equal to 38 weight % of calcium chloride.
  • the temperature is generally equal to or greater than 20 0 C, preferably equal to or greater than 40 0 C, more preferably equal to or greater than 50 0 C, and most preferably equal to or greater than 55°C.
  • the temperature is advantageously less than or equal to 80 0 C, preferably less than or equal to 70 0 C, more preferably less than or equal to 65°C. In particular the temperature is about 60 0 C.
  • the inventors have indeed determined that a temperature below 40 0 C generally leads to a degradation of the settling parameters, and a judicious choice of the temperature within the above limits is therefore beneficial for an optimal precipitation and an optimal separation (see Example A.4).
  • the separation in step (e) can be carried out by any suitable method, for example a simple settling, or by a centrifugation
  • one particular embodiment of the present invention relates to the separation in step (e) by settling, followed by a pressurized filtration (see Example B.I).
  • a continuous process makes it possible to largely avoid the "batch" effect observed in batch or semi-batch mode.
  • the precipitated particles of magnesium hydroxide and of other impurities must have characteristics that are suitable as a function of the chosen separation method. For example, if the particles do not have a suitable size, they may pass through the filter or else rapidly clog it up. As already indicated, it has been shown that the size of the precipitated particles may be favorably influenced, inter alia, by the mode of addition of the calcium hydroxide (see Example A.1). Indeed, by favoring the growth of the Mg(OH) 2 particles by the addition of milk of lime in continuous mode, the separation in step (e) is improved, especially if it is carried out by settling and/or by filtration.
  • the particle size of the solid formed may be measured, for example, using a laser particle size analyzer according to one procedure described in the tests of the present document.
  • the magnesium precipitated in step (d) advantageously has a diameter d90, that is to say a cut-off diameter such that 90% of the weight of the sample is constituted of particles having a diameter below this value, between 28 ⁇ m and 65 ⁇ m, preferably between 30 ⁇ m and 60 ⁇ m, and a mean diameter d50, that is to say a cut-off diameter such that 50% of the weight of the sample is constituted of particles having a diameter below this value, between 8 ⁇ m and 20 ⁇ m, preferably between 11 ⁇ m and 16 ⁇ m.
  • hydrochloric acid makes it possible not only to dissolve the calcium, but the main advantage is that new and unwanted chemical species are not introduced. Furthermore, by choosing a concentrated solution of hydrochloric acid, the liquid contribution is minimized and the dilution effect is thus reduced.
  • the process permits the preparation of calcium chloride starting from by-products (or "residues") of known processes, in order to be able to efficiently and economically reuse products which, without such a treatment, could not be used in certain fields of industry.
  • One major advantage of this embodiment is therefore the versatility of the dissolving step (c), the precipitating step (d) and the separating step (e). Indeed, owing to a prior step (c), it is also possible to prepare an equally purified calcium chloride solution starting from sludges (or slurry) containing calcium in various forms, especially calcium carbonate.
  • Another possible application of the process according to the invention relates to the brine purification sludges originating, for example, from the
  • the raw brine is therefore brought into contact with: - a source of hydroxide ions (OH " ) which will precipitate Mg 2+ in the form of magnesium hydroxide Mg(OH) 2 ; - a source of carbonate ions (CO 3 2 ) which will precipitate Ca 2+ in the form of calcium carbonate CaCO 3 .
  • OH " hydroxide ions
  • CO 3 2 carbonate ions
  • ammonia (NH 3 ) is used in the SOLVAY process.
  • This ammonia flows in a loop: it is absorbed in the brine upstream of the process and its absorption permits the subsequent or concomitant absorption of CO 2 .
  • the NH 3 is regenerated by distillation. This distillation brings into contact milk of lime (suspension based on slaked lime Ca(OH) 2 ) and filtered liquid (based on NaCl and on NH 4 Cl). Besides the regeneration OfNH 3 , sludges are formed.
  • a reuse variant proposed by one particular embodiment of the present invention consists in using the ES sludges and the DS liquid. These soda ash plant residues can thus be reused in a process that additionally comprises, before step (c), the steps:
