EP1984300A1 - An improved process for preparation of magnesium oxide - Google Patents

An improved process for preparation of magnesium oxide

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Publication number
EP1984300A1
EP1984300A1 EP06727340A EP06727340A EP1984300A1 EP 1984300 A1 EP1984300 A1 EP 1984300A1 EP 06727340 A EP06727340 A EP 06727340A EP 06727340 A EP06727340 A EP 06727340A EP 1984300 A1 EP1984300 A1 EP 1984300A1
Authority
EP
European Patent Office
Prior art keywords
mgo
water
slurry
bittern
lime
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06727340A
Other languages
German (de)
French (fr)
Inventor
Pushpito Kumar Ghosh
Himanshu Labhshanker Joshi
Hasina Hajibhai Deraiya
Maheshkumar Ramniklal Gandhi
Rohit Harshadrai Dave
Kaushik Jethalal Langalia
Vadakke Puthoor Mohandas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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Filing date
Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of EP1984300A1 publication Critical patent/EP1984300A1/en
Withdrawn legal-status Critical Current

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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
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to preparation of pure magnesia (MgO) from crude
  • the invention relates to preparation of such MgO without subjecting the Mg(OH) 2 to elaborate washing as practiced in the prior art and, instead, lightly calcining the crude mass to obtain a readily filterable material which is easier to purify.
  • Magnesia is an important compound that finds application in various industries. Magnesium oxide has the highest melting point of the moderately priced oxides and is therefore an important raw material for refractory bricks and other materials. It is the only material apart from ZrO 2 that can withstand long-term heating above 2000 0 C.
  • Magnesia bricks have a high heat storage capacity and a high thermal conductivity. They are used in efficient off-peak storage heaters. The heat generated by a heating element is transferred to the magnesia brick and increases its temperature. Thermal conductivity is increased by a high periclase content and a low porosity. The specific heat is only slightly lowered by SiO 2 and Al 2 O 3 , but is significantly lowered by CaO, Cr 2 O 3 , and Fe 2 O 3 . The bricks should not contain free CaO (risk of hydration) or crystal phases with different modifications.
  • MgO content ranges from ca. 65 to 99 wt %, and may even reach 99.9 %.
  • the magnesia is often ground prior to use. Extremely reactive caustic magnesia may have a surface area
  • the product is termed light burned (870 - 1000 °C) or hard burned (1550 - 1650 0 C).
  • Light-burned caustic magnesia becomes hydrated in cold water and is soluble in dilute acid. It has a loose bulk density of
  • 3 3 magnesia has a loose bulk density of 1.2 g/cm (bulk density 2 g/cm ).
  • MgO can be pressure hydrated to form Mg(OH) 2 . It can also be converted into anhydrous MgCl 2 through the reaction of eq. 1 ⁇ Electrolytic Production of Magnesium, Kh. L. Strelets, Keter Publishing House Jerusalem Ltd., 1977, p 28)
  • MgO can be thermally reduced to obtain Mg.
  • magnesia can be prepared by the decomposition of magnesite (MgCO 3 ).
  • MgCO 3 magnesite
  • the main drawback of this method is that magnesite ore can have high levels of impurity.
  • the highest quality magnesites, particularly those for refractory applications, are needed for a magnesia product with a high MgO content, a CaO : SiO 2 mass ratio of 2 - 3, and low contents of Fe 2 O 3 and Al 2 O 3 .
  • the presence of accompanying, low-melting minerals can adversely affect the properties of the sintered magnesia.
  • MgCl 2 -HcIi brine is purified to remove bromide and traces of boron and then fed via steel pipes into the spray nozzles of the reactor. It is sprayed into the cylindrical, externally insulated reactor at ca. 600 0 C. The water evaporates from the atomized brine droplets leaving a perforated chloride crust which reacts with the steam to form MgO and HCl.
  • the crude product is washed with water and hydrated in a stirred tank, and then concentrated in a thickener. The resulting slurry is difficult to filter and is washed and dewatered in a two-stage vacuum drum filter.
  • the calcined product typically contains > 99.5 wt% MgO, ⁇ 1 wt % CaO,
  • the method allows the manufacture of Mg(OH) 2 without impurities such as Fe, Mn, Al, and Ca.
  • impurities such as Fe, Mn, Al, and Ca.
  • the preparation of pure Mg(OH) 2 would no doubt have involved the washing of the solid to remove adhering NH 4 Cl, MgCl 2 , etc.
  • the main drawbacks of the process are that a supply of freshwater (> 40 m per tonne MgO) is required to wash the Mg(OH) 2 and to produce the milk of lime.
  • High-purity limestone or dolomite deposits should be available in the vicinity; they are calcined and slaked to provide Ca(OH) 2 as the precipitating agent and should therefore contain minimal quantities of elements that form insoluble carbonates, sulfates, etc.
  • the freshwater also requires to be decarbonated. Unless specially treated, caustic and sintered magnesia produced from seawater usually contain ca. 0.2 % B 2 O 3 and small amounts of CaO, SiO 2 ,
  • the main object of the present invention is to provide an improved process for the preparation of magnesia from crude magnesium hydroxide wherein the crude magnesium hydroxide in the form of a filtered cake or unfiltered paste is first converted into MgO through light calcination and the mass is then washed and filtered to remove adhering impurities with greater ease than possible in the conventional process of washing precipitated magnesium hydroxide free of impurities prior to calcination.
  • Yet another object is to produce crude magnesium hydroxide in the form of filterable slurry.
  • Yet another object is to obtain magnesium hydroxide in the form of a paste or solid-like dough that can be subjected to drying and light calcination directly without recourse to any filtration.
  • Yet another object is to produce such crude magnesium hydroxide from the reaction between MgCl 2 and alkali with or without the use of Mg(OH) 2 as seed.
  • Yet another object is to conduct the reaction either at room temperature or elevated temperatures to ensure adequate mixing of mass during reaction.
  • Yet another object is to use a sigma mixer or dough kneader — instead of a conventional reactor — for promoting reaction between MgCl 2 and alkali in the semi-solid mass.
  • Yet another object is to make the mass more filterable after light calcination at 600- 900 0 C.
  • Yet another object is to exploit the relative thermal stability of calcium chloride in the temperature domain of light calcination so as to obtain a mixture of MgO and CaCl 2 during light calcination of the crude Mg(OH) 2 . Yet another object is to simultaneously convert adhering MgCl 2 into MgO and HCl vapor in the process of light calcination.
  • Yet another object is to treat the lightly calcined mass with required quantity of water to disintegrate the lumps spontaneously and dissolve the soluble salts wherein the resultant slurry becomes easily filterable.
  • Yet another object is to ensure that the temperature rise during treatment of lightly calcined mass with water is maintained at ⁇ 50 0 C to minimize rehydration of MgO.
  • Yet another object is to wash the MgO free of salts and to further treat with water containing suitable additives to reduce the boron impurity in MgO.
  • Yet another object is to debottleneck the production of MgO by speeding up the rate determining operation, namely the washing of Mg(OH) 2 , by not washing crude Mg(OH) 2 at all and instead washing lightly calcined crude MgO with much greater degree of ease.
  • Yet another object is to conserve on use of fresh water.
  • Yet another object is to obtain CaCl 2 in the form of a concentrated solution when the precipitation reaction is conducted with lime.
  • Yet another object is to use the concentrated CaCl 2 solution for desulphatation of bittern to ensure a sulphate-free MgCl 2 raw material.
  • Yet another object is to recalcine the purified MgO at 900-1100 0 C to produce caustic calcined MgO, or at still higher temperatures to produce dead burned or sintered magnesia.
  • still another object is to use the lightly calcined MgO directly after washing, filtering and drying in applications where some degree of hydrolysis of MgO — that may occur during washing — can be tolerated, e.g., for briquette preparation prior to sintering or for preparation of milk of magnesia.
  • Still another object is to obtain MgO effortlessly without compromising on its purity. Summary of the invention
  • the aim of the present invention is directed to provide an improved process for the preparation of MgO from Mg(OH) 2 wherein the key bottleneck of the conventional process, namely the tedious nature of purification to free the Mg(OH) 2 of impurities, is overcome by eliminating the washing of crude Mg(OH) 2 , indeed even the need for its filtration in a special case of application of the invention, and instead lightly calcining the mass to convert the hydroxide into oxide which is more easily washable and filterable, thereby greatly reducing the need for fresh water while also speeding up the washing operation.
  • the light calcination process also helps to convert adhering MgCl 2 into MgO.
  • the washed MgO can be recalcined, if required, or it can be directly used in preparation of briquettes that can be then sintered to achieve refractory materials.
  • the partially hydrolysed MgO can also be used for Mg(OH) 2 preparation through pressure hydrolysis as practiced in the prior art.
