Note: Descriptions are shown in the official language in which they were submitted.
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PROCESSES FOR RECOVERING RARE EARTH
ELEMENTS FROM VARIOUS ORES
TECHNICAL FIELD
[0002] The present disclosure relates to improvements in the field of
chemistry applied to the recovery, extraction and/or isolation of rare earth
elements (REE). For example, such processes are useful for obtaining rare
earth elements from various materials and derivatives thereof such as
aluminum-bearing materials and derivatives, zinc-bearing materials and
derivatives thereof, copper-bearing materials and derivatives thereof, nickel-
bearing materials and derivatives thereof, and titanium-bearing materials and
derivatives thereof.
BACKGROUND OF THE DISCLOSURE
[0003] In various technologies, there is an increasing need for rare
earth
elements, In few countries, efforts to reestablish mining of rare earth
elements
have been undertaken. In the future, supplies of rare earth elements will
considerably depend upon economic viability of the extraction and production
processes and technological innovations requiring such rare earth elements.
[0004] There is thus a need for providing an alternative to the existing
solutions for extracting rare earth elements.
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SUMMARY OF THE DISCLOSURE
[0005] According to one aspect, there is provided a process for
recovering
at least one rare earth element from at least one material, the process
comprising :
leaching the at least one material with at least one acid
so as to obtain a leachate comprising at least one metal ion, and the at least
one rare earth element;
substantially selectively precipitating, extracting and/or
isolating the at least one metal ion from the leachate and optionally
obtaining
a precipitate; and
substantially selectively precipitating, extracting and/or
isolating the at least one rare earth element from the leachate and/or the
precipitate.
[0006] According to one aspect, there is provided a process for
extracting
at least one rare earth element from at least one material, the process
comprising :
leaching the at least one material with at least one acid
so as to obtain a leachate comprising at least one metal ion, and the at least
one rare earth element; and
selectively precipitating at least one member chosen from
the at least one rare earth element, and the at least one metal ion.
[0007] According to one aspect, there is provided a process for
recovering
at least one rare earth element from at least one material, the process
comprising :
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leaching the at least one material with at least one acid
so as to obtain a leachate comprising at least one metal ion, and at least one
rare earth element;
optionally substantially selectively precipitating, extracting
and/or isolating the at least one rare earth element from the leachate and/or
the precipitate.
substantially selectively precipitating, extracting and/or
isolating the at least one metal ion from the leachate and optionally
obtaining
a precipitate; and
substantially selectively precipitating, extracting and/or
isolating the at least one rare earth element from the leachate and/or the
precipitate.
[0008] According to another example, there is provided a process for
recovering at least one rare earth element from at least one material , the
process comprising :
leaching the the at least one material with at least one
acid so as to obtain a leachate comprising at least one metal ion, the at
least
one rare earth element, and a solid, and separating the leachate from the
solid;
substantially selectively removing at least one metal ion
from the leachate and optionally obtaining a precipitate; and
substantially selectively removing the at least one rare
earth element from the leachate and/or the precipitate.
[0009] According to another example, there is provided process for
recovering at least one rare earth element from at least one material, the
process comprising :
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leaching the at least one material with at least one acid
so as to obtain a leachate comprising at least one metal ion and the at least
one rare earth element, and a solid, and separating the leachate from the
solid; and
substantially selectively removing at least one member
chosen from the at least one rare earth element and the at least one metal ion
from the leachate.
BRIEF DESCRIPTION OF DRAWINGS
[0010] In the following drawings, which represent by way of example
only,
various embodiments of the disclosure:
[0011] Fig. 1 shows a bloc diagram of an example of a process for
preparing alumina and various other products including rare earth elements,
according to the present disclosure;
[0012] Fig. 2 shows a bloc diagram of another example of process for
preparing alumina and various other products including rare earth elements,
according to the present disclosure;
[0013] Fig. 3 shows a bloc diagram of an example of process for
extracting
rare earth elements according to the present disclosure; and
[0014] Figs. 4a and 4b show a bloc diagram of another example of a
process for extracting rare earth elements according to the present
disclosure.
DETAILLED DESCRIPTION OF VARIOUS EMBODIMENTS
[0015] Further features and advantages will become more readily
apparent
from the following description of various embodiments as illustrated by way of
examples.
[0016] It was found that that the rare earth element(s) recovery can be
made, for example, in the processes described in the present disclosure at
various stages. Moreover, it was found that such processes can be useful
even if the rare earth elements are only found as traces. It was also found
that
such processes can be particularly useful for extracting rare earth elements
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from a solution that is substantially refined or purified. For example, these
processes can be useful since they can be applied to solutions from which
several of the main components have been removed They can also be
applied to solutions before removal of several of the main components.
[0017] The expression "at least one aluminum ion", as used herein
refers,
for example, to at least one type of aluminum ion chosen from all possible
forms of Al ions. For example, the at least one aluminum ion can be Al3+.
[0018] The expression "at least one iron ion", as used herein refers,
for
example, to at least one type of iron ion chosen from all possible forms of Fe
ions. For example, the at least one iron ion can be Fe2+, Fe3+, or a mixture
thereof.
[0019] The expression "at least one zinc ion", as used herein refers,
for
example, to at least one type of zinc ion chosen from all possible forms of Zn
ions. For example, the at least one zinc ion can be Zn2+.
[0020] The expression "at least one copper ion", as used herein refers,
for
example, to at least one type of copper ion chosen from all possible forms of
Cu ions. For example, the at least one copper ion can be Cul+ or Cu2+, or a
mixture thereof.
[0021] The expression "at least one nickel ion", as used herein refers,
for
example, to at least one type of nickel ion chosen from all possible forms of
Ni
ions. For example, the at least one nickel ion can be Ni2+ or Ni3+, or a
mixture
thereof.
[0022] The expression "at least one titanium ion", as used herein
refers, for
example, to at least one type of titanium ion chosen from all possible forms
of
Ti ions. For example, the at least one titanium ion can be Ti3+ or Ti4+, or a
mixture thereof.
[0023] The expression "at least one rare earth element", as used herein
refers, for example, to at least one type of rare earth element chosen from
all
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the rare earth elements described in the present disclosure in all their
possible
forms.
[0024] The expression "Ga-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
gallium.
[0025] The expression "Ce-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
cerium.
[0026] The expression "Sc-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 A., 2 % or 1 AD w/v
of
scandium.
[0027] The expression "Sm-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 `)/0, 2 % or 1 % w/v
of
samarium.
[0028] The expression "Eu-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
europium.
[0029] The expression "Gd-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
gadolinium.
[0030] The expression "Y-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
yttrium.
[0031] The expression "Pr-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
praseodymium.
[0032] The expression "Nd-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
neodymium.
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[0033] The expression "La-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 A., 2 A) or 1 % w/v
of
lanthanum.
[0034] The expression "Er-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 %, 2 % or 1 % w/v of
erbium.
[0035] The expression "Dy-free solution", as used herein refers, for
example, to a solution that comprises about less than 5 A), 2 % or 1 % w/v of
dysprosium.
[0036] The expression "rare earth element" as used herein refers, for
example, to a rare element chosen from scandium, yttrium, lanthanum,
cerium, praseodymium, neodymium, promethium, samarium, europium,
gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and
lutetium, and/or a rare metal chosen from indium, zirconium, lithium, and
gallium. These rare earth elements and rare metals can be in various form
such as the elemental form (or metallic form), under the form of chlorides,
oxides, hydroxides etc.
[0037] The expression "the at least one rare earth element" as used
herein
refers, for example, to a at least one rare element chosen from scandium,
yttrium, lanthanum, cerium, praseodymium, neodymium, promethium,
samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
thulium, ytterbium, and lutetium, and/or to at least one rare metal chosen
from
indium, zirconium, lithium, and gallium. These rare earth elements and rare
metals can be in various form such as the elemental form (or metallic form),or
under the form of chlorides, oxides, hydroxides etc.
[0038] In the processes of the present disclosure, after the leaching,
the
substantially selectively removing of the at least one member chosen from the
at least one rare earth element and the at least one metal from the leachate
can be made in various manners. The at least one metal ion (or a second
metal ion) can be removed and then, a first metal ion can be removed and
finally, the at least one rare earth element can be removed. Alternatively,
the
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first metal ion can be removed, then the second metal ion can be removed
and finally, the at least one rare earth element can be removed. According to
another example, the at least one rare earth element can be removed, then,
the first metal ion can be removed, and finally the second metal ion can be
removed. Also, the at least one rare earth element can be removed, then, the
second metal ion can be removed, and finally the first metal ion can be
removed. Various other possible combinations can also be envisaged.
[0039] The at least one acid used for leaching the at least one
material
can be HCI, H2SO4, HNO3 or mixtures thereof. More than one acid can be
used as a mixture or separately. Solutions made with these acids can be
used at various concentration. For example, concentrated solutions can be
used. For example, 6 M or 12 M HCI can be used. For example, up to 98 % or
100 % wt H2S0.4 can be used.
[0040] For example, the at least one material can be leached with HCI
having a concentration of about 15 to about 45 weight %, of about 20 to about
45 weight %, of about 25 to about 45 weight %, of about 26 to about 42
weight %, of about 28 to about 40 weight %, of about 30 to about 38 weight
%, or between 25 and 36 weight %.
[0041] For example, the at least one material can be leached at a
temperature of about 125 to about 225 C, about 150 to about 200 C, about
160 to about 180 C, or about 165 to about 170 C.
[0042] For example, the leaching can be carried out under pressure. For
example, the pressure can be about 100 to about 300 or about 150 to about
200 psig. The leaching can be carried out for about 30 minutes to about 5
hours. For example, the leaching can be carried out at a temperature of about
60 C to about 200 C.
[0043] For example, the leaching can be carried out under pressure into
an autoclave. For example, it can be carried out at a pressure of 5 KPag to
about 850 KPag, 50 KPag to about 800 KPag, 100 KPag to about 750 KPag,
150 KPag to about 700 KPag, 200 KPag to about 600 KPag, or 250 KPag to
about 500 KPag.
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[0044] For example, the leaching can be carried out at a temperature of
at
least 80 C, at least 90 C, or about 100 C to about 110 C. In certain cases
it
can be done at higher temperatures so as to increase extraction yields of rare
earth elements in certain ores. For example, the leaching can be carried out
at a temperature of at least 100 C, at least 120 C, at least 130 C, at
least
140 C, or about 140 C to about 175 C.
[0045] For example, in the leachate, the at least one rare earth
element
can be in the form of an ion.
