Field of invention
[0001] The present invention relates to a composition for use in steel making process. The
present invention further relates to the method for production of the composition,
to the use of the composition as raw material in steel making process and to a premix
for producing the composition.
Background of the invention
[0002] During the steelmaking process, wastes, also called by-products, such as slag, dust,
and sludge are generated, which contain hazardous chemicals and metals. If not handled
correctly, these wastes can contaminate the environment, harm human health, and damage
ecosystems. These wastes are currently mostly disposed of to landfill. However, disposal
of large volumes of metallic solid waste may disturb the environmental balance of
soil and groundwater.
[0003] Recycling is becoming very important. Recycling is a process using materials (waste)
into new products to prevent waste of potentially useful materials, reduce the consumption
of fresh raw materials, reduce energy usage, reduce air pollution (from incineration)
and water pollution (from landfilling) by reducing the need for "conventional" waste
disposal. Recycling is a key component of modern waste reduction. The European Union
is also currently updating its legislation on waste management to promote a shift
to a more sustainable model known as the circular economy.
[0004] Therefore, it is known to recycle and reuse for example, BOF and LAF slag's into
cement, concrete and road base infrastructure markets, leading to significant reductions
in environmental impact, along with high-efficiency metal recovery and the manufacture
of co products from the residual slag's.
[0007] Notably,
EP0687309 A1 also discloses a process and a device for recovering iron and carbon from blast furnace
scrubber sludge (dust, particulates and sludge). After a series of treatments such
as separations by filtration or hydro cyclones, the recovered iron and carbon are
recycled to the iron making operation
[0008] The steel making industry is also affected by the concerns of recycling and circular
economy and is currently undergoing an energy transition. It must notably adapt its
dependence on raw materials in line with constantly changing regulations.
[0009] However, in view of the specific requirements of the steel making industry, use of
recycled products in this field is very challenging. For this reason, at the moment,
a lot of wastes or by-products from steel making process cannot be reused in a steel
making process. This is also the reasons why most of the literature concerning the
recycling and the reuse of steel making wastes is in the field of construction (cement,
mortars...) where it is easier to use raw materials derived from waste without dramatically
impacting the qualities of the end product.
[0010] In view of the above, there is a strong need for an improved composition for use
in steelmaking process, which allows a by-product from steel making process to be
recycled and reused as raw material in a steelmaking process.
Summary of the invention
[0011] The inventors have now surprisingly found that it is possible to provide a composition
fulfilling the above mentioned needs.
[0012] Thus, there is now provided a composition for use in a steel making process [composition
(C), herein after], wherein said composition (C) is prepared by mixing :
- (i) at least one steel scale by-product [compound (SSB), herein after] which comprises
equal to or more than 35.0 wt. % of free water, relative to the total weight of the
compound (SSB);
- (ii) at least one first additive in an amount providing a weight ratio of calcium
oxide to the free water present in the compound (SSB) equal to or more than 1.50,
wherein said first additive comprises calcium oxide in an amount of at least 80.0
wt. %, relative to the total weight of the first additive, and
characterised in that the composition (C) after mixing comprises free water in an
amount equal to or less than 5.0 wt. %, relative to the total weight of the composition
(C).
[0013] In another aspect the present invention further provides a method for the manufacturing
of a composition for a use in steel making process, as detailed above, a premix for
manufacturing the composition, as detailed above and use of the composition as raw
material in a steel making process, as detailed above.
Detailed description
[0014] As used herein and in the claims, the terms "comprising" and "including" are inclusive
or open-ended and do not exclude additional unrecited elements, compositional components,
or method steps. Accordingly, the terms "comprising" and "including" encompass the
more restrictive terms "consisting essentially of" and "consisting of".
[0015] The term "comprising", used in the claims, should not be interpreted as being restricted
to the means listed thereafter; it does not exclude other elements or steps. It needs
to be interpreted as specifying the presence of the stated features, integers, steps
or components as referred to, but does not preclude the presence or addition of one
or more other features, integers, steps or components, or groups thereof. Thus, the
scope of the expression "a composition comprising A and B" should not be limited to
the composition consisting only of A and B. It means that with respect to the present
invention, the only compositional components of the composition are A and B. Accordingly,
the terms "comprising" and "including" encompass the more restrictive terms "consisting
essentially of" and "consisting of".