  • the present invention provides an improved process for the preparation of MgO, the said process comprising the steps of: i) desulphating brine or bittern with CaCl 2 , ii) evaporating the clarified brine/bittern after separation of gypsum to separate out the common salt and carnallite (KCLMgCl 2 .6H 2 O), iii) recovering MgCl 2 rich and other salt free end bittern from step (ii), 0627
  • step (iii) further evaporating end bittern of step (iii) to obtain crystalline
  • MgCl 2 .6H 2 O 5 v) mixing MgCl 2 .6H 2 O with seeds of Mg(OH) 2 , followed by treating with alkali or hydrated lime/lime slurry to obtain the crude Mg(OH) 2 paste/slurry, vi) filtering resultant paste/slurry to obtain crude Mg(OH) 2 and calcium chloride, alternatively using crude Mg(OH) 2 paste as such without filtration, vii) drying the above crude Mg(OH) 2 paste, followed by Dalcinations to convert
  • step (i) Mg(OH) 2 into MgO, and converting adhering MgCl 2 into MgO and HCl gas viii) treating the calcined mass of MgO obtained in step (vii) with water to crumble the lumps and thereby dissolving calcium chloride and other soluble salts in water to obtain the slurry, ix) filtering the above resultant slurry, followed by washing the residue with water to make it free from impurities, x) drying the above resultant wet cake residue containing mainly MgO and recalculating it to obtain the desired highly purified MgO and xi) using the CaCl 2 solution filtrate obtained in steps (vi) and (ix), for desulphatation of brine or bittern in step (i) if lime is used in step (v).
  • the bittern used in step (i) is obtained from ocean brine, sea brine, sub-soil brine or lake brine.
  • the sulphate-containing bitterns used in step (i) are desulphated in the density range of 29-32 0 Be'.
  • the carnallite (KCl.MgCl 2 .6H 2 O) obtained in step (ii) is crystallized between 32-36 0 Be' either through solar or forced evaporation and the end bittern of step (iii) having density of 35.5-36.0 0 Be' contains 450-460 gL "1 Of MgCl 2 , 5-10 gL "1 OfNaCl 5 S-IO gL 4 Of KCl 5 S-IS gL- 1 Of Ca 5 O-S gL "1 of sulphate, 6-7 gL 4 Br " , 0.02-
  • step (iii) is used as such or preferably debrominated to recover bromine and simultaneously reduces the Br " impurity in debrominated bittern to ⁇ 0.5 gL "1 .
  • the prestine end bittern of step (iii) can be used for MgO recovery or more preferably it can be debrominated and used without crystallization step of step (iv).
  • step (iii) is evaporated in step (iv) to reduce the volume by 20-25% so as to crystallize out the MgCl 2 .6H 2 O (60-80% yield) that is free of the above salts and contains 0.020-0.015% B 2 O 3 impurity.
  • other soluble magnesium salts such as magnesium sulphate or magnesium nitrate can be used as source of magnesium.
  • the alkali used in step (v) is lime, caustic soda and ammonia.
  • the lime used in step (v) is selected from quicklime, hydrated lime, and dolime in solid or slurry form.
  • the hydrated lime used in step (v) is prepared by slaking of quicklime followed by cycloning and dewatering to yield upgraded solid hydrated lime and lime water that can be reused for slaking of fresh batch of quicklime.
  • the stoichiometric equivalent of alkali used in step (v) is in the range of 0.8-1.0.
  • the amount of Mg(OH) 2 seed used in step (v) is in the range of 0-10% mole for mole of magnesium salt taken.
  • the temperature of the precipitation reaction in step (v) is in the range of 20-120 0 C.
  • the reaction time used in the precipitation reaction in step (v) is in the range of 5 - 90 min, under, intimate mixing conditions.
  • step (vi) the drying of pasty mass obtained in step (vi) is carried out at 70-120 0 C in conventional ovens or through solar drying.
  • step (vii) the D calcination operation in step (vii) is carried out at a temperature in the range of 500-1000 0 C, preferably 600-900 0 C, in a muffle furnace or rotary calciner or vertical kiln depending on the physical form of the dry matter.
  • step (vii) converts adhering MgCl 2 into MgO with concomitant release of HCl vapour and CaCl 2 .2H 2 O into fused CaCl 2 that is hydrated with release of heat and provides the driving force for the disintegration of the crude mass and also the rapid solubilisation of the CaCl 2 .
  • the water used in step (viii) is largely comprises the recycled washings from previous batches and the amount of water taken is sufficient to dissolve all soluble salts in the MgO and also ensure the temperature of the slurry is controlled at a temperature of 40-90 0 C, preferably in the range of 55-65 0 C, for the higher solubility of salts such as CaCl 2 at higher temperature and to minimize the hydrolysis of MgO.
  • the water used in steps (viii) and (ix) contains additives to remove boron impurities in MgO or without having additives.
  • step (ix) the washing and filtration operations of step (ix) are expedited 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH) 2 .
  • step (ix) the requirement of water for purification of the calcined mass in step (ix) is reduced by a factor of 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH) 2 .
  • the wet cake obtained in step (vii) is useful for the preparation of milk of magnesia.
  • the wet cake obtained in step (vii) is dried to yield MgO or recalcined at a temperature in the range of 500-2200 0 C to obtain the desired product.
  • step (vii) when the alkali used in step (v) is ammonia, the calcinations operation of step (vii) removes all impurities to yield highly pure MgO and helps avoid the operation of steps (viii) and (ix). 7
  • the speed of the work up and saving of fresh water is not at the expense of quality and MgO having similar purity to that obtained through the conventional process of work up OfMg(OH) 2 is achieved.
  • step (vii) the intermediate product obtained in step (vii) is washed with water and filtered to remove calcium chloride as in steps (viii) & (ix)
  • the filtration operation followed by washing of steps (viii) & (ix) could be carried out with ease on a Nutsche filter or rotary disk filter or filter press.
  • the filtration is found to be rapid.
  • step (x) the calcination operation of step (x) was carried out in a muffle furnace at 900 0 C for 2-3 h and preferably by gradually ramping the temperature.
  • the MgO has a purity of 98.0-
  • the MgO obtained from end bittern of step (iii) has a B 2 O 3 impurity level of 0.10-0.12%, while the level is 0.060-0.080% when prepared from crystallized MgCl 2 .6H 2 O of step (iv), and 0.010-0.015% when prepared from recrystallized MgC-b. ⁇ HbO.
  • the B 2 O 3 level in MgO can be made still lower through appropriate treatment either of the precursor Mg(OH) 2 or of the MgO itself.
  • the lime used in step (v) is either hydrated lime or quicklime in the form of a solid or solid suspension.
  • the solution of steps (vi) and (ix) contains 20-30% CaCl 2 and it can be used directly in the desulphatation reaction of step (i) or it can be IB2006/000627
  • the inventive step of the present invention lies in the preparation of magnesia from magnesium chloride via intermediate formation of magnesium hydroxide on its reaction with alkali or hydrated lime.
  • the filtered cake or unfiltered paste of magnesium hydroxide is subsequently converted into MgO through light calcination followed by washing with water and filtration to remove adhering impurities with greater ease than conventional process of washing the precipitated magnesium hydroxide prior to calcination.
  • (10) Realising that the greatest advantage in operating the invention is the feasibility of producing crude Mg(OH) 2 in the form of a dough which can be directly dried and calcined thereby avoiding filtration altogether while at the same time helping to conserve water and increase throughput.
  • (11) Proving the concept of (10) by making Mg(OH) 2 from the reaction of solid hydrated lime (obtained by purifying lime slurry through hydrocycloning, dewatering the slurry and recycling the lime water for preparation of more lime slurry thereby conserving water as well) and a highly concentrated hot solution of MgCl 2 -rich end bittern promoted by mixing in a jacketed sigma mixer.
  • the mass was then subjected to three cycles of washing and filtration (2x50 mL + 1x75 mL) of which the middle cycle was given with 1% additive to reduce boron impurity.
  • Total filtrate volume was 213 mL while the total filtration time was 25-30 min.
  • the wet cake weighing 23.64 g was dried in an oven at 110 0 C to 14.15 g of dry mass which was calcined at 900 0 C in a muffle furnace to yield 9.67 g of MgO (I.e., 31.7 % loss on ignition) having 99.43% purity (see powder XRD in Figure IA).
  • the remaining 47 g of reaction mass was dispersed in 50 mL water and then filtered.
  • the calcined material was cooled to room temperature and treated with 0.15 L of water and thereafter washed with an additional 0.75 L of water in lots.
  • EXAMPLE 5 10 L of end bittern containing 115 gL " *Mg was evaporated which on cooling gave 7 kg of solid mass. 2 kg of the solid containing 0.329 kg Mg (1.285 kg MgCl 2 ) was taken along with 0.7 L of water and heated at 150 0 C to obtain a hot solution which was poured into a ribbon blender. 0.972 kg (94% of stoichiometric requirement for Mg(OH) 2 formation) of powdered hydrated lime (prepared from quicklime by slaking followed by hydrocycloning) was added into the blender and the contents were thoroughly blended. After ca. 30 min the pH was found to be around 8-9 indicating completion of the reaction and the blending was stopped yielding a pasty mass.