[0046] For example, after the leaching, the at least one rare earth
element
can be solubilized into the solution and can be found as a soluble ion,
associated to chlorine, a sulfate, a nitrate, or hydrates thereof. etc.
[0047] For example, after the leaching, (if required) various bases can
be
used for raising up the pH such as KOH, NaOH, Ca(OH)2, CaO, MgO,
Mg(OH)2, CaCO3, Na2CO3, NaHCO3, CO2, or mixtures thereof.
[0048] For example, the at least one material can be chosen from
aluminum-bearing materials and derivatives, zinc-bearing materials and
derivatives thereof, copper-bearing materials and derivatives thereof, nickel-
bearing materials and derivatives thereof, and titanium-bearing materials and
derivatives thereof.
[0049] For example, the at least one metal ion can comprise at least
one
aluminum ion, at least one zinc ion, at least one copper ion, at least one
nickel
ion, at least one titanium ion and/or at least one iron ion.
[0050] For example, the at least one metal ion can comprise a first
metal
ion and a second metal ion.
[0051] For example, the first metal ion can comprise at least one
aluminum
ion, at least one zinc ion, at least one copper ion, at least one nickel ion,
at
least one titanium ion and/or at least one iron ion.
[0052] For example, the second metal ion can comprise at least one
aluminum ion, at least one zinc ion, at least one copper ion, at least one
nickel
ion, at least one titanium ion and/or at least one iron ion.
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[0053] For example, the first metal ion can be at least one aluminum
ion.
[0054] For example, the second metal ion can be at least one iron ion.
[0055] For example, the at least one iron ion can be precipitated. When
precipitating the at least one iron ion, it can be precipitated by means of an
ionic precipitation and it can precipitate in the form of various salts,
hydroxides, chlorides or hydrates thereof. For example, the at least one iron
ion can be precipitated as FeCl2, FeCl3, Fe(OH)3, Fe(OH)2, hematite, geotite,
jarosite or hydrates thereof.
[0056] For example, after the precipitation of the at least one iron
ion, the
at least one rare earth element can be solubilized into the solution and can
be
found as a soluble ion, associated as an hydroxide or a salt, or hydrates
thereof.
[0057] For example, the at least aluminum ion can be precipitated. When
precipitating the at least aluminum ion, it can be precipitated by means of an
ionic precipitation and it can precipitate in the form of various salts, (such
as
chlorides, sulfates) or hydroxides or hydrates thereof. For example, the at
least one aluminum ion can be precipitated as Al(OH)3, AlC13, Al2(SO4)3, or
hydrates thereof.
[0058] For example, after the precipitation of the at least one metal
ion,
the at least one rare earth element can be solubilized into the solution and
can be found as a an ion associated to an hydroxide or a salt or hydrates
,thereof.
[0059] For example, after precipitation of the at least one metal ion,
the
residual and substantially purified or refined solution can contain the at
least
one rare earth element into a mixture of residual soluble ions, such as
S042-, Na.
[0060] The processes of the present disclosure can be effective for
treating
various materials. The at least one material can be an aluminum-bearing
material, The aluminum-bearing metarial can be an aluminum-bearing ore.
For example, clays, argillite, mudstone, beryl, cryolite, garnet, spinel,
bauxite,
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or mixtures thereof can be used as starting material. The aluminum-bearing
material can also be a recycled industrial aluminum-bearing material such as
slag. The aluminum-bearing material can also be red mud.
[0061] The processes of the present disclosure can be effective for
treating
various nickel-bearing ores. For example, niccolite, kamacite, taenite,
limonite, garnierite, laterite, pentlandite, or mixtures thereof can be used.
[0062] The processes of the present disclosure can be effective for
treating
various zinc-bearing ores. For example, smithsonite, warikahnite, sphalerite,
or mixtures thereof can be used.
[0063] The processes of the present disclosure can be effective for
treating
various copper-bearing ores. For example, copper-bearing oxide ores, can be
used. For example, chalcopyrite, chalcocite, covellite, bornite, tetrahedrite,
malachite, azurite, cuprite, chrysocolla, or mixtures thereof can also be
used.
[0064] The processes of the present disclosure can be effective for
treating
various titanium-bearing ores. For example, ecandrewsite, geikielite,
pyrophanite, ilmenite, or mixtures thereof can be used.
[0065]
[0066] For example, the at least one rare earth element can be chosen
from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,
promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium,
erbium, thulium, ytterbium, and lutetium, and from at least one rare metal
chosen from indium, zirconium, lithium, and gallium.
[0067] For example, rare earth elements can sometimes be divided into
two categories, light rare earth elements (LRE) and heavy rare earth elements
(HRE). The light rare earth elements can comprise lanthanum, cerium,
praseodymium, neodymium, and samarium (atomic numbers 57-62), and they
are usually more abundant than heavy ones.
[0068] For example, the at least one rare element can be extracted under
the form of various salts, oxides, hydroxides, and hydrates thereof.
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[0069] For example, the at least one rare earth element can be chosen
from scandium, gallium, yttrium, lanthanum, cerium, praseodymium,
neodymium, promethium, samarium, europium, gadolinium, dysprosium,
erbium, ytterbium and mixtures thereof.
[0070] For example, the at least one rare earth element is chosen from
scandium, gallium, yttrium, lanthanum, cerium, praseodymium, neodymium,
promethium, samarium, europium, gadolinium, dysprosium and mixtures
thereof.
[0071] For example, the at least one rare earth element is chosen from
scandium, gallium, yttrium, cerium and mixtures thereof.
[0072] For example, the at least one rare earth element can be yttrium.
[0073] For example, the at least one rare earth element can be
scandium.
[0074] For example, the at least one rare earth element can be gallium.
[0075] For example, the at least one rare earth element can be cerium.
[0076] For example, the processes can comprise:
leaching the at least one material with HCI so as to obtain
the leachate comprising the at least one metal ion, and the at least one rare
earth element, and the solid and separating the leachate from the solid;
substantially selectively removing the at least one metal
ion from the leachate, thereby obtaining a composition comprising the metal
ion, and the at least one rare earth element; and
substantially selectively at least partially removing the at
least one metal ion from the composition, thereby obtaining a liquor
comprising the at least one rare earth element.
[0077] For example, the at least one metal ion can be substantially
selectively removed from the leachate by substantially selectively
precipitating
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it from the leachate and removing it therefrom by carrying out a solid-liquid
separation.
[0078] For example, the at least one metal ion can be substantially
selectively removed from the leachate by substantially selectively
precipitating
it under the form of AlC13 and removing it therefrom by carrying out a solid-
liquid separation.
[0079] For example, the composition can comprise HCI, the at least one
metal ion, and the at least one rare earth element.
[0080] For example, the composition can be an acidic composition that
comprises, the at least one metal ion, and the at least one rare earth
element.
[0081] For example, the at least one iron ion can be substantially
selectively removed from the composition by carrying out an hydrolysis so as
to convert the at least one iron ion into Fe203 and removing the precipitated
Fe203 from the composition by carrying out a solid-liquid separation, thereby
obtaining the liquor comprising the at least one rare earth element.
[0082] For example, after the removal of the precipitated Fe203, the
liquor
containing the at least one rare earth element is recirculated back for being
further concentrated by being used in precipitating the at least one aluminum
ion.
[0083] For example, after the removal of the precipitated Fe203, the
liquor
containing the at least one rare earth element is recirculated back for being
further concentrated by being used in precipitating the at least one aluminum
ion under the form of AlC13.
[0084] For example, the at least one iron ion can be Fe3+ and it can be
substantially selectively partially removed from the composition, and wherein
the composition can be further treated with a reducing agent so as to convert
Fe3+ into Fe2+ and then, Fe2+, under the form of FeCl2, can be removed from
the composition by carrying out a solid-liquid separation, thereby obtaining
the
liquor comprising the at least one rare earth element.
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[0085] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated from the
liquor
by means of a liquid-liquid extraction.
[0086] For example, the at least one rare earth element can be
extracted
from the liquor by means of liquid-liquid extraction.
[0087] For example, the at least one rare earth element can be
recovered
from the liquor by means of liquid-liquid extraction.
[0088] For example, the at least one extracting agent can be chosen
from
di-(2-ethylhexyl) phosphoric acid (HDEHP), mono(2-ethylhexy1)2-ethylhexyl
phosphonate (HEH/EHP), bis(2,4,4-trimethylpentyl)monothiophosphinic acid),
octyl phenyl phosphate (OPAP), 2-ethylhexylphosphonic acid mono-2-
ethylhexyl ester (PC88A) and optionally toluene, tributyl phosphate, di-
isoamylmethyl phosphonate, 7-(4-ethy1-1-methylocty1)-8-hydroxyquinoline, di-
(2-ethylhexyl) phosphinic acid, bis(2,4,4-trimethylpentyl) phosphinic acid, 8-
hydroxyquinoline, and (2-ethylhexyl)phosphonic acid, and mixtures thereof.
[0089] For example, the at least one extracting agent can be di-(2-
ethylhexyl) phosphoric acid.
[0090] For example, the at least one extracting agent can be 2-
ethylhexylphosphonic acid mono-2-ethylhexyl ester.
[0091] For example, the at least one extracting agent can be octyl
phenyl
phosphate.
[0092] For example, the at least one extracting agent can be tributyl
phosphate.
[0093] For example, the at least one extracting agent can be chosen
from
diethylenetriamine-penthaacetic acid (DTPA), ethylenediaminetetraacetic
(EDTA), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA),
bis(2,4,4-trimethylpentyl)monothiophosphinic acid and mixtures thereof.
[0094] According to one example, when substantially selectively
precipitating, extracting and/or isolating the at least one rare earth element
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from the leachate and/or the precipitate, the at least one rare earth element
found as an ion in the leachate can be precipitated.
[0095] For example, scandium can be precipitated in the form of
Sc(OH)3,
ScCI3, ScF3, and/or [ScF6]3-(cation), wherein the cation can be sodium,
potassium, magnesium, calcium etc
[0096] Scandium can be precipitated at a pH of about 7 to about 9, or
about 7 to about 8.
[0097] For example, the leaching can be carried out at a pH of about
0.5 to
about 2.5., about 0.5 to about 1.5, or about 1; then the second metal ion can
be precipitated at a pH of at least about 9.5, 10, 10.5, 11, or 11.5; and then
the first metal ion can be precipitated at a pH of about 8 to about 9.
[0098] For example, the second metal ion can be precipitated at a pH of
about 10 to about 12.5, 10.5 to about 11.5, about 10.8 to about 11.2, about
11.5 to about 12.5, or between 10 and 11.