[0016] As used herein, the terms "optional" or "optionally" means that a subsequently described
event or circumstance can or cannot occur, and that the description includes instances
where said event or circumstance occurs and instances where it does not.
[0017] Thus, the composition [composition (C), herein after] according to the present invention
is for use in a steel making process.
[0018] In other words, the present invention relates to a composition (C) suitable to be
used as a raw material in a steel making process. Within the context of the present
invention, the expression "steel making process", refers to a process for producing
steel. Non-limiting examples of such steel making process are basic oxygen furnace
(BOF) process, electric arc furnace (EAF) process and argon oxygen decarburization
process (AOD). Preferably, the composition (C) is particularly suitable to be used
as a raw material in an electric arc furnace (EAF) process.
[0019] As said, the composition according to the present invention is prepared from at least
one steel scale by-product [compound SSB, herein after].
[0020] Within the context of the present invention, the expression "at least one steel scale
by-product [compound SSB, herein after]" is intended to denote one or more than one
steel scale by-product. Mixtures of steel scale by-product can also be used for the
purpose of the invention. In the remainder of the text, the expression "steel scale
by-product" is understood, for the purposes of the present invention, both in the
plural and the singular form.
[0021] Within the context of the present invention, the compound (SSB) is intended to refer
to a by-product, also called a waste, of a steel making process.
[0022] Scale is formed on the surface of steel during their high temperature thermal treatments
after casting. In general, at the end of a steel making process, steel is immersed
in an acidic bath (also called pickling process) to remove scale present at the surface
of the steel. The acidic solution is then collected. Thereafter, lime is added to
this acidic solution to reach a pH of about 10 and to precipitate dissolved metals.
The resulting sludge which contained the precipitated metals is collected and subjected
to a press process in order to separate the solid phase from the liquid phase. The
solid phase comprises at least metals such as iron (Fe), chromium (Cr), nickel (Ni),
molybdenum (Mo). In general, this solid phase also comprises a high content of moisture
and is also called steel scale by-product, steel scale waste or filter cake.
[0023] Preferably, the compound (SSB) is a by-product from stainless steel process or carbon
steel process or mixture thereof.
[0024] Advantageously the compound (SSB) can be in different forms such as a paste, a powder,
scraps or mixture thereof. Preferably, the compound (SSB) is a paste. The compound
(SSB) can also be chunked, milled, crushed or powdered.
[0025] As said, according to the present invention, said at least one steel scale by-product
[compound (SSB), herein after] comprises equal to or more than 35.0 wt. % of free
water, relative to the total weight of the compound (SSB).
[0026] Within the context of the present invention, the expression "free water" is intended
to refer to the portion of water which evaporates upon heating. On the contrary, in
general, the expression "bound water" refers to the water which remains bounded to
the compound upon heating. It is understood that the skilled person in the art will
measure the amount of free water according to standard and general practice known
by said skilled person in the art. Preferably, unless otherwise mentioned or indicated,
according to the present invention, the measurement of free water is performed by
subjecting the sample to a heating step at 80 °C. In general, the measurement of free
water is performed until a constant weight of the sample subjected to said measurement
is reached.
[0027] In general, said compound (SSB) comprises, or equal to or more than 40.0 wt. %, or
equal to or more than 45.0 wt. %, or equal to or more than 50.0 wt. %, or equal to
or more than 55.0 wt. %, of free water, relative to the total weight of the compound
(SSB).
[0028] It is further understood that the upper limit of free water in the compound (SSB)
is advantageously equal to or less than 80.0 wt. %, or equal to or less than 75.0
wt. %, or equal to or less than 70.0 wt. %, relative to the total weight of the compound
(SSB).
[0029] In an embodiment of the composition of the present invention, free water, as detailed
above, is present in the compound (SSB) in an amount from 35.0 wt. % to 80.0 wt. %,
or from 35.0 wt. % to 75.0 wt. %, or from 40.0 wt. % to 75.0 wt. % or from 45.0 wt.
% to 75.0 wt. %, or from 50.0 wt. % to 70.0 wt. % or from 55.0 wt. % to 70.0 wt. %,
relative to the total weight of the compound (SSB).