  • the slurry could be easily filtered on a B ⁇ chner funnel to obtain 0.275 L of filtrate containing 29.4% CaCl 2 .
  • the wet cake was washed successively with 3 x 0.300 L of water and in each case filtration was found to be facile.
  • the final washing contained 1.2% CaCl 2 .
  • the requirement of fresh water is 6-8 L/kg of MgO and all of the washings can be made to have a high CaCl 2 concentration (20-40%) which is beneficial for cost-effective desulphatation of bittern.
  • the inventions also illustrate the advantages in terms of improved filterability and conservation of water, without compromising on MgO quality.
  • Examples 5 and 6 also teach us how rock like mass crumble and disperse easily on contact with required quantity of water without any need of grinding or agitation.
  • Example 6 also teaches us that the D calcination OfMg(OH) 2 at 600 0 C not only yields MgO having good filterability but also yields fused calcium chloride which is readily water soluble and yields a high concentration of aqueous CaCl 2 .
  • Example 6 also teaches us that crude calcined MgO produced by lime route remains largely unaffected during the purification process with water and does not convert into Mg(OH) 2 to any significant extent.
  • Example 6 also teaches us that through the method of the invention it to possible to achieve >99% pure MgO using crystallized MgCl 2 .6H 2 O and inexpensive lime after upgradation.
  • Another advantage is that reaction mass even in the form of paste or dough can be handled.
  • Another important advantage is the conservation of fresh water.
  • Yet another advantage is the minimum formation of waste. Yet another important advantage is increased throughput as a result of use of reactants in more concentrated form and speeding up of the rate determining step, namely purification
  • Yet another advantage is the spontaneous disintegration of calcined lumps of MgO which eliminates the need for grinding. Yet another advantage is that the CaCl 2 in crude MgO exists in the form of fused CaCl 2 which is readily soluble in water and yields a CaCl 2 solution having 35-40% (w/v) concentration, which helps conserve water and also improves the economics of bittern desulphation.
  • Yet another advantage is the achievement of facile process of MgO preparation without compromising on product quality.

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Abstract

The present invention provides an improved process for the preparation of MgO from the reaction of magnesium salt and alkali/lime . The crude Mg(OH)2 is directly calcined and then treated with water to disintegrate the mass spontaneously to yield a slurry and dissolve away the soluble salts. This slurry is much easier to filter and wash than the original Mg(OH)2 slurry, which helps to speed up the purification operation and also conserve fresh water. Another important advantage of the present method is that even pasty or dough like reaction products that are processed using dough mixers and similar equipment can be worked up with ease. There is no compromise in the quality of MgO achieved in this manner.

Description

'AN IMPROVED PROCESS FOR THE PREPARATION OF
MAGNESIUM OXIDE'
Field of the Invention
The present invention relates to preparation of pure magnesia (MgO) from crude
Mg (OH)2. More particularly, the invention relates to preparation of such MgO without subjecting the Mg(OH)2 to elaborate washing as practiced in the prior art and, instead, lightly calcining the crude mass to obtain a readily filterable material which is easier to purify.
Background of the invention
Magnesia is an important compound that finds application in various industries. Magnesium oxide has the highest melting point of the moderately priced oxides and is therefore an important raw material for refractory bricks and other materials. It is the only material apart from ZrO2 that can withstand long-term heating above 2000 0C.
Reference may be made to Ullmann's Encyclpedia, 6th Edition (electronic version) wherein it is stated that: "The increased demands made on refractory materials as a result of higher operating temperatures and shorter tap to tap times in metallurgical furnaces and reactors can only be met by pure, high-density magnesia sinters. Small quantities of "contaminants" are disadvantageous if they form low-melting eutectics with MgO (e.g., with CMS at 1485 °C or with C2F at 1200 °C because this leads to deterioration of mechanical properties (e.g., strength and volume stability) at high temperatures. High-quality sinters therefore have a low content of high-melting silicate phases (such as C2S), a low B2O3 content, and a high degree of direct periclase - periclase contact (without intermediate silicate phases).
Magnesia bricks have a high heat storage capacity and a high thermal conductivity. They are used in efficient off-peak storage heaters. The heat generated by a heating element is transferred to the magnesia brick and increases its temperature. Thermal conductivity is increased by a high periclase content and a low porosity. The specific heat is only slightly lowered by SiO2 and Al2O3, but is significantly lowered by CaO, Cr2O3, and Fe2O3. The bricks should not contain free CaO (risk of hydration) or crystal phases with different modifications.
Caustic magnesia was formerly produced exclusively from cryptocrystalline magnesite with a low iron content but is now also obtained from all types of magnesite and Mg(OH)2.
Its MgO content ranges from ca. 65 to 99 wt %, and may even reach 99.9 %. The magnesia is often ground prior to use. Extremely reactive caustic magnesia may have a surface area
2 of up to 160 m /g. Depending on the burning temperature, the product is termed light burned (870 - 1000 °C) or hard burned (1550 - 1650 0C). Light-burned caustic magnesia becomes hydrated in cold water and is soluble in dilute acid. It has a loose bulk density of
3 2
0.3 - 0.5 g/cm and a specific surface area (BET) of 10 - 65 m Ig. Hard-burned caustic
3 3 magnesia has a loose bulk density of 1.2 g/cm (bulk density 2 g/cm ).
MgO can be pressure hydrated to form Mg(OH)2. It can also be converted into anhydrous MgCl2 through the reaction of eq. 1 {Electrolytic Production of Magnesium, Kh. L. Strelets, Keter Publishing House Jerusalem Ltd., 1977, p 28)
MgO + Cl2 + CO ► MgCl2 + CO2 + 70.8 cal/mole (eq. 1) and the anhydrous MgCl2 can be converted into Mg and Cl2 by electrolysis (eq. 2) MgCl2 ► Mg + Cl2 (eq.2).
Alternatively, MgO can be thermally reduced to obtain Mg.
Reference is made to Ullmann's Encyclopedia wherein it is reported that magnesia can be prepared by the decomposition of magnesite (MgCO3). The main drawback of this method is that magnesite ore can have high levels of impurity. The highest quality magnesites, particularly those for refractory applications, are needed for a magnesia product with a high MgO content, a CaO : SiO2 mass ratio of 2 - 3, and low contents of Fe2O3 and Al2O3. The presence of accompanying, low-melting minerals can adversely affect the properties of the sintered magnesia. Reference may also be made to a publication entitled "Magnesite - A market survey" published by Indian Bureau of Mines , Nagpur and "Magnesite" in Indian Minerals Year Book, Vol. - 2 (1989) Published By Indian Bureau of Mines, Nagpur. Page - 698 to 699, wherein magnesia is prepared by calcination of naturally occurring magnesite deposits. The drawback of this process is that magnesite ores contain varying amount of silica, iron oxide, alumina, and lime as silicates, carbonates, and oxides. Selectively mined ore is passed through various beneficiation methods like crushing and size separation, Heavy media separation, and froth flotation to reduce lime and silica content prior to calcination. Magnetic separation reduces iron concentration but is effective only when the iron is present in the form of discrete ferromagnetic minerals rather than as ferrous carbonate. Due to all this, high purity magnesia is difficult to produce by this process. Reference is made to the Sulmag II process (W. S. Ainscow: "Aufbereitung von Magnesit zu hochwertiger Sintermagnesia," TIZ 110 (1986) no. 6, 363 - 368. Sulmag II the Sinter Magnesite Process, Sulzer Brothers Ltd., Winterthur, Switzerland) for producing light- burned caustic magnesia in a gas suspension kiln from low-magnesite ores. Dissolved magnesium chloride is obtained by selective extraction with recycled NH4Cl solution (eqs.
3, 4) and all insoluble impurities are removed through filtration. Needle-shaped crystals of nesquehonite (MgCO3-3H2O) are precipitated out in the reactor and filtered (eq. 5).
Caustic magnesia with a high specific surface area is obtained by heating the nesquehonite. MgCO3 > MgO + CO2 (eq. 3)
2 NH4Cl + MgO+ H2O + Contaminants > 2 NH4OH +MgCl2 + Tailings (eq. 4)
MgCl2 + (NH4)2CO3 + 3 H2O > MgCO3 • 3 H2O X + 2 NH4Cl (eq. 5)
The above process has many advantages but would give product of very low bulk density which may not be suitable in refractory applications, which comprises the bulk of applications related to magnesia.