[0099] For example, the precipitation of the first metal ion can be
carried
out at a pH of about 7 to about 11, about 8 to about 10.5, about 8.5 to 10 or
about 9 to about 10.
[00100] For example, the precipitation of the second metal ion can be
carried out at a pH of about 3 to about 6, about 3.0 to about 5.5, about 3 to
about 5, about 3 to about 4, about 3.0 to about 3.5, about 3.5 to about 4.0,
about 4.0 to about 5.0, about 4.0 to about 4.5, or about 4.5 to about 5Ø
[00101] For example, the precipitation of the first metal ion can be
carried
out at a pH of about 5 to about 6, about 5.0 to about 5.5, or about 5.5 to
about
6Ø
[00102] For example, when precipitating AlC13, highly concentrated dry
gaseous HCI at about 90 to about 98 % can be bubbled into the composition
comprising the at least one iron ion, the at least one aluminum ion and the at
least one rare earth element.
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[00103] For example, when carrying out the hydrolysis of the at least one
iron ion so as to convert the at least one iron ion into Fe203 and removing
the
Fe203, the pH during the hydrolysis can be about below 2.5, 2.0, 1.5 or 1Ø
[00104] According to another example, the liquor can comprise the at least
one rare earth element under the form of a chloride, and wherein the liquor
can be reacted with an extracting agent in order to substantially selectively
extract gallium therefrom, thereby obtaining a Ga-free solution and an
extracted gallium solution, and separating the solutions from one another. For
example, gallium in the liquor can be under the form of GaCI3. For example,
the extracting agent can be octyl phenyl phosphate, 2-ethylhexylphosphonic
acid mono-2-ethylhexyl ester and toluene, tri-butyl phosphate or mixtures
thereof. For example, the extracted GaCI3 can then be precipitated and then
converted into Ga203.
[00105] For example, the Ga-free solution can then be reacted with another
an extracting agent in order to substantially selectively extract cerium
therefrom, thereby obtaining a Ce-free solution and an extracted cerium
solution, and separating the solutions from one another. For example, the
cerium in the Ga-free solution can be under the form of CeCI3. For example,
the another extracting agent can be tri-butyl phosphate, di-isoamylmethyl
phosphonate, di-(2-ethylhexyl) phosphoric acid, 7-(4-ethyl-1-methyloctyI)-8-
hydroxyquinoline or mixtures thereof. For example, the process can further
comprise converting the extracted cerium into Ce02.
[00106] For example, the process can further comprise reacting the Ce-free
solution with a further extracting agent in order to substantially selectively
extract scandium therefrom, thereby obtaining a Sc-free solution and an
extracted scandium solution, and separating the solutions from one another.
For example, scandium in the Ce-free solution can be under the form of
ScCI3. For example, the further extracting agent can be di-(2-ethylhexyl)
phosphoric acid, di-(2-ethylhexyl) phosphinic acid or a mixture thereof. For
example, the process can further comprise converting the extracted scandium
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into Sc203. For example the extracted scandium can be converted into Sc203
by means of NaOH.
[00107] For example, the process can further comprise reacting the Sc-free
solution with still a further extracting agent in order to substantially
selectively
extract samarium, europium or a mixture thereof, thereby obtaining a Sm-free
solution and/or Eu-free solution and extracted samarium and/or europium
solution, and separating the solutions from one another. For example, the
still
a further extracting agent can be chosen from bis(2,4,4-trimethylpentyl)
phosphinic acid, di-(2-ethylhexyl) phosphoric acid and a mixture thereof.
[00108] For example, the process can further comprise reacting the Sm-free
solution and/or Eu-free solution with still another extracting agent in order
to
substantially selectively extract gadolinium, thereby obtaining a Gd-free
solution and an extracted gadolinium solution, and separating the solutions
from one another. For example, the still another extracting agent can be 8-
hydroxyquinoline.
[00109] For example, the process can further comprise reacting the Gd-free
solution with yet another extracting agent in order to substantially
selectively
extract yttrium, thereby obtaining a Y-free solution and an extracted yttrium
solution, and separating the solutions from one another. For example, the yet
another extracting agent can be (2-ethylhexyl)phosphonic acid, di-(2-
ethylhexyl)phosphonic acid or a mixture thereof.
[00110] For example, the process can further comprise reacting the Y-free
solution with still yet another extracting agent in order to substantially
selectively extract dysprosium and/or erbium, thereby obtaining a Dy-free
solution and/or an Er-free solution and an extracted dysprosium and/or erbium
solution, and separating the solutions from one another.
[00111] According to another example, the liquor can be reacted with a first
extracting agent in order to substantially selectively extract gallium
therefrom,
thereby obtaining a Ga-free solution and an extracted gallium solution, and
separating the solutions from one another.
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[00112] For example, gallium in the liquor can be under the form of GaCI3.
For example, the first extracting agent can be tri-butyl phosphate optionally
in
kerosene.
[00113] For example, the Ga-free solution can be reacted with a
precipitating agent for precipitating at least one rare earth element present
in
the Ga-free solution, thereby obtaining a precipitate containing the at least
one rare earth element and recovering the precipitate via a solid-liquid
separation.
[00114] For example, the process can further comprise leaching the
precipitate with at least one acid so as to obtain a leach solution comprising
the at least one rare earth element. For example the acid can be HCI. For
example, the leach solution can be reacted with a second extracting agent so
as to substantially selectively extract a first group of rare earth elements,
thereby obtaining a solution comprising the extracted rare earth elements of
the first group and a raffinate comprising a second group of rare earth
elements, and separating the solution from the raffinate. For example, the
first
group can comprise yttrium and scandium. For example, the second group
can comprise cerium, neodynium, europium and praseodymium. For example,
the second extracting agent can be chosen from di-(2-ethylhexyl)phosphoric
acid and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester.
[00115] For example, the process can further comprise reacting the solution
comprising the extracted rare earth elements of the first group with HCI at
least once so as to remove impurities therefrom.
[00116] For example, the process can further comprise stripping the
solution comprising the extracted rare earth elements of the first group with
at
least one acid so as to obtain a first group strip liquor. For example, the at
least one acid can be HCI.
[00117] For example, the process can further comprise repeating at least
once the extraction with the second extracting agent.
[00118] For example, the first group strip liquor can be reacted with a third
extracting agent so as to substantially selectively extracting at least one of
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scandium, erbium and dysprosium from the first group strip liquor, thereby
obtaining a solution comprising the extracted at least one of scandium, erbium
and dysprosium, and an yttrium raffinate, and separating the solution from the
raffinate. For example, the third extracting agent can be tri-butyl phosphate.
[00119] For example, the process can further comprise stripping the
solution comprising the extracted at least one of scandium, erbium and
dysprosium solution with at least one acid so as to obtain another first group
strip liquor. For example, the at least one acid can be HCI.
[00120] For example, the another first group strip liquor can be reacted with
a fourth extracting agent so as to substantially selectively extracting erbium
and dysprosium from the another first group strip liquor, thereby obtaining a
solution comprising the extracted erbium and dysprosium, and a scandium
raffinate, and separating the solution from the raffinate.
[00121] For example, the another first group strip liquor can be reacted with
a fourth extracting agent so as to substantially selectively extracting
scandium
from the another first group strip liquor, thereby obtaining a solution
comprising the extracted scandium, and raffinate comprising erbium dand
dysprosium, and separating the solution from the raffinate.
[00122] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated by means of
an
adsorption on activated charcoal optionally modified with tributyl phosphate
or
on a polyurethane polyether foam (PUF).
[00123] For example, the at least one rare earth element can be
substantially selectively removed by means of a liquid-liquid extraction. For
example, the liquid-liquid extraction can be carried out by using an
extracting
agent.
[00124] For example, the process can comprise selectively precipitating at
least two members chosen from the at least one rare earth element that is in
the form of ions, the second metal ion and the first metal ion. For example,
each of the members can be precipitated separately or together.
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[00125] According to another example, the processes can comprise:
leaching the at least one material with HCI so as to obtain the
leachate comprising a first metal ion a second metal ion and the at least one
rare earth element, and the solid and separating the leachate from the solid;
substantially selectively removing the second metal ion from the
leachate, thereby obtaining a composition comprising the first metal ion, and
the at least one rare earth element; and
substantially selectively at least partially removing the first metal
ion from the composition, thereby obtaining a liquor comprising the at least
one rare earth element.
[00126] According to another example, the processes can comprise:
leaching the at least one material with HCI so as to obtain the
leachate comprising a first metal ion, a second metal ion, and the at least
one
rare earth element, and the solid and separating the leachate from the solid;
substantially selectively removing the second metal ion from the
leachate, thereby obtaining a composition comprising the first metal ion, and
the at least one rare earth element; and
substantially selectively at least partially removing the first metal
ion from the composition, thereby obtaining a liquor comprising the at least
one rare earth element.
[00127] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 2.5, then the second metal ion can be
precipitated at a pH of at least about 9.5, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then at least one scandium ion
can be precipitated at a pH of about 7 to about 8.
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[00128] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 1.5, then the second metal ion can be
precipitated at a pH of at least about 10.5, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then at least one scandium ion
can be precipitated at a pH of about 7 to about 8.
[00129] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 1.5, then the second metal ion can be
precipitated at a pH of at least about 11, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then at least one scandium ion
can be precipitated at a pH of about 7 to about 8.
[00130] For example, scandium can be precipitated from a by-product
generated during the process.
[00131] For example, scandium can be precipitated from a solution
generated during the process. For example, scandium can be precipitated
using HNO3.
[00132] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated by at least
one
technique chosen from ion exchange resin, extraction by means of solvent(s)
and adsorption.
[00133] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated by means of
an
ion exchange resin.
[00134] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated by means of
a
liquid-liquid extraction.
[00135] For example, the at least one rare earth element can be
substantially selectively precipitated, extracted and/or isolated by means of
an
electrowinning process.
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[00136] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 2.5, then the second metal ion can be
precipitated at a pH of at least about 9.5, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then and then the at least one
rare earth element can be substantially selectively extracted.
[00137] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 1.5, then the second metal ion can be
precipitated at a pH of at least about 10.5, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then the at least one rare
earth
element can be substantially selectively extracted.
[00138] According to another example, the leaching can be carried out
at a pH of about 0.5 to about 1.5, then the second metal ion can be
precipitated at a pH of at least about 11, then the first metal ion can be
precipitated at a pH of about 8 to about 9, and then the at least one rare
earth
element can be substantially selectively extracted.
[00139] For example, the at least one material / acid ratio can be about 1
/ 10 in weight by volume.