[0030] The compound (SSB) may further comprise equal to or more than 0.2 wt. % of fluorine,
expressed as CaF
2, relative to the total dry weight of the compound (SSB).
[0031] It is further understood that the expression "fluorine" also refers to the ionic
form, F-, fluoride.
[0032] Within the context of the present invention, unless otherwise mentioned or indicated,
the expression "dry weight" is intended to refer to the weight of the compound (SSB)
after the evaporation of the free water, as detailed above.
[0033] In general, the presence of fluorine, expressed as CaF
2, in the compound (SSB) may come from the steel making process from which the steel
scale by-product is derived. In general, during the addition of lime to neutralize
the acidic solution, CaF
2 is produced. Its content in the compound (SSB) is thus dependent on the conditions
used during the steel making process from which the steel scale by-product is derived.
[0034] In general, said compound (SSB) may comprise equal to or more than 1.0 wt. %, or
equal to or more than 5.0 wt. %, or equal to or more than 7.0 wt. %, of fluorine,
expressed as CaF
2, relative to the total dry weight of the compound (SSB).
[0035] It is further understood that the upper limit of fluorine, expressed as CaF
2, in the compound (SSB) may advantageously be equal to or less than 15.0 wt. %, or
equal to or less than 12.0 wt. %, or equal to or less than 10.0 wt. %, or equal to
or less than 8.0 wt. %, relative to the total dry weight of the compound (SSB).
[0036] In an embodiment of the composition of the present invention, fluorine, expressed
as CaF
2, as detailed above, is present in the compound (SSB) in an amount from 0.2 wt. %
to 15.0 wt. %, or from 1.0 wt. % to 12.0 wt. %, or from 5.0 wt. % to 10.0 wt. %, relative
to the total dry weight of the compound (SSB).
[0037] Preferably, the compound (SSB) can further comprise metals such as iron (Fe), chromium
(Cr), nickel (Ni), molybdenum (Mo).
[0038] According to the present invention, the compound (SSB) may further comprise iron,
expressed as Fe
2O
3, in an amount equal to or more than 10 wt. %, preferably equal to or more than 20
wt. %, equal to or more than 30 wt. %, relative the total dry weight of the compound
(SSB). It is further understood that the expression "iron" refers to iron in all its
forms (ionic forms) present in the compound (SSB).
[0039] In an embodiment of the composition of the present invention, the upper limit of
iron, expressed as Fe
2O
3, in the compound (SSB) is equal to or less than 60 wt. %, preferably equal to or
less than 50 wt. %, equal to or less than 60 wt. %, relative the total dry weight
of the compound (SSB).
[0040] Preferably, iron, expressed as Fe
2O
3, is preferably present in the compound (SSB) in an amount from 10 wt.% to 60 wt.
%, preferably from 20 wt. % to 50 wt. %, preferably from 30 wt. % to 40 wt. %, relative
the total dry weight of the compound (SSB).
[0041] According to the present invention, the compound (SSB) may further comprise chromium
in an amount equal to or more than 0.02 wt. %, preferably equal to or more than 0.06
wt. %, preferably equal to or more than 0.10 wt. %, relative the total dry weight
of the compound (SSB).
[0042] In an embodiment of the composition of the present invention, the upper limit of
chromium in the compound (SSB) is equal to or less than 15.0 wt. %, preferably equal
to or less than 12.0 wt. %, equal to or less than 10.0 wt. %, relative the total dry
weight of the compound (SSB).
[0043] Preferably, chromium is present in the compound (SSB) in an amount from 0.02 wt.
% to 15.0 wt.%, or from 0.06 wt.% to 12.0 wt. %, preferably from 0.1 wt. % to 10 wt.
%, relative the total dry weight of the compound (SSB).
[0044] According to the present invention, the compound (SSB) may further comprise nickel
in an amount equal to or more than 0.02 wt. %, preferably equal to or more than 0.06
wt. %, preferably equal to or more than 0.1 wt. %, relative the total dry weight of
the compound (SSB).
[0045] In an particular embodiment, the upper limit of nickel in the compound (SSB) is equal
to or less than 15.0 wt. %, preferably equal to or less than 12.0 wt. %, preferably
equal to or less than 10.0 wt. %, relative the total dry weight of the compound (SSB).