Reference may also be made to the technique of pyrohydrolysis. MgCl2-HcIi brine is purified to remove bromide and traces of boron and then fed via steel pipes into the spray nozzles of the reactor. It is sprayed into the cylindrical, externally insulated reactor at ca. 600 0C. The water evaporates from the atomized brine droplets leaving a perforated chloride crust which reacts with the steam to form MgO and HCl. The crude product is washed with water and hydrated in a stirred tank, and then concentrated in a thickener. The resulting slurry is difficult to filter and is washed and dewatered in a two-stage vacuum drum filter. The calcined product typically contains > 99.5 wt% MgO, < 1 wt % CaO,
< 0.05 wt% SiO2, < 0.05 wt% Fe2O3, < 0.005 wt% Al2O3, and < 0.01 % B3O3; its specific
2 3 surface area is 2 - 50 m /g, the loose bulk density ranges from 0.8 to 0.2 g/cm . The main drawback is that spray calcination is an energy intensive process and choking up of nozzles can pose a problem. Another drawback is that the MgO obtained after first calcination leads to a slurry that is indicated to be "difficult to filter" which would largely offset any advantage that might be gained.
Reference may be made to the US Patent No.: 4,255,399 Dated March 10, 1981 entitled "Process for the Recovery of Magnesium Oxide of high Purity" by Grill et. al, wherein magnesium oxide is obtained by thermal decomposition of a magnesium chloride brine previously purified. Concentrated magnesium chloride is decomposed in a thermal reactor where hot gases convert it into magnesium oxide and hydrochloric acid. The problems no doubt would be similar to those stated above.
Reference is made to U. S. Patent No. 6, 776,972, DT. 17-08-2004 wherein Vohra et al. have described the use of HCl gas generated from spray pyrolysis for reaction with limestone to prepare CaCl2 which can then be used to desulfate sea/sub-soil bittern for the facile production of carnallite double salt wherefrom KCl can be produced. The problem of spray calcination, however, remains.
Reference may be made to "Preparation of magnesium hydroxide flame retardant by ammonia method." by Li, Kemin; Zhang, Li, Wujiyan Gongye, (33(2), 14-16 (Chinese) 2001 Wujiyan Gongye Bianjib; CA 135:115882; CA Section: 78 (Inorganic Chemicals and
Reactions), wherein the flame retardant was prepared by allowing bittern after recycling
K2SO4 to react with NH4OH, hydrothermal treatment to obtain Mg(OH)2, treating by surface treatment, washing, drying, and crushing. The content of Mg(OH)2 of the flame retardant was 97%. No mention is made of any process that produces MgO from the crude unwashed Mg(OH)2.
Reference may be made to "Recovery of magnesium hydroxide, gypsum and other products from natural and technical brines, in particular from final lyes of potash works." by Krupp, RaIf (Germany ) (Ger. Offen. DE 10154004 Al 15 May 2003,9 pp. (German).; CA 138:371080), wherein, recovery Of Mg(OH)2 and gypsum from MgSO4- and MgCl2- containing brines results by precipitation of Mg-ions with NH3 or NH4OH. Gaseous NH3 is recovered by addition of CaO and recycled for the precipitation, step. The method allows the manufacture of Mg(OH)2 without impurities such as Fe, Mn, Al, and Ca. However, although not stated explicitly, the preparation of pure Mg(OH)2 would no doubt have involved the washing of the solid to remove adhering NH4Cl, MgCl2, etc.
Reference may be made to "One-step process for manufacture of magnesium hydroxide" by Wang, Fuwen; Zhang, Jun; Liu, Jianhua; Dong, Yijun (Shandong Haihua Group Corp., Ltd., Peop. Rep. China). Faming Zhuanli Shenqing Gongkai Shuomingshu CN 1332117 A 23 Jan 2002, 7 pp. (Chinese). (People's Republic of China). Bittern containing MgCl2 and ammonium hydroxide[mol ratio of MgCl2/ammonia=l/(1.3-2.0)] are reacted at 45-90° for 5-30 min, filtered, washed, dried, and pulverized to give solid magnesium hydroxide. No mention is made of the difficulties encountered in purifying Mg(OH)2 besides the disadvantage of using ammonia vis-a-vis inexpensive lime. Seawater contains magnesium and has the inherent advantage of having virtually no silica contamination. Thus high quality Mg(OH)2 can be produced mainly using seawater/brine/bittern of marine origin.
Reference may be made to the paper by J. A. Fernandez-Lozano entitled "Utilization of Seawater Brines for the Production of High Purity Magnesium Oxide and Magnesium Hydroxide" published in the Proceedings of the Fifth International Symposium on Salt - Northern Ohio Geological Society, 1979, pp 269-279 wherein the author has stated that Mg(OH)2 obtainable from the reaction of MgCl2-rich seawater brine and ammonia can be made of high purity by washing the hydroxide and that, in principle, MgO of high purity can be obtained as a result. No mention is made of the difficulties encountered in purifying Mg(OH)2 besides the disadvantage of using ammonia vis-a-vis inexpensive lime.
Reference is made to the preparation of MgO from Mg(OH)2 by calcination (eq. 6). Mg(OH)2 > MgO + H2O (eq. 6) Reference is also made to Kirk Othmer, Encyclopedia of Chemical Technology, 4th
Ed., Vol. 15, p 690 wherein it is stated that "To precipitate and recover magnesium hydroxide from solutions of magnesium salts, a strong base is added. The more commonly used base is calcium hydroxide derived from lime (CaO) or dolime (CaO-MgO)." Sodium hydroxide is used as a precipitant if a product having low CaO content is desired. Reference may be made to the paper entitled "Carbonation of Aqueous Suspensions containing Magnesium Oxides or Hydroxides" by Robert L. Evans and Hillary W. St. Clair in "Industrial and Engineering Chemistry" 1949, 41(12), 2814-2817, wherein a modification of the Pattinson process (carbonation of magnesium hydroxide to magnesium bicarbonate) is described. A suspension of magnesium hydroxide is carbonated to form a metastable solution of magnesium bicarbonate. After the separation of insoluble impurities, the solution is decarbonated by heating or aeration and the magnesium carbonate precipitates as trihydrate, the penta hydrate or the basic carbonate. The precipitate is recovered from the solution by filtration and converted to magnesium oxide by thermal decomposition. The main drawback of the process is that the process is very sensitive to the partial pressure of carbon dioxide and to the temperature. The stability of the metastable solution of magnesium bicarbonate decreases markedly as the temperature rises above normal room temperature. Moreover, the bulk density of the MgO would be too low for refractory applications.
Reference may be made to the paper "Chemical Engineering Problems in the Sea Water Magnesia Process" read by H. W. Thorp and W. C. Gilpin at a meeting of the chemical engineering group, held in the Apartment of the geological society, Burlington House, London, W. I. on Tuesday, October 25, 1949 wherein the recovery of magnesia from sea water lies in the difficulty of precipitating the magnesium hydroxide in a form which will settle rapidly and which will yield a sludge easy to de-water. It is realized that each ton of magnesia must be separated from some 300 tons of water, which amount does not include any used for washing the precipitate. It is necessary to ensure the minimum contamination by lime; the sea water is treated prior to the removal of the magnesium hydroxide, with a small proportion of lime to precipitate the bicarbonate ion as calcium carbonate. Reference is made to Ullmann's Encyclopedia wherein the production of MgO from
3 seawater and brines is described. 470 m of seawater are required to produce 1 t of MgO; in practice 600 m are needed. The process is based on the precipitation of magnesium hydroxide (solubility in water 0.0009 wt %) by addition of calcium hydroxide (solubility 0.185 wt %): Mg2+ + 2 Cf + Ca(OH)2 > Mg(OH)2 1 + Ca + + 2 Cl"
The main drawbacks of the process are that a supply of freshwater (> 40 m per tonne MgO) is required to wash the Mg(OH)2 and to produce the milk of lime. High-purity limestone or dolomite deposits should be available in the vicinity; they are calcined and slaked to provide Ca(OH)2 as the precipitating agent and should therefore contain minimal quantities of elements that form insoluble carbonates, sulfates, etc. The freshwater also requires to be decarbonated. Unless specially treated, caustic and sintered magnesia produced from seawater usually contain ca. 0.2 % B2O3 and small amounts of CaO, SiO2,
Al2O3, and Fe2O3 derived from the limestone or wastes in the seawater. The B2O3 content of the magnesia is also generally lowered to ca. 0.05 % by using a 5 - 12 % excess of lime for precipitation (overliming); this increases the pH to 12 and minimizes the adsorption of boron. Apart from all the obvious drawbacks no mention is made of the difficulties of washing Mg(OH)2 which problem is even more complex as a result of overliming.
Reference may also be made to the paper " Recovery of Magnesium Compounds from Sea Water " by W. C. Gilpin and N. Heasman in "Chemistry and Industry", 6 July 1977, 567 - 572, wherein the process of recovering magnesia from seawater and the problems with the process are clearly outlined. The drawbacks of the process are similar to those described above. It will be obvious from the prior art that wherever Mg(OH)2 has been used as intermediate in MgO manufacture, it is first purified to obtain pure Mg(OH)2 prior to calcination to obtain MgO. Unfortunately, being slimy in nature, Mg(OH)2 as obtained in the precipitation reaction is difficult to filter and purification becomes more and more difficult to attain high levels of purity.