[00140] According to another example, the processes can further
comprise at least one of
at least partially removing the second metal ion from the
leachate by substantially complexing the second metal ion with an extracting
agent;
selectively precipitating the second metal ion;
selectively precipitating the first metal ion; and
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at least partially removing the first metal ion from the
leachate by substantially complexing the first metal ion with another
extracting
agent.
[00141] According to another example, the processes comprise:
leaching the at least one material with HCI so as to
obtain a leachate comprising a first metal ion and a second metal ion and a
solid residue, and separating the leachate from the solid residue;
at least partially removing the second metal ion from the
leachate by substantially selectively precipitating the second metal ion by
reacting the leachate with a base so as to obtain an aqueous composition rich
in the first metal ion and comprising the at least one rare element and a
precipitate, and removing the precipitate from the composition;
purifying the aqueous composition by substantially
selectively precipitating the first metal ion, thereby obtaining another
composition comprising the at least one rare element and another precipitate,
removing the precipitate from the composition; and
substantially selectively extracting the at least one rare
element from the another composition.
[00142] According to another example, the processes can comprise:
leaching the at least one material with HCI so as to obtain
a leachate comprising a first metal ion and a second metal ion and a solid
residue, and separating the leachate from the solid residue,
at least partially removing the second metal ion from the
leachate by substantially selectively precipitating the second metal ion by
reacting the leachate with a base so as to obtain an aqueous composition rich
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in the first metal ion and comprising the at least one rare element and a
precipitate, and removing the precipitate from the composition;
substantially selectively extracting the first metal ion from
the aqueous composition by means of a hollow fiber membrane, or by a
liquid-liquid extraction, and removing the extracted first metal ion, thereby
obtaining an aqueous composition depleted in the first metal ion comprising
the at least one rare element; and
substantially selectively extracting the at least one rare
element from the aqueous composition.
[00143] According to another example, the processes can comprise:
leaching the at least one material with HCI so as to obtain
a leachate comprising a first metal ion and a second metal ion and a solid
residue, and separating the leachate from the solid residue;
at least partially removing the second metal ion from the
leachate by substantially selectively complexing the second metal ion with an
extracting agent so as to obtain an aqueous composition rich in the first
metal
ion comprising the at least one rare earth element;
purifying the aqueous composition by substantially
selectively precipitating the first metal ion, thereby obtaining another
composition comprising the at least one rare element and another precipitate,
removing the precipitate from the composition; and
substantially selectively extracting the at least one rare
element from the another composition.
[00144] According to another example, the processes can comprise:
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leaching the at least one material with HCI so as to obtain
a leachate comprising a first metal ion and a second metal ion and a solid
residue, and separating the leachate from the solid residue;
at least partially removing the second metal ion from the
leachate by substantially selectively complexing the second metal ion with an
extracting agent so as to obtain an aqueous composition rich in the first
metal
ion comprising the at least one rare earth element;
substantially selectively extracting the first metal ion from
the aqueous composition by means of a hollow fiber membrane, or by a
liquid-liquid extraction, and removing the extracted first metal ion, thereby
obtaining an aqueous composition depleted in the first metal ion comprising
the at least one rare element; and
substantially selectively extracting the at least one rare
element from the aqueous composition depleted in the first metal ion.
[00145] According to another example, the processes can comprise:
leaching the at least one material with HCI so as to
obtain a leachate comprising a first metal ion and a second metal ion and a
solid residue, and separating the leachate from the solid residue;
at least partially removing the first metal ion from the
leachate by substantially selectively precipitating the first metal ion so as
to
obtain an aqueous composition rich in the second metal ion comprising the at
least one rare element and a precipitate, and removing the precipitate from
the composition;
substantially selectively precipitating the second metal ion
from the aqueous composition rich in the second metal ion, and removing the
precipitate therefrom, thereby obtaining thereby obtaining an aqueous
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composition depleted in the second metal ion and comprising the at least one
rare element; and
substantially selectively extracting the at least one rare
element from the aqueous composition depleted in the second metal ion.
[00146] For example, the first metal ion can comprises at least one
aluminum ion.
[00147] For example, the second metal ion can comprise at least one
iron ion.
[00148] For example, the at least one aluminum ion can be precipitated
under the form of AlC13 in a crystallizer, for example, by sparging gaseous
HCI.
[00149] For example, the at least one iron ion can be precipitated under
the form of Fe203 by means, for example, of an hydrolysis.
[00150] For example, the aqueous composition rich in the first metal ion
can be purified by complexing the first metal ion with an extracting agent so
as to obtain a complex, separating the complex form the composition and
precipitating the first metal ion.
[00151] For example, the aqueous composition rich in the first metal ion
can be purified by complexing impurities contained in aqueous composition
rich in the first metal ion with an extracting agent, at least partially
removing
the complexed impurities from the composition and precipitating the first
metal
ion.
[00152] According to another example the processes can comprise:
1- leaching argillite with at least one acid (for example a solution of HCI
or gaseous HCI (for example at pH of about 0.5 to about 1.5 or about
0.8 to about 1.2). The leaching cal also be carried out under pressure;
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2- removing iron by ionic precipitation by raising th at pH of about 10 to
about 12 or about 11 to about 12 (or extracting it with extracting
agents) and filtering out all non-soluble hydroxides;
3- precipitating aluminum at a pH of about 7.5 to about 9.0 or about 7.8
to about 8.2 and and filtering aluminium hydroxide as a solid;
4- optionally purifying aluminum (Al(OH)3) using at least one of a liquid-
liquid extraction, a membrane and an extracting agent suitable for
complexing aluminum ions; and
5- precipitating, extracting and/or isolating at least one rare earth
element can be carried out after at least one of steps 1, 2, 3 and 4.
[00153] For more details and explanations regarding at least certain
portions of steps 1 to 4, see W02008141423.
[00154] According to another example the processes can comprise:
1- leaching argillite with an acid (for example a solution of HCI 18-
32wt%. The leaching can also be carried out under pressure such as
about 350 KPag to about 500 KPag during about 4 to about 7 hours ;
2- removing iron by ionic precipitation by raising the at pH of about 10
to about 12 or about 11 to about 12 (or extracting it with extracting
agents) and filtering out all non-soluble hydroxides;
3- precipitating aluminum at a pH of about 7.5 to about 9.0 or about 7.8
to about 8.2 and and filtering aluminium hydroxide as a solid;
4- optionally purifying aluminum (Al(OH)3) using at least one of a liquid-
liquid extraction, a membrane and an extracting agent suitable for
complexing aluminum ions; and
5- precipitating, extracting and/or isolating at least one rare earth
element can be carried out after at least one of steps 1, 2, 3 and 4.
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[00155] According to another example as shown in Fig. 1, the processes
can involve the following steps (the reference numbers in Fig. 1 correspond to
the following steps) :
1- The aluminum-bearing material is reduced to an average
particle size of about 50 to about 80 pm.
2- The reduced and classified material is treated with hydrochloric
acid which allows for dissolving, under a predetermined temperature and
pressure, the aluminum with other elements like iron, magnesium and other
metals including rare earth. The silica remains totally undissolved.
3- The mother liquor from the leaching step then undergoes a
separation, a cleaning stage in order to separate the purified silica from the
metal chloride in solution.
4- The spent acid (leachate) obtained from step 1 is then brought
up in concentration with dry and highly concentrated gaseous hydrogen
chloride by sparging this one into a crystallizer. This results into the
crystallization of aluminum chloride hexahydrate (precipitate) with a minimum
of other impurities. Depending on the concentration of iron chloride at this
stage, further crystallization step(s) can be required. The precipitate is
then
separated from the liquid.
5- The aluminum chloride hexahydrate is then calcined (for
example by means of a rotary kiln, fluid bed, etc) at high temperature in
order
to obtain the desired alumina. Highly concentrated gaseous hydrogen
chloride is then recovered and excess is brought in aqueous form to the
highest concentration possible so as to be used (recycled) in the acid
leaching
step.
6- Iron chloride (the liquid obtained from step 4) is then pre-
concentrated and hydrolyzed at low temperature in view of the Fe203
(hematite form) extraction and acid recovery from its hydrolysis. All heat
recovery from the calcination step (step 5), the leaching part exothermic
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reaction (step 1) and other section of the process is being recovered into the
pre-concentrator.
10- After the removal of hematite, a solution rich in rare earth
elemants can be processed by using any one of the processes described in
the present disclosure for recovering rare earth elements from aluminum-
bearing materials. For example, the recovered rare earth elements can be in
various forms such oxides, chlorides, hydroxides etc. As previously indicated
in the present disclosure, the expression "rare earth element" can also
encompass "rare metal" and thus, in step 10, rare metals can also be
recovered. For example, rare metals can be under the form of rare metals
oxides. Thus, in Figs. 1 and 2, the step 10 can be, for example, the processes
shown in Fig. 3 or in Figs. 4a and 4b.
Other non-hydrolyzable metal chlorides (Me-CI) such as MgCl2 and
others then undergo the following steps:
7- The solution rich in magnesium chloride and other non-
hydrolyzable products at low temperature is then brought up in concentration
with dry and highly concentrated gaseous hydrogen chloride by sparging it
into a crystallizer. This results into the precipitation of magnesium chloride
as
an hexahydrate.
8- Magnesium chloride hexahydrate is then calcined (either
through a rotary kiln, fluid bed, etc.) and hydrochloric acid at very high
concentration is thus regenerated and brought back to the leaching step.
9- Other Me-CI undergo a standard pyrohydrolysis step where
mixed oxides can be produced and hydrochloric acid at the azeotropic point
(20.2% wt.) is regenerated.
[00156] For example, the liquid can be concentrated to a concentrated liquid
having an iron chloride concentration of at least 30% by weight; and then the
iron chloride can be hydrolyzed at a temperature of about 155 to about 350 C
while maintaining a ferric chloride concentration at a level of at least 65%
by
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weight, to generate a composition comprising a liquid and precipitated
hematite, and recovering the hematite.
[00157] For example, the liquid can be concentrated to a concentrated liquid
having an iron chloride concentration of at least 30% by weight; and then the
iron chloride can be hydrolyzed at a temperature of about 155 to about 350 C
while maintaining a ferric chloride concentration at a level of at least 65%
by
weight, to generate a composition comprising a liquid and precipitated
hematite; recovering the hematite; and recovering rare earths from the liquid.
For example, the process can further comprise, after recovery of the rare
earths, reacting the liquid with HCI so as to cause precipitation of MgC12,
and
recovering same.
[00158] As previously indicated, various aluminum-bearing materials can be
used as starting material of the processes disclosed in the present
disclosure.