[0046] Preferably, nickel is present in the compound (SSB) in an amount from 0.02 wt. %
to 15.0 wt.%, or from 0.06 wt.% to 12.0 wt. %, preferably from 0.1 wt. % to 10 wt.
%, relative the total dry weight of the compound (SSB).
[0047] According to the present invention, the compound (SSB) may further comprise molybdenum
in an amount equal to or more than 0.02 wt. %, preferably equal to or more than 0.05
wt. %, preferably equal to or more than 0.1 wt. %, relative the total dry weight of
the compound (SSB).
[0048] In an embodiment of the composition of the present invention, the upper limit of
molybdenum in the compound (SSB) is equal to or less than 15.0 wt. %, preferably equal
to or less than 12.0 wt. %, preferably equal to or less than 10 wt. %, relative the
total dry weight of the compound (SSB).
[0049] Preferably, molybdenum is present in the compound (SSB) in an amount from 0.02 wt.
% to 15.0 wt.%, or from 0.06 wt.% to 12.0 wt. %, preferably from 0.1 wt. % to 10 wt.
%, relative the total dry weight of the compound (SSB).
[0050] Preferably, chromium, nickel and molybdenum are present in the compound (SSB) in
a cumulated amount from 0.1 wt. % to 50 wt. %, preferably from 0.2 wt. % to 40 wt.
%, preferably from 0.5 wt. % to 30 wt. % relative to the total dry weight of the compound
(SSB).
[0051] As said, the composition (C), as detailed above, is prepared by mixing the compound
(SSB), as detailed above, with at least one first additive.
First additive
[0052] Within the context of the present invention, the expression "at least one first additive"
is intended to denote one or more than one first additive. Mixtures of first additive
can also be used for the purpose of the invention. In the remainder of the text, the
expression "first additive" is understood, for the purposes of the present invention,
both in the plural and the singular form.
[0053] As said, the composition (C), as detailed above, is prepared by mixing the compound
(SSB), as detailed above, with at least one first additive in an amount providing
a weight ratio of calcium oxide to the free water present in the compound (SSB) equal
to or more than 1.50.
[0054] In other words, the first additive is mixed with the compound (SSB) in such a way
to have a weight ratio of calcium oxide to free water of the compound (SSB) equal
to or more than 1.50;

.
[0055] It is further understood that the lower limit of the amount of the first additive
which is mixed with the compound (SSB) should be sufficient to provide the amount
of calcium oxide, as detailed above.
[0056] Advantageously, the first additive is mixed with the compound (SSB) in an amount
providing a weight ratio of calcium oxide to the free water present in the compound
(SSB) equal to or more than 1.75, preferably equal to or more than 1.80, more preferably
equal to or more than 1.90, even more preferably equal to or more than 2.00.
[0057] Advantageously, the first additive is mixed with the compound (SSB) in an amount
providing a weight ratio of calcium oxide to the free water present in the compound
(SSB) equal to or less than 2.50, preferably equal to or less than 2.25, more preferably
equal to or less than 2.15 even more preferably equal to or less than 2.10.
[0058] In a preferred embodiment of the method of the present invention, the first additive
is advantageously mixed with the compound (SSB) in an amount providing a weight ratio
of calcium oxide to the free water present in the compound (SSB) from 1.50 to 2.50,
more preferably from 1.80 to 2.25, most preferably from 2.0 to 2.15.
[0059] According to the present invention, the first additive comprises calcium oxide in
an amount of at least 80.0 wt. %, relative to the total weight of the first additive.
In other words, the expression "first additive" is intended to refer to a compound
comprising at least 80.0 wt. % of calcium oxide or a composition comprising at least
80.0 wt. % of calcium oxide or a mixture thereof.
[0060] Advantageously, the first additive comprises calcium oxide in an amount of at least
85.0 wt. %, preferably in an amount of at least 90.0 wt. %, more preferably in an
amount of at least 95.0 wt. %, even more preferably in an amount of at least 98.0
wt. %, relative to the total weight of the first additive.
[0061] According to a preferred embodiment of the composition of the present invention,
the first additive is a compound comprising or consisting essentially of calcium oxide,
as detailed above, wherein the total amount of the calcium oxide is equal to or more
than 80.0 wt.%, or more than 85.0 wt.% or more than 90.0 wt.% or more than 95.0 wt.%
or desirably more than 98.0 wt.% relative to the total weight of the compound.
