III IIIHHHHHH USOO5112584A

United States Patent (19) 11 Patent Number: 5,112,584

Mejdell et al. (45) Date of Patent: May 12, 1992
(54) METHOD FOR PRODUCTION OF 3,980,753 9/1976 Grill et al. ........................... 423/63
MAGNESUM CHILORIDE 4,100,254 7/1978 Grohmann et al. ................ 423/497
75) Inventors: Glor T. Mejdell; Hanne M. Baumann, FOREIGN PATENT DOCUMENTS
both of Porsgrunn; Kjell W. Tveten, 2471351 6/1981 France .
Skien, all of Norway 21261 of 1915 United Kingdom .
73) Assignee: Norsk Hydro a.s., Oslo, Norway 1572053 7/1980 United Kingdom.
OTHER PUBLICATIONS
(21) Appl. No.: 509,956
(22 Filed: Apr. 17, 1990 Bailar, J. C. et al., "Chemistry' Academic Press, New
York, 1978, pp. 419–420.
Related U.S. Application Data Primary Examiner-John Niebling
63 Continuation-in-part of Ser. No. 221,452, Jul. 15, 1988, Assistant Examiner-Brian M. Bolam
abandoned. Attorney, Agent, or Firm-Wenderoth, Lind & Ponack
30 Foreign Application Priority Data 57 ABSTRACT
Jul. 15, 1987 NO Norway ................................. 872945 Method for production of magnesium chloride, to be
used for production of magnesium, by leaching of mag
51) int. Cl. ................................................ C01F 5/32 nesite in hydrochloric acid. A two-stage leaching pro
52 U.S. C. .................................... 423/161; 423/163; cess is used where in a first reactor magnesite lumps are
423/497; 423/498 dissolved in hydrochloric acid. The magnesium chlo
58 Field of Search ....... ... 423/498, 497, 163, 161, ride containing solution is led to a second reactor,
423/173
where finely ground magnesite or hydrochloric acid is
56 References Cited added to obtain approximate equivalence between mag
U.S. PATENT DOCUMENTS nesium and chlorine. To precipitate the impurities an
excess of magnesium oxide or magnesium hydroxide is
2,288,610 7/1942 Dean ................................... 423/63 added in one or several purification stages.
2,398.493 4/1946 Butt et all ... 204/70
2,473,534 6/1949 Lloyd .................................. 423/63
3,479,135 1/1969 Pray et al............................ 423/497 10 Claims, 1 Drawing Sheet

CO2

MgO

s 7
an as a 8 2

4. /

22
U.S. Patent . May 12, 1992 5,112,584

S.