Objectives of the invention
The main object of the present invention is to provide an improved process for the preparation of magnesia from crude magnesium hydroxide wherein the crude magnesium hydroxide in the form of a filtered cake or unfiltered paste is first converted into MgO through light calcination and the mass is then washed and filtered to remove adhering impurities with greater ease than possible in the conventional process of washing precipitated magnesium hydroxide free of impurities prior to calcination.
Yet another object is to produce crude magnesium hydroxide in the form of filterable slurry.
Yet another object is to obtain magnesium hydroxide in the form of a paste or solid-like dough that can be subjected to drying and light calcination directly without recourse to any filtration.
Yet another object is to produce such crude magnesium hydroxide from the reaction between MgCl2 and alkali with or without the use of Mg(OH)2 as seed.
Yet another object is to conduct the reaction either at room temperature or elevated temperatures to ensure adequate mixing of mass during reaction.
Yet another object is to use a sigma mixer or dough kneader — instead of a conventional reactor — for promoting reaction between MgCl2 and alkali in the semi-solid mass.
Yet another object is to make the mass more filterable after light calcination at 600- 9000C.
Yet another object is to exploit the relative thermal stability of calcium chloride in the temperature domain of light calcination so as to obtain a mixture of MgO and CaCl2 during light calcination of the crude Mg(OH)2. Yet another object is to simultaneously convert adhering MgCl2 into MgO and HCl vapor in the process of light calcination.
Yet another object is to treat the lightly calcined mass with required quantity of water to disintegrate the lumps spontaneously and dissolve the soluble salts wherein the resultant slurry becomes easily filterable.
Yet another object is to ensure that the temperature rise during treatment of lightly calcined mass with water is maintained at <50 0C to minimize rehydration of MgO.
Yet another object is to show that even when rehydration occurs to some extent, filterability of the mass remains superior than of the precipitated Mg(OH)2. Yet another object is to show that the MgO does not in any manner occlude the salts irreversibly as a result of which the MgO can be readily washed free of the salts.
Yet another object is to wash the MgO free of salts and to further treat with water containing suitable additives to reduce the boron impurity in MgO.
Yet another object is to debottleneck the production of MgO by speeding up the rate determining operation, namely the washing of Mg(OH)2, by not washing crude Mg(OH)2 at all and instead washing lightly calcined crude MgO with much greater degree of ease.
Yet another object is to conserve on use of fresh water.
Yet another object is to obtain CaCl2 in the form of a concentrated solution when the precipitation reaction is conducted with lime.
Yet another object is to use the concentrated CaCl2 solution for desulphatation of bittern to ensure a sulphate-free MgCl2 raw material.
Yet another object is to recalcine the purified MgO at 900-11000C to produce caustic calcined MgO, or at still higher temperatures to produce dead burned or sintered magnesia. still another object is to use the lightly calcined MgO directly after washing, filtering and drying in applications where some degree of hydrolysis of MgO — that may occur during washing — can be tolerated, e.g., for briquette preparation prior to sintering or for preparation of milk of magnesia. Still another object is to obtain MgO effortlessly without compromising on its purity. Summary of the invention
The aim of the present invention is directed to provide an improved process for the preparation of MgO from Mg(OH)2 wherein the key bottleneck of the conventional process, namely the tedious nature of purification to free the Mg(OH)2 of impurities, is overcome by eliminating the washing of crude Mg(OH)2, indeed even the need for its filtration in a special case of application of the invention, and instead lightly calcining the mass to convert the hydroxide into oxide which is more easily washable and filterable, thereby greatly reducing the need for fresh water while also speeding up the washing operation. The light calcination process also helps to convert adhering MgCl2 into MgO.
It is further demonstrated through the invention that residual salts in the MgO such as NaCl and CaCl2 are not occluded irreversibly and that such salts are easily washed off with water, as a result of which the purity of MgO achievable is the same as that which can be realized through the elaborate process of pre-purification of Mg(OH)2 with large water consumption practiced in the prior art. Additional washing with suitable additives can simultaneously reduce boron impurity in the MgO. A simultaneous benefit is the high concentration of CaCl2 achievable through this process which makes desulphatation more cost-effective by reducing the evaporation load post desulphatation. The washed MgO can be recalcined, if required, or it can be directly used in preparation of briquettes that can be then sintered to achieve refractory materials. The partially hydrolysed MgO can also be used for Mg(OH)2 preparation through pressure hydrolysis as practiced in the prior art.
Description of the invention
Accordingly, the present invention provides an improved process for the preparation of MgO, the said process comprising the steps of: i) desulphating brine or bittern with CaCl2, ii) evaporating the clarified brine/bittern after separation of gypsum to separate out the common salt and carnallite (KCLMgCl2.6H2O), iii) recovering MgCl2 rich and other salt free end bittern from step (ii), 0627
iv) further evaporating end bittern of step (iii) to obtain crystalline
MgCl2.6H2O5 v) mixing MgCl2.6H2O with seeds of Mg(OH)2, followed by treating with alkali or hydrated lime/lime slurry to obtain the crude Mg(OH)2 paste/slurry, vi) filtering resultant paste/slurry to obtain crude Mg(OH)2 and calcium chloride, alternatively using crude Mg(OH)2 paste as such without filtration, vii) drying the above crude Mg(OH)2 paste, followed by Dalcinations to convert
Mg(OH)2 into MgO, and converting adhering MgCl2 into MgO and HCl gas viii) treating the calcined mass of MgO obtained in step (vii) with water to crumble the lumps and thereby dissolving calcium chloride and other soluble salts in water to obtain the slurry, ix) filtering the above resultant slurry, followed by washing the residue with water to make it free from impurities, x) drying the above resultant wet cake residue containing mainly MgO and recalculating it to obtain the desired highly purified MgO and xi) using the CaCl2 solution filtrate obtained in steps (vi) and (ix), for desulphatation of brine or bittern in step (i) if lime is used in step (v). In an embodiment of the present invention the bittern used in step (i) is obtained from ocean brine, sea brine, sub-soil brine or lake brine.
In yet another embodiment the sulphate-containing bitterns used in step (i) are desulphated in the density range of 29-32 0Be'.
In yet another embodiment the carnallite (KCl.MgCl2.6H2O) obtained in step (ii) is crystallized between 32-36 0Be' either through solar or forced evaporation and the end bittern of step (iii) having density of 35.5-36.0 0Be' contains 450-460 gL"1 Of MgCl2, 5-10 gL"1 OfNaCl5 S-IO gL4 Of KCl5 S-IS gL-1 Of Ca5 O-S gL"1 of sulphate, 6-7 gL4 Br", 0.02-
0.04 % B2O3. In yet another embodiment the end bittern of step (iii) is used as such or preferably debrominated to recover bromine and simultaneously reduces the Br" impurity in debrominated bittern to <0.5 gL"1.
In yet another embodiment the prestine end bittern of step (iii) can be used for MgO recovery or more preferably it can be debrominated and used without crystallization step of step (iv).
In yet another embodiment the end bittern of step (iii) is evaporated in step (iv) to reduce the volume by 20-25% so as to crystallize out the MgCl2.6H2O (60-80% yield) that is free of the above salts and contains 0.020-0.015% B2O3 impurity.. In yet another embodiment other soluble magnesium salts such as magnesium sulphate or magnesium nitrate can be used as source of magnesium.
In yet another embodiment the alkali used in step (v) is lime, caustic soda and ammonia.
In yet another embodiment the lime used in step (v) is selected from quicklime, hydrated lime, and dolime in solid or slurry form.
In yet another embodiment the hydrated lime used in step (v) is prepared by slaking of quicklime followed by cycloning and dewatering to yield upgraded solid hydrated lime and lime water that can be reused for slaking of fresh batch of quicklime.
In yet another embodiment the stoichiometric equivalent of alkali used in step (v) is in the range of 0.8-1.0.
In yet another embodiment the amount of Mg(OH)2 seed used in step (v) is in the range of 0-10% mole for mole of magnesium salt taken.
In yet another embodiment the temperature of the precipitation reaction in step (v) is in the range of 20-120 0C. In yet another embodiment the reaction time used in the precipitation reaction in step (v) is in the range of 5 - 90 min, under, intimate mixing conditions.
In yet another embodiment the drying of pasty mass obtained in step (vi) is carried out at 70-1200C in conventional ovens or through solar drying. In yet another embodiment the D calcination operation in step (vii) is carried out at a temperature in the range of 500-1000 0C, preferably 600-900 0C, in a muffle furnace or rotary calciner or vertical kiln depending on the physical form of the dry matter.
In yet another embodiment the D calcination operation in step (vii) converts adhering MgCl2 into MgO with concomitant release of HCl vapour and CaCl2.2H2O into fused CaCl2 that is hydrated with release of heat and provides the driving force for the disintegration of the crude mass and also the rapid solubilisation of the CaCl2.