[0062] In general, the skilled in the art knows how to select the first additive to provide
the weight ratio as detailed above.
[0063] According to the present invention, the first additive may further comprise at least
one calcium salt, other than calcium oxide, in an amount equal to or less than 20
wt. %, preferably equal to or less than 15 wt. %, more preferably equal to or less
than 10 wt. %, relative to the total weight the first additive. Within the context
of the present invention, the expression "at least one calcium salt" is intended to
denote one or more than one calcium salt. In the rest of the text, the expression
"at least one calcium salt" is understood, for the purposes of the present invention,
both in the plural and the singular. Non-limiting examples of such calcium salts are
calcium carbonate, calcium hydroxide, calcium sulfate, or calcium nitrate.
[0064] According to an embodiment of the present invention, the first additive may further
comprise at least one magnesium salt selected from the group consisting of magnesium
carbonate, magnesium oxide, and magnesium hydroxide. Within the context of the present
invention, the expression "at least one magnesium salt" is intended to denote one
or more than one magnesium salt. In the rest of the text, the expression "at least
one magnesium salt" is understood, for the purposes of the present invention, both
in the plural and the singular.
[0065] In this embodiment, the content of magnesium, expressed as magnesium oxide, present
in the first additive is equal to or less than 10.0 wt. %, preferably equal to or
less than 7.0 wt. %, more preferably equal to or less than 5.0 wt. %, relative to
the total weight of the first additive.
[0066] The first additive according to the present invention may further comprise impurities
in an amount equal to or less than 5.0%, preferably equal to or less than 4.0 wt.
%, more preferably equal to or less than 2.5 wt. %, relative to the total weight of
the first additive. Non limiting examples of such impurities are silicon, aluminum,
iron, sodium, potassium, sulfur, phosphorous alone or in combination. The impurities
may also be in salt form, in oxide form, in combination with calcium or combination
thereof.
[0067] Said first additive may be a compound or a composition or mixture thereof.
[0068] Said first additive may be synthetically prepared by a variety of methods known in
the art or can be of natural origin.
[0069] Non-limiting examples of first additive of natural origin may be made from mined
(raw) minerals such as limestones. In general, limestone comprises CaCOs in a total
amount of more than 95.0 wt.%, or more than 96.0 wt.%, or more than 97.0 wt.%, or
desirably more than 98.0 wt.%, relative to the total weight of the limestone.
[0070] In a preferred embodiment of the invention, the first additive is a quicklime. In
general quicklime is made from limestones, in particular by calcining limestones.
[0071] In this embodiment, when the first additive is a quicklime, said quicklime has a
reactivity, t
60, of at most 10 minutes. The quicklime reactivity is evaluated with the European reactivity
on slaking test, EN 459-2: Building lime - Part 2: Tests methods. In general, the
quicklime reactivity is expressed as t
60, which is the time needed to reach 60 °C when 150 g of quicklime is added to 600
cm
3 of water. Preferably, the quicklime complies with the chemical requirements of a
calcium lime CL80-R5 according to the European standard EN 459-1.
[0072] The inventors have now found that when the composition (C) is prepared by mixing
the compound (SSB), as detailed above, with the at least one first additive, as detailed
above, in an amount providing a weight ratio of calcium oxide to the free water present
in the compound (SSB) equal to or more than 1.50, the free water of the resulting
composition (C) is significantly reduced.
[0073] According to the present invention, the composition (C), after mixing the compound
(SSB), as detailed above, with the at least one first additive, as detailed above,
comprises free water in an amount equal to or less than 5.0 wt. %, relative to the
total weight of the composition (C).
[0074] The inventors have found that the composition (C) of the present invention, can be
safely used in a steel making process. A free water equal to or less than 5 wt. %
in the composition (C) is an important figure as this is the threshold for safely
reintroducing this composition as a raw material in a steel making process. Indeed,
a low content of free water in the raw material is mandatory in a steel making process
to avoid rapid expansion of the free water into gas. Due to the high temperatures
used in a steel making process, the free water becomes a gas which takes up a greater
volume. This rapid expansion of the liquid water into a gas can be so sudden that
the liquid steel is ejected out of the vessel. This causes a major safety risk and
potentially damages equipment. Therefore, the use of the first additive according
to the invention is cost-effective since it avoids the use of further drying steps.