Examples with clays and bauxite have been carried out. However, the person
skilled in the art will understand that the continuous processes can handle
high percentages of silica (>55%) and impurities as well as relatively low
percentages of aluminum (for example as low as about 15%) and still being
economically and technically viable. Satisfactory yields can be obtained (>93-
95%) on A1203 and greater than 75% on rare earth elements. No pre-thermal
treatment in most cases are required. The processes disclosed in the present
disclosure involve special techniques on leaching and acid recovery at very
high strength, thereby offering several advantages over alkaline processes.
[00159] In step 1 the mineral, whether or not thermally treated is crushed,
milled, dried and classified to have an average particle size of about 50 to
about 80 pm.
[00160] In step 2, the milled raw material is introduced into the reactor
and
will undergo the leaching phase.
[00161] The leaching hydrochloric acid used in step 2 is a recycled or
regenerated acid from steps 5, 6, 8 and 9 and its concentration can vary from
15% to 45% weight. percent. Higher concentration can be obtained using a
membrane separation, a cryogenic and/or high pressure approach. The acid
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leaching can be carried out under pressure and at temperature close to its
boiling point thus, allowing a minimal digestion time and extended reaction
extent (90%-100%). Leaching (step 2) can be accomplished in a semi-
continuous mode where spent acid with residual free hydrochloric acid is
replaced by highly concentrated acid at a certain stage of the reaction or
allowing a reduced acid/mineral ratio, thereby reducing reaction time and
improving reaction kinetics. For example, kinetic constant k can be : 0.5 ¨
0.75 g/mole.L
[00162] As previously indicated, alkali metals, iron, magnesium, calcium,
potassium, rare earth elements and other elements will also be in a chloride
form at different stages. Silica will remain undissolved and will undergo
(step
3) a liquid/solid separation and cleaning stage. The processes of the present
disclosure tend to recover maximum amount of free hydrochloric acid left and
chlorides in solution in order to maximize hydrochloric acid recovery yield,
using techniques such as rake classifying, filtration with band filters,
centrifugation, and others. Mother liquor free of silica is then named as
spent
acid (various metal chlorides and water) and goes to the crystallization step
(step 4).
[00163] In step 4, the spent acid (or leachate) with a substantial amount of
aluminum chloride is then saturated with dry and highly concentrated gaseous
hydrogen chloride obtained or recycled from step 5, which results in the
precipitate of aluminum chloride hexahydrate (AIC13 = 6H20). The precipitate
retained is then washed and filtered or centrifuged before being fed to the
calcination stage (step 5). The remaining of the spent acid from step 4 is
then
processed to acid recovery system (steps 6 to 8) where pure secondary
products will be obtained.
[00164] In step 5, aluminum oxide (alumina) is directly obtained from high
temperature conditions. The highly concentrated hydrogen chloride in
gaseous form obtained can be fed to steps 4 and 7 for crystallization. The
excess hydrogen chloride is absorbed and used as regenerated acid to the
leaching step 2 as highly concentrated acid, higher than the concentration at
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the azeotropic point (>20.2%). For example, such a concentration can be
about 25 to about 45 weight % or between 25 and 36 weight %.
[00165] After step 4, various chlorides derivatives of (mainly iron chlorides,
magnesium chloride and rare earth element in the form of chlorides) are next
subjected to an iron extraction step. Such a step can be carried out for
example by using the technology disclosed in WO 2009/153321.
[00166] In step 6, a hydrolysis at low temperature (155-350 C) is carried out
and pure Fe203 (hematite) is being produced and hydrochloric acid of at least
15% concentration is being regenerated. The method as described in WO
2009/153321 is processing the solution of ferrous chloride and ferric
chloride,
possible mixtures thereof, and free hydrochloric acid through a series of
steps
pre-concentration step, oxidation step where ferrous chloride is oxidized into
ferric form, and finally through an hydrolysis step into an operational unit
called hydrolyser where the ferric chloride concentration is maintained at 65
weight % to generate a rich gas stream where concentration ensures a
hydrogen chloride concentration of 15-20.2% and a pure hematite that will
undergo a physical separation step. Latent heat of condensation is recovered
to the pre-concentration and used as the heating input with excess heat from
the calcination stage (step 5).
[00167] The mother liquor left from the hydrolyser (step 6), after iron
removal, is rich in other non-hydrolysable elements and mainly comprises
magnesium chloride or possible mixture of other elements (various chlorides)
and rare earth elements.
[00168] Rare earth elements in form of chlorides are highly concentrated in
percentage into the hydrolyser operational unit (step 6) and are extracted
from
the mother liquor (step 10) where the processes defined in the present
disclosure for recovering rare earth elements from aluminum-bearing
materials can be employed. For example, rare earth elements under various
forms can thus be extracted. For example, it can be under the form of oxides.
REO. The processes of the present disclosure for recovering rare earth
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elements can allow, for example, to concentrate to a high concentration the
following rare earth elements, within the hydrolyser: scandium (Sc), galium
(Ga), yttrium (Y), dysperosium (Dy), cerium (Ce), praseodynium (Pr),
neodynium (Nd), europium (Eu), samarium (Sm), gadolinium (Gd), lanthanum
(La), erbium (Er). Of course, the at least one rare earth element that will be
recovered will depend upon the nature of the startin material (aluminum-
bearing material).
[00169] The spent acid liquor from steps 6 and 10 rich in value added
metals, mainly magnesium, is processed to step 7. The solution is saturated
with dry and highly concentrated gaseous hydrogen chloride from step 5,
which results in the precipitation of magnesium chloride hexahydrate. The
precipitate retained, is fed to a calcination stage step 8 where pure MgO
(>98% wt.) is obtained and highly concentrated hydrochloric acid (for example
of at least 38 %) is regenerated and diverted to the leaching step (step 2).
An
alternative route for step 7 is using dry gaseous hydrochloric acid from step
8.
[00170] In step 9, metal chlorides unconverted are processed to a
pyrohydrolysis step (700-900 C) to generate mixed oxides and where
hydrochloric acid from 15-20.2% wt. concentration can be recovered.
[00171] According to another example as shown in Fig. 2, the processes
can be similar to the example shown in Fig, 1 but can comprise some variants
as below discussed.
[00172] In fact, as shown in Fig. 2, the process can comprise (after step 6 or
just before step 10) an internal recirculation back to the crystallization
step 4.
In such a case, The mother liquor from the hydrolyser (step 6) can be
recirculated fully or partially to the crystallization of step 4 where a
concentration increase will occur with respect to the non-hydrolyzable
elements including rare earth elements.
[00173] Such a step can be useful for significantly increasing the
concentration of rare earth elements, thereby facilitating their extraction in
step 10.
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[00174] With respect to step 7, the solution rich in magnesium chloride and
other non-hydrolyzable products at low temperature is, as previously
discussed, then brought up in concentration with dry and highly concentrated
gaseous hydrogen chloride by sparging it into a crystallizer. This can result
into the precipitation of magnesium chloride as an hexahydrate (for example
after sodium and potassium chloride removal).
[00175] As shown in Fig. 2, an extra step 11 can be added. Sodium chloride
can undergo a chemical reaction with sulfuric acid so as to obtain sodium
sulfate and regenerate hydrochloric acid at the azeotropic point. Potassium
chloride can undergo a chemical reaction with sulfuric acid so as to obtain
potassium sulfate and regenerate hydrochloric acid at the azeotropic point.
[00176] Certain prophetical examples are hereby provided in the present
disclosure for substantially selectively recovering, precipitating, extracting
and/or isolating at least one rare earth element. This can be done, for
example from the leachate and/or the precipitate and any other downstream
derivatives, solutions, precipitates, compositions or liquors.
[00177] For example, recovering, precipitating, extracting and/or isolating
at
least one rare earth element can be carried out by:
- precipitating least one rare earth element (for example at a pH of
about 6 to about 8, 7 to about 8, or 7 to about 7.5);
- using an ion exchange resin (for example, as described in US
4,816,233;
- extraction by means of solvent(s) (for example a liquid-liquid
extraction can be carried out using di-(2-ethylhexyl) phosphoric acid
(HDEHP (also called DEHPA or D2EHPA)), mono(2-ethylhexy1)2-
ethylhexyl phosphonate (HEH/EHP), octyl phenyl phosphate (OPAP),
2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A)and
optionally toluene (for example as described in Kao et al. in Chemical
Engineering Journal, Volume 119, Issues 2-3, June 15, 2006, pages
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167-174 or by means of extracted using an alkyl phosphate
for example as described in US 3,013,859;
- using an extracting agent (for example using bis(2,4,4-
trimethylpentyl)monothiophosphinic acid or a derivative thereof);
- adsorption on activated charcoal (activated carbon adsorption)
optionally modified with tributyl phosphate or on a polyurethane
polyether foam (PUF); (for example as described in Zhou et al. in
RARE METALS, Vol. 27, No. 3, 2008, p223-227;
- extraction with hollow fiber membranes; and
- using an electrowinning technology (for example as described in US
2004/0042945.
[00178] For example, scandium can be precipitated (optionally using HNO3)
from a residual solution generated during the process (for example when iron
is precipitated and/or when aluminum is precipitated).
[00179] For example, when substantially selectively precipitating,
extracting
and/or isolating at least one rare earth element from the leachate and/or the
precipitate and any other downstream derivatives, various sequences can be
carried out i.e. depending on the nature of the starting material and the rare
earth elements present, a given rare earth element can be more easily
extracted before or after another given rare earth element.
[00180] For example, as shown in Fig. 3, in a mixture or liquor comprising
HCI, water and rare elements in the form of chlorides, the mixture can be
treated with an extracting agent in order to extract GaCI3 therefrom, thereby
obtaining a Ga-free solution. Such an extracting agent can be, for example,
octyl phenyl phosphate (OPAP)or 2-ethylhexylphosphonic acid mono-2-
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ethylhexyl ester (PC88A)and toluene. GaC13 can then be precipitated and then
converted into Ga203 by heating it.
[00181] Then, the Ga-free solution can be treated with an extracting agent
(for example SME 529TM tri-butyl phosphate or di-isoamylmethyl
phosphonate, di-(2-ethylhexyl) phosphoric acid, 7-(4-ethy1-1-methylocty1)-8-
hydroxyquinoline (Kelex 100TM) in n-heptane with the addition of 10% n-
decanol.) for substantially selectively extracting cerium chloride therefrom
so
as to obtain a Ce-free solution. CeCI3 can be eventually converted into Ce02.