  • the solid obtained contains predominantly calcium carbonate, for example more than 90%.
  • the magnesium is solubilized almost completely, for example, more than 90%, and is thus removed from the process.
  • the quantity of washing water of the precipitate of calcium carbonate implemented at the step (b) is chosen to have advantageously a sodium content in the final washed solid equal to or less than 10 weight %, preferably equal to or less than 5 weight %, more preferably equal to or less than 2 weight %, and most preferably equal to or less than 1 weight % of sodium expressed on dried solid.
  • the solid fraction from step (b) is then treated successively in steps (c), (d) and (e) that correspond to the steps described previously:
  • the carbon dioxide used in step (a) may come from the process itself, namely from step (c) and/or for example from a process for producing quicklime by calcination of calcium carbonate.
  • step (c) does not produce enough carbon dioxide to carbonate the ES sludges, it is thus possible to top it up with carbon dioxide originating from other sources such as for example the carbon dioxide produced in the SOLVAY process, the advantage of such a recycling being the reduction in the net emission of CO 2 .
  • step (c) produces an excess of carbon dioxide for carbonating the ES sludges, the extra carbon dioxide may be reused for other industrial applications.
  • the carbon dioxide obtained is of high purity and has a concentration generally equal to or greater than 95 volume %, preferably equal to or greater than 97 volume %, more preferably equal to or greater than 98 volume % of dry gas. It could be subjected to a washing operation with optionally alkalinized water in order to rid it of traces of hydrochloric acid vapour and other soluble pollutants. This washing operation could be carried out in one or more steps, with industrial equipment used for this type of usage, such as for example spray scrubbers, equipped with mist eliminators in order to rid the gas of droplets of washing liquid. It could also be carried out on one or more scrubbers provided with random or structured packing.
  • an additional variant provides, after step (e), a step (f) of desiccating the purif ⁇ ed calcium chloride solution, for example by evaporation or any other suitable method, so as to obtain solid purified CaCl 2 .
  • the diameter d90 corresponds to the diameter such that 90% of the weight of the sample is constituted of particles having a diameter below this value
  • the diameter d50 of the particles corresponds to the diameter such that 50% of the weight of the sample is constituted of particles having a diameter below this value
  • the diameter dlO corresponds to the diameter such that 10% of the weight of the sample is constituted of particles having a diameter below this value.
  • the span of the particle size curve is defined as the ratio: (d90 - dl0)/d50.
  • a realkalinization carried out in continuous mode is more effective in terms of settling than a realkalinization in semi-batch mode: that is to say the initial settling velocity and the percentage of clear volume relative to the volume of sludges to be treated are higher during a realkalinization in continuous mode.
  • the fact that Mg(OH) 2 has a higher d90 diameter during a realkalinization in continuous mode, as shown in Table Ia, is favourable to a better solid/liquid separation, in particular in the case of a settling operation and a filtration.
  • Table 2a Results of the settling tests with or without PRODEFLOC A2107 (mg/kg: mg commercial flocculant as is/ kg realkalinized slurry)
  • the Mg(OH) 2 precipitates poorly.
  • the settling velocities and the volume of clear liquid at the end of the settling operation remain at high values.
  • the Mg(OH) 2 precipitates greatly.
  • the settling characteristics are good, but they deteriorate significantly when the pH is increased up to a pH of 9.0.
  • Table 7 describes the results of trace element measurements of the calcium chloride solution obtained by acid attack of carbonated brine purification sludges before realkalinization, then after realkalinization for various tests.
  • the calcium chloride solution obtained is settled then filtered under vacuum firstly through a rapid laboratory filter, then filtered through a cellulose ester MILLIPORE membrane having a porosity of 8 ⁇ m.
  • the trace elements were measured by ICP (Inductively Coupled Plasma) atomic emission spectrometry, apart from arsenic and mercury, which were measured by atomic absorption spectrometry, and fluorine, which was measured by anion chromatography.
  • ICP Inductively Coupled Plasma