Moreover, it allows the recycling and the reuse of the by-product, notably of the
high value metals and alloys that are contained in the compound (SSB).
[0075] The present invention provides a solution for the recovering and recycling of steel
scale by-product and facilitating the subsequent reuse of this by-product in a steel
making process while improving the performance of this process. In view of the public
policies favoring recycling, notably in the steel making field, the present invention
has an important economic potential.
[0076] It is further understood that the definition of free water, as described above for
the compound (SSB), equally applies for the composition (C).
[0077] Preferably, said composition (C) comprises equal to or less than 4.5 wt. %, equal
to or less than 4.0 wt. %, preferably equal to or less than 3.5 wt. %, more preferably
equal to or less than 3.0 wt. %, most preferably equal to or more than 2.5 wt. %,
most preferably equal to or more than 2.0 wt. %, even more preferably equal to or
less than 1.5 wt. %, of free water relative to the total weight of the composition
(C).
[0078] It is further understood that the lower limit of free water in the composition (C)
is advantageously equal to or more than 0.0 wt. % or equal to or more than 0.2 wt.
%, preferably equal to or more than 0.3 wt. %, preferably equal to or more than 0.4
wt. %, more preferably equal to or more than 0.5 wt. %, even more preferably equal
to or more than 0.7 wt. %, most preferably equal to or more than 1.0 wt. %, relative
to the total weight of the composition (C).
[0079] In an embodiment of the composition of the present invention, free water, as detailed
above, is advantageously present in the composition (C) in an amount from 0.0 wt.
% to 5.0 wt. %, preferably from 0.2 wt. % to 4.5 wt. %, preferably from 0.3 wt. %
to 4.0 wt. %, more preferably from 0.5 wt. % to 3.5 wt. %, more preferably from 0.7
wt. % to 3.0 wt. % from 1.0 wt. % to 3.0 wt. % or from 1.0 wt. % to 2.0 wt. %, relative
to the total weight of the composition (C).
[0080] Advantageously, according to the present invention, the composition (C), after mixing
the compound (SSB), as detailed above, with the at least one first additive, as detailed
above, further comprises fluorine, expressed as CaF
2, in an amount equal to or less than 20.0 wt.%, preferably equal to or less than 15.0
wt. %, preferably equal to or less than 10.0 wt. %, relative to the total dry weight
of the composition (C).
[0081] It is further understood that the definition of dry weight, as described above for
the compound (SSB), equally applies for the composition (C).
[0082] According to a certain embodiment of the invention, a second additive may be added
to the composition (C), as detailed above, wherein said second additive is comprising,
relative to the total weight of said second additive, at least 20.0 wt. % of magnesium,
expressed as magnesium oxide.
[0083] The amount added to the composition (C), as detailed above, is determined by the
amount of fluorine, expressed as CaF
2, in the composition (C) and the nature of the second additive.
[0084] Advantageously, the second additive is added in an amount providing in the composition
(C) a weight ratio of magnesium, expressed as magnesium oxide, to fluorine, expressed
as CaF
2, equal to or more than 5.0.
Second additive
[0085] Within the context of the present invention, the expression "at least on second additive"
is intended to denote one or more than one second additive. Mixtures of second additive
can also be used for the purpose of the invention. In the remainder of the text, the
expression "second additive" is understood, for the purposes of the present invention,
both in the plural and the singular form.
[0086] Within the context of the present invention, the expression "second additive" is
intended to refer to a compound comprising at least one magnesium salt or a composition
comprising at least one magnesium salt or a mixture thereof.
[0087] Within the context of the present invention, the expression "at least one magnesium
salt" is intended to denote one or more than one magnesium salt.
[0088] In the rest of the text, the expression "at least one magnesium salt" is understood,
for the purposes of the present invention, both in the plural and the singular.
[0089] Non-limiting examples of suitable magnesium salts may be made of magnesium carbonate,
magnesium hydroxide, magnesium oxide, magnesium sulphate, magnesium silicate or magnesium
nitrate.