In yet another embodiment the water used in step (viii) is largely comprises the recycled washings from previous batches and the amount of water taken is sufficient to dissolve all soluble salts in the MgO and also ensure the temperature of the slurry is controlled at a temperature of 40-900C, preferably in the range of 55-650C, for the higher solubility of salts such as CaCl2 at higher temperature and to minimize the hydrolysis of MgO.
In yet another embodiment the water used in steps (viii) and (ix) contains additives to remove boron impurities in MgO or without having additives.
In yet another embodiment the washing and filtration operations of step (ix) are expedited 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH)2.
In yet another embodiment the requirement of water for purification of the calcined mass in step (ix) is reduced by a factor of 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH)2.
In yet another embodiment the wet cake obtained in step (vii) is useful for the preparation of milk of magnesia.
In still another embodiment the wet cake obtained in step (vii) is dried to yield MgO or recalcined at a temperature in the range of 500-22000C to obtain the desired product.
In yet another embodiment when the alkali used in step (v) is ammonia, the calcinations operation of step (vii) removes all impurities to yield highly pure MgO and helps avoid the operation of steps (viii) and (ix). 7
In yet another embodiment the speed of the work up and saving of fresh water is not at the expense of quality and MgO having similar purity to that obtained through the conventional process of work up OfMg(OH)2 is achieved.
In yet another embodiment of the present invention the intermediate product obtained in step (vii) is washed with water and filtered to remove calcium chloride as in steps (viii) & (ix)
In yet another embodiment of the present invention, the filtration operation followed by washing of steps (viii) & (ix) could be carried out with ease on a Nutsche filter or rotary disk filter or filter press. In yet another embodiment of the present invention the filtration is found to be rapid.
In yet another embodiment of the present invention the calcination operation of step (x) was carried out in a muffle furnace at 9000C for 2-3 h and preferably by gradually ramping the temperature. In yet another embodiment of the present invention the MgO has a purity of 98.0-
98.9% when produced directly from the end bittern of step (iii) and a purity in the range of 99.1-99.7 when prepared from crystallized or recrystallized MgCl2.6H2O of step (iv). In yet another embodiment of the present invention the MgO obtained from end bittern of step (iii) has a B2O3 impurity level of 0.10-0.12%, while the level is 0.060-0.080% when prepared from crystallized MgCl2.6H2O of step (iv), and 0.010-0.015% when prepared from recrystallized MgC-b.δHbO.
In yet another embodiment of the present invention the B2O3 level in MgO can be made still lower through appropriate treatment either of the precursor Mg(OH)2 or of the MgO itself. In yet another embodiment the lime used in step (v) is either hydrated lime or quicklime in the form of a solid or solid suspension.
In yet another embodiment the solution of steps (vi) and (ix) contains 20-30% CaCl2 and it can be used directly in the desulphatation reaction of step (i) or it can be IB2006/000627
clarified through filtration and/or addition of acid to redissolve Mg(OH)2 prior to executing step (i) or making other use of it if desulphatation of bittern is not required.
The inventive step of the present invention lies in the preparation of magnesia from magnesium chloride via intermediate formation of magnesium hydroxide on its reaction with alkali or hydrated lime. The filtered cake or unfiltered paste of magnesium hydroxide is subsequently converted into MgO through light calcination followed by washing with water and filtration to remove adhering impurities with greater ease than conventional process of washing the precipitated magnesium hydroxide prior to calcination.
The important features of the present invention are:
(1) Recognising that the main drawback of MgO production from Mg(OH)2 is the poor filterability of the latter due to its colloidal nature. This makes purification of the Mg(OH)2 a time consuming affair and demanding in terms of the volume of fresh water required per ton of MgO.
(2) Recognizing that when the goal is MgO, there is no need necessarily to purify the precursor Mg(OH)2
(3) Observing that aqueous slurry of pure MgO is easier to filter than aqueous slurry of pure Mg(OH)2. (4) Observing that whereas the initial product mixture is relatively easy to filter, the filtration process becomes increasingly tedious as the Mg(OH)2 becomes more and more free of salt.
(5) Concluding from the available literature that rehydration of MgO is a facile process at high temperature and pressure but less so under ambient conditions although some amount of Mg(OH)2 formation undoubtedly occurs as evident from the examples of the present invention. Reasoning thereafter that temperature rise during leaching of salts from the calcined MgO mass can be controlled by cooling the calcined mass to room temperature and adding adequate volume of water to minimize temperature rise.
(6) Reasoning thereafter that if crude Mg(OH)2 is lightly calcined and treated with water, then adhering MgCl2 would get converted into MgO to increase MgO yield, while the residual salts in MgO (NaCl and CaCl2 when precipitation is carried out with NaOH and lime, respectively) will dissolve in the water unless occluded in MgO and the mass should be more easily filterable using the logic of (3) and (5) above. When ammonia is used as the precipitating agent, the by-product NH4Cl would sublime away even under the conditions of light Dalcinations and there would be no need of any manner of purification whatsoever.
(7) Hypothesizing that even if the crude MgO of (6) above is in the form of lumps, such lumps should spontaneously disintegrate once contacted with water to yield a slurry which would avoid the need for any grinding of the material and yet would provide the intimate contact necessary for washing away the soluble matter in MgO.
(8) Performing experiments to demonstrate that what is hypothesized in (6) and (7) above are indeed true and the crude MgO lumps require no grinding and can be more easily purified than the precursor Mg(OH)2.
(9) Taking advantage of the post Dalcinations purification process to reduce not only soluble salts but also B2O3 through use of additives incorporated in the washing solution.
(10) Realising that the greatest advantage in operating the invention is the feasibility of producing crude Mg(OH)2 in the form of a dough which can be directly dried and calcined thereby avoiding filtration altogether while at the same time helping to conserve water and increase throughput. (11) Proving the concept of (10) by making Mg(OH)2 from the reaction of solid hydrated lime (obtained by purifying lime slurry through hydrocycloning, dewatering the slurry and recycling the lime water for preparation of more lime slurry thereby conserving water as well) and a highly concentrated hot solution of MgCl2-rich end bittern promoted by mixing in a jacketed sigma mixer. (12) Recognising that if solid MgCl2.6H2O is crystallized out from bittern to increase its purity, then such solid can be melted in the sigma mixer and reacted with upgraded and dewatered lime slurry under hot conditions to produce a dough like mass which can be further dried prior to Dalcinations or directly subjected to Dalcinations followed by purification of the mass as outlined in (6) and (7) above. (13) Extending the concept to other bases such as NaOH and dolime. (14) Using Mg(OH)2 seed to improve the granular nature of the Mg(OH)2 formed from the precipitation reaction.
(15) Proving through recalculation experiments that when the invention is practiced most judiciously, there is virtually no loss on ignition (LOI) during the second Dalcinations and thereby establishing that it may not be necessary to recalcine the mass after purification with water and instead it can be directly utilized for briquetting and thereafter sintered to yield refractory materials which is the main utility of the MgO.
(16) Also reasoning that the purified mass can be used directly for production of milk of magnesia through pressure hydration as practiced in the prior art. (17) Recognising that when precipitation OfMg(OH)2 is carried out with inexpensive lime to make the process cost-effective, further cost-effectiveness can be realized by making use of the by-product CaCl2 for desulphatation of bittern which is required to prevent contamination of magnesia with gypsum. (18) Recognising that the Dalcinations of the Mg(OH)2 to yield crude MgO would enable CaCl2 to be obtained in concentrated solution form during the purification process which would further improve the cost-effectiveness of the desulphatation process as the subsequent evaporation load would be reduced.
The following examples are given by the way of illustration and therefore should not be construed to limit the scope of the invention.
EXAMPLE - I
1 L (4.79 moles of MgCl2) of end bittern having specific gravity of 1.324 and chemical composition Ca = 0.504 % (w/v), Mg = 11.50%, SO4 = ND, Na = 0.41%, K = 0.4%, B2O3 = 0.032 was partially evaporated by forced evaporation to reduce its volume to 800 ml. The resultant mass was cooled to room temperature followed by filtration to obtain 619.7 g crystalline magnesium chloride having chemical composition, Ca = 0.22%, Mg = 11.17%, B2O3 = 0.0147 % and 370 ml of filtrate having specific gravity 1.338 and B2O3 = 0.0657%. 100 g (0.465 moles MgCl2) of the solid product was added into an NaOH solution (37 g NaOH of 98% purity in 50 mL water) and mixed under stirring. The temperature rose to 88 0C and the consistency became semi-solid. 147 g of the total of directly calcined at 6000C to obtain 41.28 g of calcined mass which was then treated with 50 mL water. The lumps crumbled and a uniform slurry was spontaneously formed within 5 min. This was filtered on a 2.5" dia. Buchner funnel. The mass was then subjected to three cycles of washing and filtration (2x50 mL + 1x75 mL) of which the middle cycle was given with 1% additive to reduce boron impurity. Total filtrate volume was 213 mL while the total filtration time was 25-30 min. The wet cake weighing 23.64 g was dried in an oven at 110 0C to 14.15 g of dry mass which was calcined at 900 0C in a muffle furnace to yield 9.67 g of MgO (I.e., 31.7 % loss on ignition) having 99.43% purity (see powder XRD in Figure IA). The remaining 47 g of reaction mass was dispersed in 50 mL water and then filtered. It was then subjected to three cycles of washing and filtration (3x25 mL) to yield a total of 137 mL of filtrate, the total filtration time being 90-100 mins. The wet cake weighing 19.14 g was dried in an oven at 110 0C to yield 6.92 g of dry mass which was calcined at 900 0C in a muffle furnace to yield 4.59 g of MgO (33.7% loss on ignition) having 96.15% purity (see powder XRD in Figure IB). It can be seen from this example that even though the Buchner funnel used was the same in both cases it took one third to one fourth of the time to filter the slurry in the case where the mass was initially calcined and then washed. Since two third of the total reaction mass was processed in this manner, i.e., the filter bed was twofold thicker and water volume for washing was twofold higher, the actual speeding up of filtration is even more pronounced. It can further be seen that the process of the present invention yielded MgO of higher purity.