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
PCT/EP2010/051723 2009-02-12 2010-02-11 Preparation of purified calcium chloride WO2010092117A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
RU2011137433/05A RU2011137433A (ru) 2009-02-12 2010-02-11 Получение очищенного хлорида кальция
CN2010800074965A CN102317212A (zh) 2009-02-12 2010-02-11 纯化的氯化钙的制备
EP10703471A EP2396278A1 (en) 2009-02-12 2010-02-11 Preparation of purified calcium chloride

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0950868 2009-02-12
FR0950868A FR2941939B1 (fr) 2009-02-12 2009-02-12 Preparation de chlorure de calcium epure

Publications (1)

Publication Number Publication Date
WO2010092117A1 true WO2010092117A1 (en) 2010-08-19

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PCT/EP2010/051723 WO2010092117A1 (en) 2009-02-12 2010-02-11 Preparation of purified calcium chloride

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EP (1) EP2396278A1 (zh)
CN (1) CN102317212A (zh)
FR (1) FR2941939B1 (zh)
RU (1) RU2011137433A (zh)
WO (1) WO2010092117A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786074A (zh) * 2012-09-03 2012-11-21 南通市明鑫化工有限公司 一种氯化钙的生产工艺
CN111039315A (zh) * 2019-11-21 2020-04-21 南昌航空大学 一种制备5n级氯化钙溶液的方法
CN114159962A (zh) * 2021-12-01 2022-03-11 山东海化集团有限公司 一种利用氨碱法制碱废渣生产高浓度氯化钙溶液和高纯度纤维硫酸钙的方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103011641B (zh) * 2012-12-19 2014-10-01 武汉理工大学 利用氯碱废液处理磷石膏反应制备高活性α型半水石膏胶凝材料的方法
CN103395815B (zh) * 2013-07-26 2014-03-12 台山市新宁制药有限公司 从工业氯化钙制备高纯度氯化钙的制备方法
CN106185999B (zh) * 2016-08-30 2018-08-21 北京国电富通科技发展有限责任公司 一种从脱硫废水中制取氯化钙的工艺
CN106830046A (zh) * 2017-03-07 2017-06-13 太原科技大学 一种氯化钙溶液的制备方法
CN110203958B (zh) * 2019-05-31 2022-04-01 青岛海湾集团有限公司 一种氨碱法生产氯化钙工艺中消除总还原物对外观影响的方法
CN113264546B (zh) * 2021-05-18 2023-02-21 鲁西化工集团股份有限公司氯碱化工分公司 一种副产酸生产工业氯化钙溶液的工艺及系统与应用

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FR950868A (fr) 1943-01-06 1949-10-10 Sperry Gyroscope Co Ltd Appareil à résonateurs à cavité et son procédé de fabrication
DE1035629B (de) * 1956-05-16 1958-08-07 Solvay Verfahren zum Reinigen von Schwermetallverunreinigungen enthaltenden Alkali- bzw. Erdalkalichloridloesungen
GB890257A (en) * 1959-01-16 1962-02-28 Israel State Process for the manufacture of magnesium hydroxide
US3451774A (en) * 1966-06-01 1969-06-24 Dow Chemical Co Method of preparing magnesium hydroxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR950868A (fr) 1943-01-06 1949-10-10 Sperry Gyroscope Co Ltd Appareil à résonateurs à cavité et son procédé de fabrication
DE1035629B (de) * 1956-05-16 1958-08-07 Solvay Verfahren zum Reinigen von Schwermetallverunreinigungen enthaltenden Alkali- bzw. Erdalkalichloridloesungen
GB890257A (en) * 1959-01-16 1962-02-28 Israel State Process for the manufacture of magnesium hydroxide
US3451774A (en) * 1966-06-01 1969-06-24 Dow Chemical Co Method of preparing magnesium hydroxide

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"Engineers Techniques, Treatise on Chemical Engineering", December 1997, EDITIONS TI
"Les Techniques de l'Ingénieur, Traite de Genie Chimique", December 1997, EDITIONS TI
"Les Techniques de l'Ingénieur, Traite de Genie Chimique, Chapitre Decantation, J3450, Determination experimentale des vitesses de sedimentation", March 1999, EDITIONS TI
PHILLIPS V A ET AL: "THE GROWTH OF MG(OH)2 CRYSTALS FROM MGCL2 AND CA(OH)2 IN A BRINE ENVIRONMENT", JOURNAL OF CRYSTAL GROWTH, ELSEVIER, AMSTERDAM, NL, vol. 41, no. 2, 1 December 1977 (1977-12-01), pages 235 - 244, XP001149666, ISSN: 0022-0248 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102786074A (zh) * 2012-09-03 2012-11-21 南通市明鑫化工有限公司 一种氯化钙的生产工艺
CN111039315A (zh) * 2019-11-21 2020-04-21 南昌航空大学 一种制备5n级氯化钙溶液的方法
CN111039315B (zh) * 2019-11-21 2023-01-31 南昌航空大学 一种制备5n级氯化钙溶液的方法
CN114159962A (zh) * 2021-12-01 2022-03-11 山东海化集团有限公司 一种利用氨碱法制碱废渣生产高浓度氯化钙溶液和高纯度纤维硫酸钙的方法
CN114159962B (zh) * 2021-12-01 2023-05-16 山东海化集团有限公司 一种利用氨碱法制碱废渣生产高浓度氯化钙溶液和高纯度纤维硫酸钙的方法

Also Published As

Publication number Publication date
RU2011137433A (ru) 2013-03-20
EP2396278A1 (en) 2011-12-21
FR2941939B1 (fr) 2011-12-09
FR2941939A1 (fr) 2010-08-13
CN102317212A (zh) 2012-01-11

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