[0090] According to a preferred embodiment of the composition of the present invention,
the at least one magnesium salt is selected from the group consisting of magnesium
carbonate, magnesium oxide, and magnesium hydroxide.
[0091] As said, the composition of the present invention, as detailed above, may be prepared
by using at least one second additive in an amount providing in the composition (C)
a weight ratio of magnesium, expressed as magnesium oxide, to fluorine, expressed
as CaF
2, equal to or more than 5.0.
[0092] In other words, the second additive is used in such a way to have a composition (C)
wherein the weight ratio of magnesium, expressed as magnesium oxide, to fluorine,
expressed as CaF
2, is equal to or more than 5.0;

[0093] In general, the skilled in the art knows how to determine the amount of the second
additive needed to provide the weight ratio, as detailed above. The amount of the
second additive is dependent on the content of magnesium in the second additive and
on the fluorine, expressed as CaF
2, in the composition (C) after mixing the compound (SSB), as detailed above, with
the at least one first additive, as detailed above.
[0094] In a certain embodiment of the present invention, the composition (C) is prepared
by further adding the second additive in an amount from 400 wt. % to 2500 wt. %, preferably
from 1000 wt. % to 2000 wt. %, preferably from 1500 wt.% to 1800 wt. %, relative to
the weight of fluorine, expressed as CaF
2, in the composition, after mixing the compound (SSB), as detailed above, with the
at least one first additive, as detailed above.
[0095] It is further understood that the lower limit of the amount of the second additive
which is used should be sufficient to provide the content of magnesium, expressed
as magnesium oxide, as detailed above.
[0096] Advantageously, the second additive is used in an amount providing in the composition
(C) a weight ratio of magnesium, expressed as magnesium oxide, to fluorine, expressed
as CaF
2, equal to or more than 7.0, preferably equal to or greater than 10.0, more preferably
equal to or greater than 12.0, most preferably equal to or greater than 15.0, even
more preferably equal to or greater than 20.0.
[0097] Advantageously, the second additive is used in an amount providing in the composition
(C) a weight ratio of magnesium, expressed as magnesium oxide, to fluorine, expressed
as CaF
2, equal to or less than 25.0, preferably equal to or less than 20.0, more preferably
equal to or less than 15.0, most preferably equal to or less than 12.0, even more
preferably equal to or less than 10.0.
[0098] In a preferred embodiment of the method of the present invention, the second additive
is used in an amount providing in the composition (C) a weight ratio of magnesium,
expressed as magnesium oxide, to fluorine, expressed as CaF
2, from 5.0 to 25.0, preferably from 7.0 to 20.0, more preferably from 10.0 to 15.0,
most preferably from 12.0 to 15.0, or from 7.0 to 10.0.
[0099] According to the present invention, said second additive comprises magnesium, expressed
as magnesium oxide, in an amount of at least 20.0 wt. %, relative to the total weight
of the second additive. In general, the skilled in the art knows how to select the
second additive to provide the weight ratio as detailed above.
[0100] According to a preferred embodiment of the composition of the present invention,
the second additive comprises or consists essentially of a magnesium salt, as detailed
above, wherein the total amount of magnesium, expressed as magnesium oxide, is of
at least at least 25.0 wt.%, or of at least 30.0 wt.%, or of at least 35.0 wt. %,
or desirably of at least 35.0 wt.% relative to the total weight of the second additive.
Advantageously, the magnesium content, expressed as magnesium oxide, is less than
90.0 wt.%, or less than 80.0 wt.%, or less than 70.0 wt.%, or less than 60.0 wt.%,
or less than 55.0 wt.%, or less than 50.0 wt.%, or desirably less than 45.0 wt.%,
relative to the total weight of the second additive.
[0101] According to a preferred embodiment of the composition of the present invention,
the second additive may further comprise at least one calcium salt selected from the
group consisting of calcium carbonate, calcium oxide, and calcium hydroxide.