SQ
Vr
 5, 112,584 2
1
will be insufficient for the production of high quality
METHOD FOR PRODUCTION OF MAGNESUM magnesium metal.
CHLORIDE As some of the raw materials used are high in cal
cium, the process comprises addition of sulphates in the
CROSS REFERENCE TO RELATED 5 following purification steps to remove calcium as cal
APPLICATION cium sulphate. This procedure will render a brine far
This application is a continuation-in-part of Ser. No. too high in sulphur to be acceptable for metal produc
07/221,452 filed July 15, 1988, now abandoned. tion.
The process according to Jedlicka and to U.S. Pat.
BACKGROUND OF THE INVENTION O No. 3,980,753 are described as batch processes using a
The present invention concerns a method for produc stirred reactor for leaching of the raw material. It is
tion of magnesium chloride with sufficiently high purity preferred to use a particle size less than respectively 0.3
for production of magnesium metal, by dissolving mag mm and 3 mm for the raw material. When dissolving
nesite (MgCO3) in hydrochloric acid and with subse finely ground magnesite in hydrochloric acid, it should
quent purification of the raw solution by precipitation 15 be evident that the particles must be suspended in the
of undesired impurities, liquid to obtain reasonable reaction rates. Because of the
Raw magnesite ore is found in many qualities accord mixing, a stirred reactor will operate at a concentration
ing to the place of origin and with different reactivities. of unreacted HCl equal to the outgoing liquid. This
Macrocrystalline magnesite can have crystalites greater concentration should be kept moderately low to avoid
than 5 mm, and cryptocrystalline magnesite can have 20 substantial losses of HCl by the leaving gas.
crystalites smaller than 0.01 mm. By leaching of The capacity of a stirred reactor is limited by its
MgCO3 the grain boundaries are first attacked, in such ability to remove gas bubbles from the liquid phase. It
a way that each single crystal grain is loosened. There is should be evident that the reactor will overflow if the
therefore a great difference of reactivity between cryp 25 superficial gas velocity exceeds the rising velocity of
tocrystalline and macrocrystalline material.
It is known that magnesite has been used as a basis for the bubbles in the liquid phase. Thus the production
production of magnesium chloride. From Hans Jed Perry,must load be kept well below this limit. According to
licka: "Production of Magnesia (--99% MgO) by the 18-71, fig.18-117Engineer's
Chemical
the rising
Handbook, 5th edition, p.
velocity of bubbles in a
Ruthner-HCl-Route', Andritz-Ruthner Industrianla
gen Aktiengesellschaft, Aichholzgasse 51-53, A-1 120 30 stirred reactor will at maximum be in the order of 0.06
Vienna, pp 5-7, there is a known method for production m/s.
of magnesium oxide based on leaching of magnesite SUMMARY OF THE INVENTION
with hydrochloric acid. Magnesium, as well as iron,
aluminium, chromium, manganese, calcium etc. in the The object of this invention is to obtain a process for
raw material are dissolved by the formation of chlo 35 production of magnesium chloride with high productiv
rides. ity per reactor surface and to obtain good separation of
In this process finely ground magnesite is used. The gas/fluid.
process is based on a raw material having a grain size Another object of the invention is to obtain a suffi
smaller than 0.3 mm. In addition to a resource demand ciently pure product with respect to impurities as for
ing and expensive grinding process, foaming problems 40 example sulphate, phosphate and nickel. It is therefore
often arise when such a finely ground material is used. important to obtain a process with sufficient precipita
Fine grains have a tendency to stick to the surface of the tion and which also gives a solution with good filterabil
bubbles and form a stable foam which makes the separa ity.
tion of the gas from the fluid difficult. This gives low A third object of the invention is to develop a process
production per volume of the reactor. 45 which makes it possible to use a broad range of magne
According to this process possible remaining hydro site ore, both cryptocrystalline as well as macrocrystal
chloric acid is neutralized by adding ultra-basic reactive line. It is also an object to be able to use raw material in
flue-dust until a pH-value between 4 and 6 is reached. It a broad range of size and thereby reduce the crushing
is stated that by this pH value hydroxides of all trivalent and sieving to a minimum.
impurities are completely precipitated. Our experience 50 These objects are accomplished by a method for
is, however, that within this pH range the precipitation production of magnesium chloride for use in the pro
of divalent heavy metals, e.g. nickel, will be insufficient. duction of magnesium metal, by leaching magnesite
From U.S. Pat. No. 3,980,753 there is known a pro
cess for production of magnesia of very high purity lumps, mm,
the greater part of which have a size of 5-400
are fed to a first reactor and dissolved by introduc
55
(98-99%). The brine therefore must be low in Ca and ing hydrochloric
alkali metals. The magnesia is produced from a magne and wherein liberated acid countercurrent to the magnesite,
site waste material which can be raw magnesite, brucite, rently upwards in theCO2 and acid brine flow concur