[00182] Then, the Ce-free solution can be treated with an extracting agent
such as di-(2-ethylhexyl) phosphoric acid or di-(2-ethylhexyl) phosphinic acid
so as substantially selectively extract Sc and to provide a Sc-free solution.
The extracted Sc can be treated with an oxidizer (such as NaOH) so as to
provide Sc203.
[00183] Then, the various remaining rare earth elements (Pr, Nd, Sm, Eu,
La, Gd, Y, Dy, Er etc.) in the Sc-free solution can be extracted in different
possible orders.
[00184] For example, it has to be noted that the process schematized in Fig.
3 can be used as a component of various other processes such as the
process schematized in Fig. 1 or in Fig. 2. For example, the step 10 of Figs.
1
and 2 can be the process schematized in Fig. 3.
[00185] For example, as shown in Figs. 4a and 4b, a process for extracting
rare earth elements can comprise:
Ferric reduction to ferrous using iron;
Separation of gallium from the ferrous chloride solution;
Precipitation and pre-concentration of rare earth elements from the
raffinate;
Re-leaching and fractioning of the rare earth elements into light (LRE)
and heavy (HRE) groups;
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Separation of yttrium from scandium and heavy rare earth elements;
and
Separation of scandium and heavy rare earth elements
[00186] The reduction of
ferric to ferrous with a reducing agent (such as
metallic iron) can be used so as to prevent iron coextraction or iron
precipitation. The reaction time can be very short and it can generate heat.
[00187] As shown in Figs. 4a
and 4b, The ferric chloride feed solution
101 can be fed to an agitated reaction tank and a reducing agent (for example
metallic iron 102 ) can added so as to allow for converting ferric chloride to
ferrous chloride (see "Ferric Removal"). After a solid-liquid separation (s/I
separation), the resulting filtrate 103 can be further treated in a gallium
extraction circuit. A filter cake, containing solid material and iron, can be
dewatered and the resulting slurry can then be prepared for disposal.
[00188] Gallium can then be
extracted with an organic solution
containing an extracting agent (for example tri-butyl phosphate (TBP)
dissolved in kerosene) (see "Gallium Recovery"). The rare earth and iron can
thus be left in the raffinate. The extraction can vary as a function of the
chloride ion concentration. For example, the higher chloride ion
concentration,
the stronger tendency for gallium complex formation and the better extraction.
[00189] For example, for
gallium (recovery from hydrochloric acid
solutions, reagents such as tri-butyl phosphate or tertiary amines (e.g.
Alamine 336) can be used. For example, when increasing hydrochloric acid
(HCI) concentration, gallium extraction can rise to a maximum and can then
decrease again. For example, HCI concentration can be increased up to
about 4 M HCI for the gallium extraction. Under these conditions, gallium can
be present in the form of HGaCI4 complex and TBP extracted gallium as a
trisolvate (HGaC1.4*3TBP) (for example when the extracting agent is TBP).
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[00190] Co-extracted iron, accumulated in the organic phase can be
scrubbed with hydrochloric acid (see "Gallium Strip Liquor"). The resulting
organic solution, containing gallium can be fed to a stripping circuit where
gallium is stripped with water 104. The raffinate 106, containing ferrous
chloride and the rare earth elements, can then be fed to the rare earth
precipitation section (see "Bulk REE Removal"). The final strip liquor 105
contains gallium.
[00191] For example, oxalate precipitation of rare earth elements result
in very low solubility of the compounds in aqueous solution. The precipitation
of rare earth oxalates can be achieved by addition of a precipitation reagent
107. For example, oxalic acid 107 can be used for the precipitation. For
example, precipitating agent that are effective for precipitating rare earth
elements of the trivalent (such as oxalate (from oxalic acid)) can be used.
For
example, such precipitating agents can have provide a very low solubility in
aqueous solution to so-formed precipitate.
[00192] An overflow from the primary rare earth elements precipitation
109 can be fed to a ferrous treatment circuit. After filtration, the filter
cake,
containing the rare earth elements, can be fed to a washing and dewatering
unit. A resulting slurry 108 can then be prepared for re-leaching (see "REE-
Re-leaching"). Re-leaching of the rare earth filter cake can be carried out
using hydrochloric acid 110.
[00193] From a pre-concentrated and pH adjusted chloride solution 111,
that contains for example about 150 to about 250 g/L, rare earth elements
yttrium, scandium and the heavy rare earth (HRE) are extracted (see "Primary
REE Recovery") with an extracting agent (for example (di-(2-
ethylhexyl)phosphoric acid (D2EHPA) or 2-ethylhexylphosphonic acid mono-
2-ethylhexyl ester (PC88A (also called lonquestTM 801) in kerosene)).
Scandium, the other HRE and also yttrium can be extracted and leaving the
light rare earth elements (LRE) in a raffinate 113.
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[00194] A loaded organic phase can then be selectively scrubbed with
hydrochloric acid (2 M HCI) to remove the co-extracted LRE. A secondary
scrubbing section can remove europium by using weak hydrochloric acid (1 to
1.5 M HCI). The extract, containing yttrium, scandium and the HRE, can then
be stripped with strong acid (3.5 M HCI) 112.
[00195] The HRE strip liquor 114, containing yttrium and scandium, can
be treated further to obtain more than 90 % Y203 and Sc203 in a first circuit
of
a double solvent extraction purification process. In a first step, the aqueous
solution, containing about 25 g / L (of rare earth elements in the form of
oxides) and 0.4 M HCI, can be brought into contact with an extracting agent
(for example (di-(2-ethylhexyl)phosphoric acid (D2EHPA) or 2-
ethylhexylphosphonic acid mono-2-ethylhexyl ester (PC88A (also called
lonquestTm 801) in kerosene)) (see "Secondary REE Recovery"). The loaded
organic phase is then scrubbed with diluted hydrochloric acid. Scandium,
yttrium and HRE can be extracted by the reagent and finally stripped with
strong hydrochloric acid 115 at a high oxide / acid ratio. The final strip
liquor
would have a concentration in rare earth elements oxides of about 40 g/L and
about 1 M HCI. This solution is partially neutralized.
[00196] This pre-treated strip liquor 116 can be further extracted
with an
extracting agent (for example tri-butyl phosphate (TBP) in kerosene). The
treatment can be done in a multi stage procedure, and ending up in a final
stripping of the loaded organic with water 117. All HRE and scandium can
thus extracted, leaving yttrium in a raffinate 119. A final strip liquor 118,
containing HRE, forms the source for further separation of scandium and
heavy rare earth. In order to do so, various possible extracting agents can be
used such as di-(2-ethylhexyl) phosphoric acid.
[00197] The separation of scandium from other HRE, (for example
dysprosium and erbium) can be carried out using a further solvent extraction
purification circuit, similar to the yttrium separation and purification
process
and previously described. Thus, the extracting agent can be the same or a
different one, the strip solution 120 can be the same than 117, thereby
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providing a scandium raffinate 121 and a strip liquor 122 comprising europium
and erbium.
[00198] As an
alternative, yttrium can be extracted as described in US
3,751,553. In fact,
yttrium
can be extracted starting from a xenotime concentrate. It can be done by
using three solvent extraction circuits. In a first step, DEHPA can be used to
separate yttrium. In a second step, tri (caprylmethyl) ammonium nitrate
(Aliquat 336) can be used to extract and separate cerium and leave yttrium in
the raffinate. In a third step, Tm, Yb, and Lu can be extracted by means of
tri
(caprylmethyl) ammonium thio cyanate. In this extraction loop, yttrium
behaves like a cerium element. From this step, high-purity of yttrium oxide
can
be obtained.
[00199] According to
another alternative, yttrium oxide can be extracted
in two steps i.e. tri (caprylmethyl) ammonium nirate can be used to separate a
mixture La ¨ Er/Y ¨ Lu and then, a purification of yttrium is carried out
using
versatic acid.
[00200] Solvent
extraction is a selective separation procedure for
isolating and concentrating valuable elements from an aqueous solution with
the aid of an organic solution. In the procedure the aqueous solution
containing the element of interest, often at a low concentration and together
with other dissolved substances (pollutants), is mixed (extraction) with an
organic solvent containing a reagent. The element of interest reacts with the
reagent to form a chemical compound that is more soluble in the organic than
in the aqueous solution. As a consequence, the element of interest is
transferred to the organic solution.
[00201] Subsequently,
in order to recover the extracted substance, the
organic solution is mixed (stripping) with an aqueous solution whose
composition is such that the chemical compound between the element and
the reagent is split and, thus, the element is recovered in the "new" aqueous
solution, in a pure form. The concentration of the element in the "new"
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aqueous solution may be increased, often to 10-100 times that of the original
aqueous solution, through adjustment of the liquid flow rates. Freed from the
extracted element, the organic solution is returned for further extraction,
either
directly or after a fraction of it has been cleansed of impurities.
[00202] Important factors that govern this solvent extraction process
can
be, for example, the number of extraction, scrubbing and stripping stages,
organic solvent concentration and diluent.
[00203] In a typical solvent extraction process, the aqueous phase,
containing the rare earth elements, can be for example a chloric or nitric
acidic solution. The organic phase comprises an extracting agent as those
recited in the present disclosure or alternatives in an organic solvent such
as
an aliphatic diluent.
[00204] Solvent extraction technique can be used as separation and
purification procedure for the rare earth elements. Some of the following
properties are particularly relevant when selecting an extracting agent or
chemical extractant:
High selectivity over other unwanted metals and acids during the
extraction process,
High transfer capacity on the extractant,
Good chemical stability,
Fast kinetics.
[00205] For example, precipitation denotes the removal of the rare
earth
elements from solution by the addition of a chemical reagent to form a new,
less soluble (solid) compound. For example, a complete precipitation can be
carried out by oxalate, hydroxide, or other compounds.
[00206] Hydroxide precipitation and double sulphate can also be used.
For large scale operation, ammonia can be used for carrying out hydroxide
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precipitation from nitrate or chloride solutions. The double sulphates
RE2(604)3*Na2SO4*nH20 can be precipitated by either addition of sodium
sulphate to the solution containing rare earth elements. The precipitation
reaction of trivalent rare earth elements in aqueous solution is according to
the following equation:
REE3+ +3 H20 REE(OH)3 + 3 H+
[00207] The below presented examples are non-limitative and are used
to better exemplify the processes of the present disclosure.
Example 1
Preparation of an aluminum-bearing material sample
[00208] The aluminum-bearing material (for example argillite) can be
finely crushed in order to help along during the following steps. For example,
micronization can shorten the reaction time by few hours (about 2 to 3 hours).