EXAMPLE - 2
25 g of AR grade MgCl2.6H2O (0.122 moles) having 99% purity was thoroughly mixed with 9.5 g of hydrated lime (0.122 moles) [Ca(OH2) = 95% assay] to form wet pasty solid mass having weight 34 g which on drying at 100 - HO0C for two hours yielded 28.31 g dry mass. The loss on drying was 16.73%. This dried mass was calcined at 6000C for two hours and after Dalcinations, 15.87 g of calcined material, giving a loss on ignition 43.94%, was collected. This calcined mass was subjected to wash with water, successively three times, to recover maximum amount of calcium chloride, simultaneously purifying the product also. In the first wash of 25 mL, the CaCl2 concentration was found to be 40.8%,
18 B2006/000627
recovering 10.2 g (0.092 moles) of CaCl2 which was 75.4% of the expected amount of calcium chloride (expected amount based on hydrated lime is 13.54 g; 0.122 moles). In all total 0.2 L of wash water was used for washing operation thus recovering total 11.8 g (0.106 moles; 87.1% yield) of CaCl2. As in the case of Example 1, filtration was much more facile than in the conventional process of purification of Mg(OH)2. The washed wet cake was calcined at 9000C for two hours to obtain 3.89 g (0.095 moles; 77.9% isolated yield) of calcined magnesium oxide, having chemical composition: MgO = 98.80%, and CaO = 1.53 %. This example shows that the washing of the intermediate calcined product at 6000C facilitates the washing and filtration without compromising on product quality. Moreover, the CaCl2 could be obtained in highly concentrated form which would be beneficial for desulphatation as the subsequent evaporation load would reduce.
EXAMPLE - 3
0.10 L (0.479 moles Of MgCl2 ) of the end bittern of Example 1 was mixed under stirring with 30 g [0.385 moles Of Ca(OH)2] of hydrated lime having assay 95% w/w (80.3% of the stochiometric requirement for Mg(OH)2 formation). The resultant slurry was filtered under vacuum, which was slow. Wet cake weighing 95.12 g and 45 mL of filtrate having chemical composition: CaCl2 = 30.06%, [total 13.53 g (0.122 moles) CaCl2], Mg = 2.94% were collected. Out of the total 42.73 g (0.385 moles) assumed CaCl2 formation, (based on hydrated lime addition), 31.6% of CaCl2 was obtained in this filtrate. Wet cake was calcined at 600° C for three hours and 46.1 g of calcined material was obtained. The calcined material easily disintegrated in 70 mL of water. 62 mL of filtrate having 35% CaCl2 concentration and total 21.73 g (0.196 moles) of CaCl2, was obtained, which was 50.9% of the expected amount of calcium chloride. Other three washings, each of 50 mL (total 150 mL) were repeated using additive in 1% concentration to minimize boron impurities in the product. 144 mL of filtrate containing total 4.7 g CaCl2 (0.042 moles of CaCl2) was obtained. The overall recovery of CaCl2 was 39.96 g, (0.36 moles) which was 93.5% of expected one. Filtration in each washing was found to be facile. Washed wet cake weighing 40.5 g was dried in an oven at 100-1100C for two hours and 16.88 g dried material was obtained. This was calcined at 9000C for two hours to obtain 13.60 g (0.329 moles) calcined MgO, with 19.43% loss, having composition: MgO = 96.65%, CaO= 006/000627
2.04% and Boron as B2O3 = 0.0312%. The recovery of MgO with respect to hydrated lime is found to be 85.45%. This example indicates that the end bittern can be utilized for preparation of MgO with one additional filtration step for obtaining cake for intermediate Dalcinations. The boron content of the product can be reduced through washing with additive.
EXAMPLE - 4
2.0 L of end bittern (9.58 moles of MgCl2) as per the composition in example 1 above was heated to evaporate water upto 1500C to reduce the volume to 1.2 L. The hot bittern was taken in a Sigma mixer in which 0.725 kg (8.81 moles; 92% of stoichiometric requirement for Mg(OH)2 formation) of commercial hydrated lime having Ca(OH)2 = 89.9% (w/w) was added and mixed well for half an hour to form a pasty mass. Out of total 2.573 kg pasty mass expected assuming no loss of weight, 0.305 kg was was dried in an oven at 110 C to obtain 0.27 kg of dried material was calcined at 600° C for two hours to yield 0.215 kg calcined mass. The calcined material was cooled to room temperature and treated with 0.15 L of water and thereafter washed with an additional 0.75 L of water in lots. The wet cake was dried and calcined at 900° C to get 61.27 g of calcined MgO (1.44 moles) having chemical composition MgO = 93.95%, CaO = 2.488%, Cl = 1.768%, Boron as B2O3 = 0.107%.
EXAMPLE 5 10 L of end bittern containing 115 gL"*Mg was evaporated which on cooling gave 7 kg of solid mass. 2 kg of the solid containing 0.329 kg Mg (1.285 kg MgCl2) was taken along with 0.7 L of water and heated at 1500C to obtain a hot solution which was poured into a ribbon blender. 0.972 kg (94% of stoichiometric requirement for Mg(OH)2 formation) of powdered hydrated lime (prepared from quicklime by slaking followed by hydrocycloning) was added into the blender and the contents were thoroughly blended. After ca. 30 min the pH was found to be around 8-9 indicating completion of the reaction and the blending was stopped yielding a pasty mass. Out of the total 3.672 kg of pasty mass expected assuming no loss of weight, 1 kg was dried at HO0C for two hours in an electric oven to obtain 0.845 kg of dry mass. The material was then calcined in the form of lumps at 600 C for two hours in an electric muffle furnace to get 0.481 kg of solid (expected amount = 0.52 kg for MgO + CaCl2) . 0.24 kg of the calcined mass was cooled to room temperature and then added into 0.45 L of water at room temperature. The solid lumps of calcined solid began to crumble yielding a warm slurry (5O0C). The slurry could be easily filtered on a Bϋchner funnel to obtain 0.275 L of filtrate containing 29.4% CaCl2. The wet cake was washed successively with 3 x 0.300 L of water and in each case filtration was found to be facile. The final washing contained 1.2% CaCl2. The cake was then dried and recalcined at 9000C to yield 0.068 kg of MgO having the following analysis: MgO = 95.14 % (see powder XRD in Figure 2). CaO = 1.435 %, Cl = 0.477 %. With recycle of the washings, the requirement of fresh water is 6-8 L/kg of MgO and all of the washings can be made to have a high CaCl2 concentration (20-40%) which is beneficial for cost-effective desulphatation of bittern.
EXAMPLE 6
1 L of end bittern of Example 5 was heated to evaporate water. When the volume became 800 niL heating was stopped and the solution allowed to cool to room temperature whereupon 587 g solid MgCl2.6H2O and 362 mL of 36.7 0Be' bittern was obtained. 200 g of the solid (0.954 mol Mg) was heated to 1150C to liquefy the mass and into this 3 g of Mg(OH)2 seed was added under stirring followed by addition of AR grade lime cake [60.51 g (0.817 mol) in 60.5 mL water] in lots over 3 minutes. After addition of lime temperature was recorded as 100 0C, the contents were fairly fluid, and heating was stopped. The mass was stirred for an additional 15-20 minutes and by the time it reached room temperature the appearance was pasty. This pasty mass (303.7 g; pH ca. 8) was dried in an oven at 15O0C and thereafter calcined at 6000C (see powder XRD of Figure 3A). The calcined mass (126 g) was air cooled to room temperature and then contacted with 200 mL of water whereupon the temperature rose to 640C (this temperature rise was mainly due to the hydration and dissolution of fused CaCl2 as proved separately by experiments with pure fused CaCl2). The slurry was easily filtered to yield CaCl2 solution containing 32.3% CaCl2 and the residue was also easily washed with 50x2 mL deionised water, then dried at HO0C (see powder XRD of Figure 3B) and part of the masss was calcined at 9000C (see powder XRD of Figure 3C). For 11.0 g of dry mass, 10.8 g of calcined mass having 99.13% purity (only 0.66 % CaO impurity) was obtained. It can be seen from the powder XRD profiles of Figures 3B and 3C that these are virtually identical, suggesting that the mass remains mainly in the form of MgO even after subjecting it to purification through washing with water, which is in line with the extremely low (1.8%) LOI (loss on ignition).