reactor, and wherein CO2 and
dolomite or other magnesium containing ores. The ma
terial is dissolved in hydrochloric acid of 15-32% con gaseous HCl are separated off, and where the solution
centration. Impurities are precipitated by adjusting the 60 leaving the first reactor is led to a second reactor where
pH to 4-9 and the purified magnesium chloride solution finely ground magnesite or hydrochloric acid is added
is thermally decomposed into magnesia and hydrochlo to obtain approximately chemical equivalence between
ric gas. magnesium and chlorine, followed by precipitation of
For removal of undesired impurities as phosphates impurities from the resultant solution.
and heavy metals, the solution is oxidized and the pH is 65 BRIEF DESCRIPTION OF THE DRAWING
raised to 4-9 (6-8 preferred) to precipitate the contami
nants mainly as hydroxides. This pH will only bring the The drawing schematically shows a method accord
content of Nidown to a few (2-3) mg/kg liquid, which ing to the present invention.
 5, 112,584
3 4.
DETAILED DESCRIPTION OF THE
is further led via a waste gas pipe 7 to an absorption
INVENTION
tower 8 for recovering its content of hydrochloric acid
vapour by absorption in water.
By this invention a method is developed where mag To avoid high contents of hydrochloric acid in the
nesium chloride of sufficient quality to be used for elec 5 gas leaving the reactor, the acid temperature and the
trolysis can be produced, using magnesite of varying production load for a given quality of magnesite is
reactivity and purity. To dissolve the magnesite, a two chosen in such a way that at least 85% of the supplied
stage process is used. Magnesite lumps are dissolved in hydrochloric acid will react to form magnesium chlo
a first reactor where hot hydrochloric acid is fed into ride at this stage. By greater yields (above 85%) a con
the bottom of the reactor, and the magnesium chloride 10 siderable reduction of the vapour pressure of HCl above
containing solution is drained off some distance below the solution is gained.
the top of the reactor, in such a way that a layer of The first dissolving reactor (1), being packed with
lumps is situated above the fluid level. New magnesite lumps of magnesite ore, contains far more solids per
lumps are fed to the upper part of the reactor. By using volume than possible in a stirred reactor. The specific
lumps foaming is prevented, and better separation of 15 surface per volume is normally inversely proportional
gas/fluid is achieved. A part of the perceptible heat in to the particle diameter. When attacked by the acid, the
released CO2 in the leaching process is used for preheat coarse particles give off single crystals which will be
ing of lumps in the upper part of the reactor. Dependent detained in the vacancies between the lumps, increasing
on which raw material is used, one will get an excess or the total accessible surface and thus enhancing the over
deficit, respectively, of hydrochloric acid in the over 20 all reaction rate. These crystals will measure approx. 1
flow to the second reactor. The proportion between mm when the ore is macrocrystalline, and less than 0.01
magnesium and chlorine ions is therefore adjusted in the mm when cryptocrystalline.
second reactor by adding either finely ground magne
site or concentrated hydrochloric acid, in such a way The packed bed of magnesite lumps appears, as one
that equivalence, or a slight excess of acid is obtained. 25 should expect, to be very efficient in coalescing the
In the purification process undesired impurities small bubbles of CO2 given off to the liquid by the reac
(phosphates and heavy metals) are removed by increas tion.
ing the pH of the solution, adding an excess of lightly Depending on the size of the grains and the velocity
calcined reactive MgO or Mg(OH)2, eventually com of gas and fluid through the reactor, a greater or smaller
bined with oxidation of oxidizable ions with a suitable 30 part of the single crystals will follow the fluid flow out
oxidation agent. It is favourable to add oxide (hydrox through the overflow pipe 5 to the second leaching
ide) in several stages-first to neutralize free acid and reactor 6.
thereafter to add an appropriate excess. The reaction rate will therefore be strongly depen
Other features of the invention are described in more dent on the grain structure. Thus it is found that some
detail below and are also shown in the figure, which 35 cryptocrystalline magnesites with single crystals
schematically shows the manufacturing process. smaller than 0.01 mm will react up to 100 times faster
Magnesite at least 60% of which is in the range of than macrocrystalline magnesites with single crystals in
5-400 mm is filled into the first leaching reactor 1 the range 1-3 mm. Depending on the origin and the
through a feeding mechanism 2 at the top of the reactor. crystal structure of the magnesite the composition of
Especially preferred are magnesite lumps of which 40 the solution in the overflow line 5 will vary from
80-100% have a size of 5-100 mm, the rest being below strongly acidic solution with a small amount of magne
5 mm. A flow of hydrochloric acid solution with a site grain contained by use of a macrocrystalline magne
concentration of 20-38%, preferably 28-34%, is led via site, to a nearly neutral solution with a large excess of