In order to remove most of the iron, a leaching step at room temperature is
optionally carried out between the crushing step and the calcination step.
This operation is, for example, carried out with hydrochloric acid HCI (12 M
or
32 wt%) and an argillite / acid ratio (weight / volume) of 1:5 is used.
Depending on experimental conditions (sizes of the particles, time of
treatment, agitation system), about 65 % to about 93 % of the iron can then
be dissolved . However, this leaching step can also bring in a certain
percentage of the aluminum (0 - 5 %). The last step of the preparation of
argillite comprises calcining the pretreated argillite. This can be
accomplished
at a calcinating temperature greater than 550 C for a period of about 1 to 2
hours. For example, a heat treatment makes it possible to increase the
quantity of extracted aluminum by about 30 % to about 40 % for the same
period of time. In others words, the quantity of extracted aluminum is
doubled.
When leaching at room temperature is carried out, a phase separation before
calcination can be made in order to recover the acid and reduce heating
costs.
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Acid leaching
[00209] Acid leaching can comprise reacting the crushed and roasted
argillite with at least one acid solution (for example HCI) at elevated
temperature during a given period of time. For example, the argillite / acid
ratio can be of about of 1:10 (weight / volume), the HCI concentration can be
of about 6 M or about 18 to 20 wt%, the temperature can be of about 100 C
to about 110 C, and the reaction time can be of about 30 minutes to about 7
hours. Under such conditions, more than about 90 % of the aluminum and
about 100 % of the iron can be extracted in addition to impurities.
Alternatively, the leaching can be carried out at a temperature of about 150
C
to about 175 C at a pressure of about 350 KPag to about 500 KPag during
about 4 to about 7 hours.
[00210] During the second half of such a treatment (for example the last
2 or 3 hours), a portion of the excess acid can be recovered by flashing and
condensation. Once the extraction is terminated, the solid (argillite
impoverished in metals) can be separated from the liquid by decantation or by
filtration, after which it is washed. The residual leachate and the washing
water may be completely evaporated. The corresponding residue can
thereafter be counter currently washed many times with water so as to
decrease acidity and to lower the quantities of base used (for example,
NaOH, KOH, Ca(OH)2, Mg(OH)2, etc. ) that are required to adjust the pH
during iron removal. The acid recovered will can be re-utilized after having
adjusted its titer either by adding either gaseous HCI, or by adding
concentrated HCI (12 M). After the reaction, the titer of the acid can vary
from
about 4 M to about 6 M depending on experimental conditions. With respect
to the solid, it represents about 65 % to about 75 % of the initial mass of
argillite, it can be valorized and be used again either as an ion exchange
resin, or as an adsorbent.
[00211] Alternatively, the HCI leaching can be carried out under
pressure (so to increase the reaction temperature) into an autoclave.
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[00212] The rare earth element(s) recovery can be made, for example,
at this stage, after carrying out the above mentioned acid leaching.
Removal of iron
[00213] Several alternatives are proposed in the present disclosure for
carrying out iron removal. For example, iron removal can be carried out by
substantially selectively precipitating iron ions at certain pH values.
Alternatively, some extracting agents can be used as described in
W02008141423. A membrane can also be used in combination with such
extracting agents
[00214] For example, removal of iron can be carried out by ionic
precipitation of the latter in basic medium for example at a pH of at least 10
or
at a pH of about 11.5 to about 12.5. The pH can also be about 3 to about 6,
or about 3 to about 5 or about 3 to about 4. Such a step can be made by
adding a solution of NaOH, for example at a concentration of 10 M. Other
bases such as KOH can also be used. Then, all that is required is to separate
the solid portion from the liquid portion by filtration, decantation or
centrifugation and to rinse the solid by means of a diluted base, such as a
solution of NaOH (for example NaOH at a concentration of 0.01 M to 0.02 M).
Then, the solid is washed conter currently with water. The liquid portion
comprises aluminum and alkaline-earths A substantially complete removal of
the iron and of nearly all the impurities (other metals) can thus be achieved
as
insoluble and washed hydroxides. Optionally, it is possible to recover iron by
using a refining step by liquid-liquid extraction through a hollow fiber
membrane.
[00215] Alternatively, removal of iron can be carried out by using an
extracting agent and a hollow fiber membrane. Various extracting agents that
could substantially selectively complex iron ions over aluminum ions (or
aluminum ions over iron ions) could be used in such a step depending an Al /
Fe ratio. For example, extraction can be carried out by using HDEHP (or
DEHPA) di(2-ethylhexyl)phosphoric acid) as an extracting agent adapted to
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complex iron ions. A concentration of about 1 M of HDEHP can be used in an
organic solvent, such as heptane or any hydrocarbon solvent. Such an
extraction can require relatively short contact times (few minutes). For
example, the pH of the order of 2 can be used and aqueous phase / organic
phase ratio can be of about 1:1. It was observed that is possible to extract
from 86 % to 98 % iron under such conditions. It will be understood that in
the
present case, iron is trapped in the organic phase. To recover iron in an
aqueous phase, a reverse extraction with hydrochloric acid (2 M or 6 M) and
organic phase / acidic phase ratio of about 1:0.5 can then be carried out. In
such a case, the resulting aqueous phase is rich in Fe3+ ions.
[00216] The rare earth element(s) recovery can be made, for example,
at this stage, after carrying out the above mentioned iron recovery.
[00217] With solvent extraction using countercurrent techniques,
hydrochloric acid stripping and then contacting with MgO solution, therefore
precipitating the rare earth elements in the form of hydroxide and then
converting the products into their corresponding oxide into a calcination
device.
Aluminum recovery
[00218] This step can also be carried in various ways. For example,
aluminum ions can be precipitated under the form of Al(OH)3 (for example an
hydrated form of Al(OH)3) at a pH of about 7 to about 9 or about 7.5 to about
8.5 or about 8. Alternatively, the aluminum ions can be reacted with an
extracting agent as descried in W02008141423.
[00219] The solution obtained from the previous step using either the
precipitation or the extraction technique is relatively clean and mainly
contains
aluminum for example about 90 % to about 95 % or even as high as about
90 % to about 99.8 % (without the alkaline-earths in the case of
precipitation).
Recovery of the latter can be carried out by liquid-liquid extraction for
example
by using a same hollow fiber membrane and an extracting agent that is
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adapted to complex at least substantially selectively aluminum over other
metals or residues. For example, bis(2,4,4-trimethylpentyl) phosphinic acid
(such as the one sold under the name CyanexTM 272) can be used as an
extracting agent specific to aluminum. For example, this extracting agent can
be used at a concentration of about 20 % v/v in an organic solvent such as
heptane. The ratios between the aqueous phase and the organic phase can
be of about 1:1 to about 1:3. For example, the extraction temperatures can be
of about 40 C and the pH can be maintained at about 2.5 to about 3.5. It was
observed that such a technique makes it possible to extract more than 70 - 90
`)/0 of the aluminum. After the aluminum has been trapped in the organic
phase, it can be recovered in the form of a concentrate of Al3+ ions by using
a
back extraction. For example, the reverse extraction can be carried out at a
temperature of about 40 C with hydrochloric acid (for example at a
concentration of 6 M). Under this condition, more than 90 % of aluminum can
be recovered.
[00220] The rare earth element(s) recovery can be made, for example,
at this stage, after carrying out the above mentioned aluminum recovery.
[00221] Then, Al3+ can be converted into aluminum hydroxide (for example
an hydrated form of Al(OH)3) by addition of a base such as NaOH. Finally,
Al(OH)3 can be converted into alumina (alumina A1203) by r calcinating
Al(OH)3 for example at a temperature of about 800 C to1200 C.
[00222] Further purification can be performed by recrystallization.
Rare earth elements recovery
[00223] Rare earth elements recovery can then be made, for example, at
this stage by using any of the technology previously mentioned for doing so.
For example, the at least one rare earth element contained in the residual
solutions obtained from the above-mentioned process. For example, the at
least one rare earth element can be in low concentration for example at a
concentration of less than about 50, about 25, 15, 10, 5, 4, 3, 2 or 1 ppm in
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the lixiviate or leachate or a solution obtained during the process .The rare
earth elements can be concentrated in the latter stage of the process prior to
extraction with solvent(s). It was demonstrated that through an internal
concentration loop, concentration can be significantly increased (for example
from 100 to 1000 times) thereby providing more effective conditions for
substantially selectively precipitating, extracting and/or isolating at least
one
rare earth element.
Example 2
[00224] As a starting material a sample of clay (argillite) was obtained from
the Grande Vallee area in Quebec, Canada.
[00225] These results represent an average of 80 tests carried out from
samples of about 900 kg each. These tests were carried out by a using a
process as shown in Fig. 1.
[00226] Crude clay in the freshly mined state after grinding and
classification had the following composition:
A1203 : 15% - 26%;
Si02 : 45% - 50%;
Fe203 : 8% - 9%;
MgO: 1% ¨ 2%;
Rare earth elements: 0.04% - 0.07%;
LOI : 5% - 10%.
[00227] This material is thereafter leached in a two-stage procedure at 140-
170 C with 18-32 weight % HCI. The HCI solution was used in a
stoichiometric excess of 10-20% based on the stoichiometric quantity required
for the removal of the acid leachable constituents of the clay. In the first
leaching stage of the semi-continuous operation (step 2), the clay was
contacted for 2.5 hours with required amount or certain proportion of the
total
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amount of hydrochloric acid. After removal of the spent acid, the clay was
contacted again with a minimum 18 weight % hydrochloric acid solution for
about 1.5 hour at same temperature and pressure.
[00228] The leachate was filtered and the solid was washed with water and
analyzed using conventional analysis techniques (see step 3 of Fig. 1). Purity
of obtained silica was of 95.4% and it was free of any chlorides and of HCI.
[00229] After the leaching and silica removal, the concentration of the
various metal chlorides was:
AlC13 : 15-20%;
FeCl2 : 4-6%;
FeCl3: 0.5-2.0%;
MgC12 : 0.5-2.0 %;
Free HCI : 5-50 g/I
[00230] Spent acid was then crystallized using about 90 to about 98% pure
dry hydrochloric acid in gas phase in two stages with less than 25 ppm iron in
the aluminum chloride hexahydrate formed. The concentration of HCI in
solution (aqueous phase) was about 25 to about 32 % The recovered
crystallized material (hydrate form of AlC13 having a minimum purity of 99.8
%)
was then calcined at 930 C or 1250 C, thus obtaining the a-portion of the
alumina.