The above examples teach us the manner of application of the invention, particularly as applied to semi-solid reaction mass wherein raw materials are utilized in their most concentrated forms, otherwise not feasible through the conventional technology.
The inventions also illustrate the advantages in terms of improved filterability and conservation of water, without compromising on MgO quality. Examples 5 and 6 also teach us how rock like mass crumble and disperse easily on contact with required quantity of water without any need of grinding or agitation. Example 6 also teaches us that the D calcination OfMg(OH)2 at 6000C not only yields MgO having good filterability but also yields fused calcium chloride which is readily water soluble and yields a high concentration of aqueous CaCl2. Example 6 also teaches us that crude calcined MgO produced by lime route remains largely unaffected during the purification process with water and does not convert into Mg(OH)2 to any significant extent. Example 6 also teaches us that through the method of the invention it to possible to achieve >99% pure MgO using crystallized MgCl2.6H2O and inexpensive lime after upgradation.
Advantages of the Invention The main advantage of the invention is the avoidance of the tedious process of purifying
Mg(OH)2.
Another advantage is that reaction mass even in the form of paste or dough can be handled.
Another important advantage is the conservation of fresh water.
Yet another advantage is the minimum formation of waste. Yet another important advantage is increased throughput as a result of use of reactants in more concentrated form and speeding up of the rate determining step, namely purification
OfMg(OH)2.
Yet another advantage is the spontaneous disintegration of calcined lumps of MgO which eliminates the need for grinding. Yet another advantage is that the CaCl2 in crude MgO exists in the form of fused CaCl2 which is readily soluble in water and yields a CaCl2 solution having 35-40% (w/v) concentration, which helps conserve water and also improves the economics of bittern desulphation.
Yet another advantage is the achievement of facile process of MgO preparation without compromising on product quality.

Claims

T/IB2006/000627We claim
1. An improved process for the preparation of MgO, the said process comprising the steps of: i) desulphating brine or bittern with CaCl2, ii) evaporating the clarified brine/bittern after separation of gypsum to separate out the common salt and carnallite (KCLMgCl2-OH2O), iii) recovering MgCl2 rich and other salt free end bittern from step (ii), iv) further evaporating end bittern of step (iii) to obtain crystalline MgCl2-OH2O, v) mixing MgCl2.6H2O with seeds of Mg(OHTh, followed by treating with alkali or hydrated lime/lime slurry to obtain the crude Mg(OH)2 paste/slurry, vi) filtering resultant paste/slurry to obtain crude Mg(OH)2 and calcium chloride, alternatively using crude Mg(OH)2 paste as such without filtration,
(vii) drying the above crude Mg(OH)2 paste, followed by calcination to convert
Mg(OH)2 into MgO, and converting adhering MgCl2 into MgO and HCl gas
(viii) treating the calcined mass of MgO obtained in step (vii) with water to crumble the lumps and thereby dissolving calcium chloride and other soluble salts in water to obtain the slurry, ■ (ix) filtering the above resultant slurry, followed by washing the residue with water to make it free from impurities,
(x) drying the above resultant wet cake residue containing mainly MgO and recalculating it to obtain the desired highly purified MgO and
(xi) using the CaCl2 solution filtrate obtained in steps (vi) and (ix), for desulphatatioii of brine or bittern in step (i) if lime is used in step (v).
2. A process as claimed in claim 1 wherein the bittern used in step (i) of claim 1 is obtained from ocean brine, sea brine, sub-soil brine or lake brine.
3. A process as claimed in claims 1-2 wherein the sulphate-containing bitterns used in step (i) of claim 1 are desulphated in the density range of 29-32 0Be'.
4. A process as claimed in claims 1-3 wherein the carnallite (KCLMgCl2-OH2O) obtained in step (ii) of claim 1 is crystallized between 32-36 0Be' either through solar or forced evaporation and the end bittern of step (iii) of claim 1 having density of 35.5-36.0 0Be' contains 450-460 gL"1 OfMgCl2, 5-10 gL"1 of NaCl, 5-10 gL"1 of KCl, 5-15 gL"1 of Ca, 0-5 gL"1 of sulphate, 6-7 gL"1 Br", 0.02-0.04 % B2O3.
5. A process as claimed in claims 1-4 wherein the end bittern of step (iii) of claim 1 is used as such or preferably debrominated to recover bromine and simultaneously reduces the Br" impurity in debrominated bittern to <0.5 gL"1.
6. A process as claimed in claims 1-5 wherein the end bittern of step (iii) of claim 1 is evaporated in step (iv) of claim 1 to reduce the volume by 20-25% so as to crystallize out the MgCl2.6H2O in 60-80% yield.
7. A process as claimed in claims 1-6 wherein other soluble magnesium salts such as magnesium sulphate or magnesium nitrate can be used as source of magnesium.
8. A process as claimed in claims 1-7 wherein the alkali used in step (v) of claim 1 is lime, caustic soda, and ammonia.
9. A process as claimed in claims 1-8 wherein the lime used in step (v) of claim 1 is selected from quicklime, hydrated lime, and dolime in solid or slurry form.
10. A process as claimed in claims 1-9 wherein the hydrated lime used in step (v) of claim 1 is prepared by slaking of quicklime followed by cycloning and dewatering to yield upgraded solid hydrated lime and lime water that can be reused for slaking of fresh batch of quicklime.
11. A process as claimed in claims 1-10 wherein the stoichiometric equivalent of alkali used in step (v) of claim 1 is in the range of 0.8-1.0.
12. A process as claimed in claims 1-11 wherein the amount Of Mg(OH)2 seed used in step (v) of claim 1 is in the range of 0-10% mole for mole of magnesium salt taken.
13. A process as claimed in claims 1-12 wherein the temperature of the precipitation reaction in step (v) of claim 1 is in the range of 20-120 0C.
14. A process as claimed in claims 1-13 wherein the reaction time used in the precipitation reaction in step (v) of claim 1 is in the range of 5 - 90 min, under intimate mixing conditions.
15. A process as claimed in claims 1-14 wherein the drying of pasty mass obtained in step (vi) of claim 1 is carried out at 70-1200C in conventional ovens or through solar drying.
16. A process as claimed in claims 1-15 wherein the calcination operation in step (vii) of claim 1 is carried out at a temperature in the range of 500-1000 0C, preferably 600-900 0C5 in a muffle furnace or rotary calciner or vertical kiln depending on the physical form of the dry matter.
17. A process as claimed in claims 1-16 wherein the calcination operation in step (vii) of claim 1 converts adhering MgCl2 into MgO with concomitant release of HCl vapour and CaCl2.2H2O into fused CaCl2 that is hydrated with release of heat and provides the driving force for the disintegration of the crude mass and also the rapid solubilisation of the CaCl2.
18. A process as claimed in claims 1-17 wherein the water used in step (viii) of claim 1 is largely comprises the recycled washings from previous batches and the amount of water taken is sufficient to dissolve all soluble salts in the MgO and also ensure the temperature of the slurry is controlled at a temperature of 40-900C, preferably in the range of 55-650C, for the higher solubility of salts such as CaCl2 at higher temperature and to minimize the hydrolysis of MgO.
19. A process as claimed in claims 1-18 wherein the water used in steps (viii) and (ix) of claim 1 contains additives to remove boron impurities in MgO or without having additives.
20. A process as claimed in claims 1-19 wherein the washing and filtration operations of step (ix) of claim 1 are expedited 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH)2.
21. A process as claimed in claims 1-20 wherein the requirement of water for purification of the calcined mass in step (ix) of claim 1 is reduced by a factor of 2-5 fold as a result of the improved filterability of the lightly calcined MgO vis-a-vis Mg(OH)2.
22. A process as claimed in claims 1-21 wherein the wet cake obtained in step (vii) of claim 1 is useful for the preparation of milk of magnesia.
23. A process as claimed in claims 1-22 wherein the wet cake obtained in step (vii) of claim 1 is dried to yield MgO or recalcined at a temperature in the range of 500- 22000C to obtain the desired product.
24. A process as claimed in claims 1-23, wherein the operations of steps (viii) and (ix) of claim 1 are not required when alkali used in step (v) is ammonia and the calcination operation of step (vii) removes all impurities to yield highly pure MgO.
25. A process as claimed in claims 1-24 wherein the purity of MgO obtained is >99%.
26. An improved process for the preparation of MgO, substantially as herein described with reference to the examples and drawing accompanying this specification.
EP06727340A 2006-01-31 2006-03-22 An improved process for preparation of magnesium oxide Withdrawn EP1984300A1 (en)

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