a supply pipe 3, into the bottom of the first leaching microcrystals in the fluid when microcrystalline magne
reactor 1. The acid is preheated to 40°-95 C., prefera site is used. Either acid or finely ground magnesite must
bly 40°-90° C. Acid brine and carbon dioxide will flow 45 therefore be added to the second reactor to obtain the
cocurrently together upwards in the reactor, the desired composition.
amount of gaseous CO2 increasing, and the content of If desired the temperature difference between outlet
free acid decreasing as it flows. The higher content of and inlet in the first leaching reactor 1 can be reduced
HCl vapour in the gas vising from the bottom of the 5
reactor will be absorbed in the brine, giving near equi 0 by recirculation of the solution from the second reactor
6. This is, however, not shown in the figure.
librium values for the gas and liquid at the outlet. The second reactor is a stirred tank reactor 6. De
During the dissolving of magnesite the following pending on the stoichiometric ratio between free acid
reaction takes place: and magnesite particles contained in the overflow line 5,
MgCO3-2 HCl-MgCl2-H2O+ CO2--CO2 (1) 55 finely milled (<3 mm, preferably <0.5 mm) magnesite
is added via a dosage equipment 9, or concentrated
The reaction product is drawn off through a pipe 4 hydrochloric acid is added via a supply line 10.
some distance below the top of the reactor 1 and is led The feed of magnesite, and hydrochloric acid, respec
via an overflow-pipe 5 to the second leaching reactor 6. tively to the second reactor is adjusted in such a way
The upper part of the reactor 1 is used for separation that preferably more than 98% of the amounts of acid
of fluid and gas (carbon dioxide and vapour containing and magnesite added to the two reactors will react. The
HCl). The magnesite lumps in the reactor improve the carbon dioxide gas released by the reaction is led via the
separation of gas and fluid by coalescing the gas bub gas line 11 to the common scrubber 8, while the fluid
bles. Thus problems of foaming and droplets entrained from the second reactor is led via an overflow line 12 to
in the waste gas are efficiently counteracted. The car 65 a first purification reactor. Magnesite contains several
bon dioxide gas which is developed by the reaction will, impurities (Fe, Ni, Mn, Si, Al, etc.) of which some are
above the fluid level, utilize some of its heat content for also dissolved during the leaching. To obtain a satisfac
preheating of the magnesite fed to the reactor. The gas tory product it is therefore necessary to precipitate the
 5
5,112,584 6
undesired contaminations from the raw solution in a The capacity described in example 2 is already 6
form that readily can be filtered off. In the figure the times the theoretical maximum of a stirred reactor.
purification stages are shown consisting of one or sev EXAMPLE 4
eral stirred tank reactors 13,14,15 in series with over
flow lines 16, 17,18 between these. Heavy metals are In a pilot plant a first reactor 1 was filled with macro
5
precipitated as hydroxides in one or two stages. This is crystalline magnesite lumps (5-50mm), and 25 1/h 30%
preferably done by adding finely crushed (<0.5 mm), . HCl at a temperature of 80° C. was fed to the bottom of
reactive, magnesium oxide or hydroxide to the tanks via the reactor. The reactor had a diameter of 250 mm and
one or several feeders 19,20. These oxides are fed in an total height 1250 mm where the reaction fluid was
excess of 0.1-7 kg/m3 solution, preferably 0.1-4 kg/m3, 10 drained off 900 mm above the bottom. The solution
compared to what is needed to neutralize free acid and which was transferred to the second reactor 6, con
precipitate the contaminants in the solution. tained 4.5% free hydrochloric acid at a temperature of
By the alkalinity which is obtained by the excess of 85. The second reactor 6 had a fluid volume of 44 land
magnesium oxide, the actual acid soluble heavy metal was equipped with a stirrer. Finely ground magnesite
impurities will precipitate as hydroxides, and can be 15 was fed to the solution in such an amount that the solu
removed by filtration. If an especially low content of tion leaving the tank contained 0.5% free HCl. The
iron in the filtrate is desirable, this can be attained by solution also contained 400 mg Fe/1, 5 mg Ni/1 and 23
oxidation of bivalent iron ions to trivalent by ions add mg P/1. The purification stages consisted of three
ing oxidation agents (sodium hypochlorite, hydrogen stirred tanks in series, each of 10 l. To the first purifica
peroxide, etc.) to the second reactor or in the first purifi 20 tion tank 13 about 100 g/h lightly calcined MgO was
cation stage. This is not shown in the figure. supplied to bring the solution up to a pH sufficiently
The solution containing precipitated impurities in the high for precipitating trivalent iron oxide. To the sec
last purification stage leaves this stage via an overflow ond purification tank 14 further 80 g MgO/h was
line 18 to a continuous vacuum filter 21 where the solid added. Furthermore approximately 50 ml/h 10% H2O2
substances are removed for disposal. For this purpose 25 was added to this tank, sufficiently to oxidize all iron to
belt filters seem to be suitable, but also other types of trivalent iron. The last precipitation tank's only function