[00231] HCI concentration in gas phase exiting the calcination stage was
having a concentration of about 21 to about 32 % by weight and was used
(recycled) for crystallization of the AlC13 and MgC12. Excess of hydrochloric
acid is absorbed at the required and targeted concentration for the leaching
steps.
[00232] Iron chloride (about 90% to about 95% in ferric form) is then sent to
a hydrothermal process in view of its extraction as pure hematite (Fe203).
This
can be done by using the technology described in WO 2009/153321 of low
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temperature hydrolysis with full heat recovery from calcining, pyrohydrolysis
and leaching stage.
[00233] Before step 10 (in both processes of Figs. 1 and 2) it was
demonstrated that about 90 to about 98 % by weight of the elements (Al, Fe,
Mg and rare earths elements such as (Sc, Ga, Y, Ce) found in the starting
material were recovered. It can be estimated that the processes for recovering
rare earth elements from an aluminum-bearing material disclosed in the
present disclosure can be efficient for recovering about 90 % of the rare
earth
elements. Thus, with respect to the examples of processes provided in Figs. 1
and 2, it can be estimated that the overall yield for recovering the at least
one
rare earth element from the aluminum-bearing material would be about 80 'Yo
to about 90 %.
[00234] Rare earth elements can be extracted from the mother liquor of the
hydrolyzer (where silica, aluminum, iron and a great portion of water have
been removed) following pre-concentration from crystallization to the
hydrolyzer. In the form of chlorides the rare earth elements (RECI) are
considerably concentrated and ready to be extracted. Rare earth elements
have demonstrated to concentrate by a factor 5 to 10 in average within the
hydrolyzer itself on a single pass through it (without any concentration
loop).
The concentration factors obtained within the hydrolyser (single pass) were as
follows:
Ce : > 6
La: > 9
Nd: > 7
[00235] The person skilled in the art would thus clearly understand that
such a concentration could be considerably more increased when carrying out
a concentration loop.
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[00236] Remaining magnesium chloride is sparged with dry and highly
concentrated hydrochloric acid and then calcinated to MgO while recovering
acid at its azeotropic point.
[00237] Mixed oxides containing other non-hydrolyzable components were
then undergoing a pyrohydrolysis reaction at 700-800 C and recovered acid
(15-20.2% wt.) was rerouted for example to the leaching system.
Overall yields obtained:
A1203 : 93-95% recovery;
Fe203 : 98-99.5% recovery;
Rare earth elements : 95% minimum recovery (mixture);
MgO: 96-98% recovery;
Material discarded : 0-5% maximum;
HCI global recovery: 99.75% minimum;
HCI strength as feed to leaching 15-32%;
Red mud production : none.
Example 3
[00238] A similar feed material (bauxite instead of clay) was processed as
per in example 2 up to the leaching stage and revealed to be easily leachable
under the conditions established in example 2. It provided an extraction
percentage of 100% for the iron and over 95 % for aluminum. The process
was found to be economically viable and no harmful by-products (red mud)
were generated. A rare earth elements recovery (as a mixture) of about 90 to
about 95 % (by weight as compared to the starting material) was observed
Samples tested had various concentrations of A1203 (up to 51%), Fe203 (up to
27%) and MgO (up to 1.5%).
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[00239] The processes of the present disclosure provide a plurality of
important advantages and distinction over the known processes
[00240] The processes of the present disclosure can provide fully
continuous and economical solutions that can successfully extract alumina
from various type of minerals while providing ultra pure secondary products of
high added value including highly concentrated rare earth elements. The
technology described in the present disclosure can allow for an innovative
amount of total acid recovery and also for a ultra high concentration of
recovered acid. When combing it to the fact that combined with a semi-
continuous leaching approach that favors very high extraction yields and
allows a specific method of crystallization of the aluminum chloride and
concentration of other value added elements such as rare earth elements.
[00241] Specifically through the type of equipment used (for example
vertical roller mill) and its specific operation, raw material grinding,
drying and
classifying can be applicable to various kinds of mineral hardness (furnace
slag for example), various types of humidity (up to 30%) and incoming particle
sizes. The particle size established provides the advantage, at the leaching
stage, of allowing optimal contact between the minerals and the acid and then
allowing faster kinetics of reaction. Particles size employed reduces
drastically the abrasion issue and allows for the use of a simplified
metallurgy/lining when in contact with hydrochloric acid.
[00242] A further advantage of the processes of the present disclosure is
the combined high temperature and high incoming hydrochloric acid
concentration. Combined with a semi continuous operation where the free
HCI driving force is used systematically, iron and aluminum extraction yields
do respectively reach 100% and 98% in less than about 40 % of the
reference time of a basic batch process. Another advantage of higher HCI
concentration than the concentration at azeotropic point is the potential of
capacity increase. Again a higher HCI concentration than the concentration of
HCI at the azeotropic point and the semi-continuous approach represent a
substantial advance in the art.
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[00243] Another advantage in that technique used for the mother liquor
separation from the silica after the leaching stage countercurrent wash, is
that
band filters provide ultra pure silica with expected purity exceeding 98%.
[00244] The crystallization of AlC13 into AlC13 = 6H20 using dried, cleaned
and highly concentrated gaseous HCI as the sparging agent allows for a pure
aluminum chloride hexahydrate with only few parts per million of iron and
other impurities. A minimal number of stages can be required to allow proper
crystal growth.
[00245] The direct interconnection with the calcination of AlC13 = 6H20 into
A1203 which does produce very high concentration of gas allows the exact
adjustment in continuous of the HCI concentration within the crystallizer and
thus proper control of the crystal growth and crystallization process.
[00246] The applicants have now discovered fully integrated and continuous
processes with total hydrochloric acid recovery for the extraction of alumina
and other value added products such as rare earth elements from various
materials that contain aluminum (clay, bauxite, slag, red mud etc.) containing
aluminum. In fact, the processes allows for the production of pure alumina
and other value added products purified such as purified silica, pure
hematite,
pure other minerals (ex: magnesium oxide) and rare earth elements. In
addition, the processes do not require thermal pre-treatment before the acid
leach operation. Acid leach can be carried out using semi-continuous
techniques with high pressure and temperature conditions and very high
regenerated hydrochloric acid concentration.
[00247] The advantage of the high temperature calcination stage, in
addition for allowing to control the a-form of alumina required, is effective
for
providing a concentration of hydrochloric acid in the aqueous form (>38%)
that is higher than the concentration of HCI at the azeotropic point and thus
providing a higher incoming HCI concentration to the leaching stage. The
calcination stage hydrochloric acid network can be interconnected to two (2)
crystallization systems and by pressure regulation excess HCI can be being
absorbed at the highest possible aqueous concentration. The advantage of
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having a hexahydrate incoming feed allows for a continuous basis to recover
acid at a concentration that is higher than the azeotropic concentration. This
HCI balance and double usage into three (3) common parts of the process
and over azeotropic point is a substantial advance in the art.
[00248] Another advantage is the use of the incoming chemistry (ferric
chloride) to the iron oxide and hydrochloric acid recovery unit where all
excess heat load from any calcination part, pyrohydrolysis and leaching part
is
being recovered to preconcentrate the mother liquor in metal chloride, thus
allowing, at very low temperature, the hydrolysis of the ferric chloride in
the
form of very pure hematite and the acid regeneration at the same
concentration than at its azeotropic point.
[00249] A further major advantage of the instant process at the ferric
chloride hydrolysis step is the possibility to concentrate rare earth elements
in
form of chlorides at very high concentration within the hydrolyser reactor.
The
advantage is that the processes of the present disclosure benefit from the
various steps where gradual concentration ratios are applied. Thus, at this
stage, having the silica, the aluminum, the iron and having in equilibrium a
solution close to saturation (large amount of water evaporated, no presence of
free hydrochloric acid) allows for taking rare earth elements in parts per
million into the incoming feed and to concentrate them in high percentage
portion directly at the hydrolyser. Purification of the specific oxides of the
rare
earth elements (REO) can then be performed using known techniques when
in percentage levels. The advantage is doubled here: concentration at very
high level of rare earth elements using integrated process stages and most
importantly the approach prevents from having the main stream (very diluted)
of spent acid after the leaching step with the risk of contaminating the main
aluminum chloride stream and thus affecting yields in A1203. Another
important improvement of the art is that on top of being fully integrated,
selective removal of components allows for the concentration of rare earth
elements to relatively high concentration (percentages).
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[00250] Another advantage of the process is again a selective crystallization
of MgCl2 through the sparging from either the alumina calcination step or the
magnesium oxide direct calcination where in both cases highly concentrated
acid both in gaseous phase or in aqueous form are being generated. As per
aluminum chloride specific crystallization, the direct interconnection with
the
calciner, the HCI gas very high concentration allows for exact adjustment in
continuous of the crystallizer based on quality of magnesium oxide targeted.
Should this process step (MgO production or other value added metal oxide)
be required based on incoming process feed chemistry, the rare earth
elements extraction point then be done after this additional step; the
advantage being the extra concentration effect applied.
[00251] The pyrohydrolysis allows for the final conversion of any remaining
chloride and the production of refined oxides that can be used (in case of
clay
as starting material) as a fertilizer and allowing the processing of large
amount
of wash water from the processes with the recovery hydrochloric acid in close
loop at the azeotropic point for the leaching step. The advantage of this last
step is related to the fact that it does totally close the process loop in
terms of
acid recovery and the insurance that no residues harmful to the environment
are being generated while processing any type of raw material, as previously
described.
[00252] A major contribution to the art is that the proposed fully integrated
processes of the present disclosure is really allowing, among others, the
processing of bauxite in an economic way while generating no red mud or
harmful residues. In addition to the fact of being applicable to other natural
of
raw materials (any suitable aluminum-bearing material or aluminous ores), the
fact of using hydrochloric acid total recovery and a global concentration that
is
higher than the concentration at the azeotropic point (20% to 38%), the
selective extraction of value added secondary products and compliance
(while remaining highly competitive on transformation cost) with
environmental requirements, represent major advantages in the art.
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[00253] It was thus demonstrated that the present disclosure provides fully
integrated processes for the preparation of pure aluminum oxide using a
hydrochloric acid treatment while producing high purity and high quality
products (minerals) and recovering rare earth elements.
[00254] The person skilled in the art will thus understand that the processes
of the present disclosure can be used in combination with various processes
for treating aluminum-bearing materials. In fact, various different treatments
can be carried out to the aluminum-bearing materials in the processes of the
present disclosure including recovery of at least one rare element.
[00255] The scope of the claims should not be limited by specific
embodiments and examples provided in the disclosure, but should be given
the broadest interpretation consistent with the disclosure as a whole.