filters (rotating drum filters, etc.) could be used. was to increase the residence time and had no further
The filtrate, a clean, but alkaline magnesium chloride inlets. The suspension was filtered on a small rotating
solution with a concentration in accordance with the filter, and about 400 ml/h 30% HCl was added to the
strength of the hydrochloric acid used, leaves the filter 30 filtrate to bring the pH of the solution down to about 7.
21 via a line 22 to a stirred tank 23 where the pH of the The resulting solution contained 33.5% MgCl2, while
solution is reduced to the desired value by adding hy the content of impurities, as for example Fe, Ni and P
drochloric acid through a line 24. This adjustment is was reduced to respectively <10, < 1 and <0.5 mg/l.
necessary to avoid precipitation of magnesium oxychlo
ride, which otherwise would precipitate by cooling and 35 EXAMPLE 5
extended storage. The same pilot plant as described in Example 1 was
The product of the process, the magnesium chloride used. The first leaching reactor was filled with crypto
solution, will leave through overflow 25 from the tank crystalline magnesite lumps (5-50 mm) and fed with 20
23 for intermediate storage. 1/h 30% HCl at 70. The solution which was drained
To further illustrate the invention several experi 40 off from this reactor, was nearly neutral (<0.05% free
ments were carried out:
HCl), but was white as milk because of the unreacted
EXAMPLE grains of magnesite entrained in the solution. To the
Air was blown through a reactor filled with magne second leaching reactor 6, 51.30% HCl was added per
site lumps (5-25 mm) and partly filled with water. It 45 hour. The solution from this tank was approximately
was found that the superficial gas velocity could be clear and contained about 0.5% free acid. The solution
raised to 0.8 m/s before the water level was effected. was further treated as in Example 1 and gave a product
which contained <10 mg/1 Fe and 0.5 mg/l Ni. The
EXAMPLE 2 resulting solution contained 33.5% MgCl2.
In a reactor according to the invention, filled with 50 We claim:
magnesite lumps in the size of 30-50 mm, was added 4.3 1. A method for production of magnesium chloride
m3/m2h 30% hydrochloric acid at 93 C. The resulting for use in production of magnesium metal, by leaching
brine in overflow contained 4.6% HCl. In the off gas magnesite in hydrochloric acid, which consists essen
was measured 30 vol% CO2, 2 vol% HCl and the rest tially of
water vapour. Based on the mass balance, gas composi 55 feeding magnesite-containing lumps, the greater part
tion and temperature, the gas production was 714 m/ of which have a size of 5-400 mm, to a first reactor
m2h. The superficial gas velocity was 0.2 m/s. to form a packed bed of the lumps,
dissolving the magnesite by introducing hydrochloric
EXAMPLE 3 acid into the first reactor countercurrent to the
The same reactor as mentioned in example 2, was 60 lumps, and wherein liberated CO2 and acid brine
filled with magnesite lumps in the size of 17-25 mm. flow cocurrently upwards in the first reactor,
There was added 6.8 m3/m2h of 30% HCl at a tempera separating CO2 and gaseous HC off from the first
ture of 88 C. The resulting brine in overflow contained reactor,
2.38% HCl. Based on mass balance, gas composition introducing the resultant magnesium chloride-con
and temperature, the superficial gas velocity was 0.35 65 taining solution from the first reactor into a second
m/s. reactor,
There were no observations that contradict the esti adding either magnesite of a grain size less than 3 mm
mated superficial gas velocities in example 1. or hydrochloric acid to the second reactor to ob
 5,112,584
7 8
tain approximately chemical equivalence between actor is drained off from the first reactor below the top
magnesium and chlorine, and of the packed bed, and the packed bed above the solu
precipitating impurities from the resultant solution. tion acts as a packed tower for off gas scrubbing.
2. The method according to claim 1, wherein the 7. The method according to claim 1, wherein the
magnesite added to the second reactor has a grain size impurities are precipitated as hydroxides in one or more
less than 0.5 mm. purification stages by adding 0.1-7 kg/m magnesium
3. The method according to claim 1, wherein oxide or an equivalent amount of magnesium hydrox
60-100% of the magnesite-containing lumps fed to the ide, in excess of the amount which is consumed for
first reactor have a size of 5-100 nm, any remainder of neutralization of free acid.
said lumps having a size less than 5 mm. O 8. The method according to claim 7, wherein the
4. The method according to claim 3, wherein impurities are heavy metal.
80-100% of the magnesite-containing lumps fed to the 9. The method according to claim 7, wherein 0.1-4
first reactor have a size of 5-100 mm. kg/cm3 of the magnesium oxide or an equivalent
5. The method according to claim 1, wherein the amount of the magnesium hydroxide is added.
hydrochloric acid introduced into the first reactor is 15 10. The method according to claim 1, which further
20-38% hydrochloric acid with a temperature 40-95 comprises filtering the precipitated impurities from the
C. solution and then adjusting the pH of the solution by
6. The method according to claim 1, wherein the adding HCl.
magnesium chloride-containing solution in the first re sk k

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