[0102] According to a preferred embodiment of the composition of the present invention,
the second additive comprises or consists essentially of the magnesium salt, as detailed
above and the calcium salt, as detailed above, wherein the total amount of magnesium,
expressed as magnesium oxide, and calcium, expressed as calcium oxide, is more than
80.0 wt.%, or more than 85.0 wt.% or more than 90.0 wt.% or more than 95.0 wt.% or
desirably more than 98.0 wt.% relative to the total weight of the compound, and wherein
the magnesium content, expressed as magnesium oxide, is of at least 20.0 wt.%, or
of at least 25.0 wt.%, or desirably of at least 30.0 wt.%, relative to the total weight
of the second additive. Advantageously, the magnesium content, expressed as magnesium
oxide, is less than 90.0 wt.%, or less than 80.0 wt.%, or less than 70.0 wt.%, or
less than 60.0 wt.%, or less than 55.0 wt.%, or less than 50.0 wt.%, or desirably
less than 45.0 wt.%, relative to the total weight of the second additive. Advantageously,
the calcium content, expressed as calcium oxide, is less than 80.0 wt.%, or less than
70.0 wt.%, or less than 60.0 wt.%, or less than 50.0 wt.%, or less than 40.0 wt.%,
or less than 30.0 wt.%, or desirably less than 20.0 wt.%, relative to the total weight
of the second additive.
[0103] Desirably, the magnesium content, expressed as magnesium oxide, varies from 20.0
wt. % to 80.0 wt.%, or from 20.0 wt.% to 70.0 wt.%, or from 25.0 wt.% to 60.0 wt.%
or from 30.0 wt.% to 50.0 wt.%, or from 30.0 wt.% to 45.0 wt.%, relative to the total
weight of the second additive.
[0104] Said second additive may be synthetically prepared by a variety of methods known
in the art or can be of natural origin.
[0105] Non-limiting examples of second additive of natural origin may be made of mined (raw)
minerals such as dolomite and dolomitic limestones.
[0106] In general, dolomitic limestone comprises MgCOs and CaCOs, in which the MgCOs and
CaCOs are present in a total amount of more than 95.0 wt.%, or more than 96.0 wt.%,
or more than 97.0 wt.%, or desirably more than 98.0 wt.%, relative to the total weight
of the dolomitic limestone, and wherein the MgCO3 content may vary from 20.0 wt.%
to 45.0 wt.%, or from 25.0 wt.% to 40.0 wt.%, or from 30.0 wt.% to 40.0 wt.% relative
to the total weight of MgCOs and CaCOs.
[0107] In general, dolomite comprises MgCOs and CaCOs, in which the MgCOs and CaCOs are
present in a total amount of more than 95.0 wt.%, or more than 96.0 wt.%, or more
than 97.0 wt.%, or desirably more than 98.0 wt.%, relative to the total weight of
the dolomitic limestone, and wherein the MgCOs and CaCOs content are present in a
1:1 molar ratio.
[0108] Non-limiting examples of synthetically prepared second additive suitable to be used
in the composition of the present invention may be partly or fully burnt dolomite
consisting of calcium oxide and magnesium oxide (also called calcined dolomite or
dolomitic quick lime or dolime), calcium hydroxide and magnesium oxide (also called
semi-hydrated dolomitic lime) or calcium hydroxide and magnesium hydroxide (also called
type S hydrated lime).
[0109] Alternatively, the second additive consists essentially of at least one magnesium
salt, as detailed above.
[0110] Within the context of the present invention, the term "consisting essentially of"
is to be understood to mean that any additional component different from the magnesium
salt, as detailed above, is present in an amount of at most 1.0 wt.%, or at most 0.5
wt.%, or at most 0.1 wt.%, based on the total weight of the second additive. Non-limiting
examples of such additive are magnesia, magnesite, olivine and brucite.
[0111] It is further understood that the first additive and the second additive according
to the present invention are two different compounds or compositions.
[0112] The inventors have surprisingly found that when a second additive, as detailed above,
is used to prepare the composition (C), as detailed above, the negative impact of
CaF
2 on the slag viscosity during the steel making process is reduced. It has been found
that CaF
2 is a slag fluidizer. This means that when a composition containing a high quantity
of CaF
2 is used as raw material in a steel making process, the viscosity of the slag generated
during the process is low. This slag having a low viscosity no longer correctly covers
the liquid steel which results in a reduction of the thermal insulation and increases
the risk of nitrogen pick that can then reduce the yield for the process. Therefore,
the use of the second additive according to the invention results in an improvement
of the yield of the steel making process while using a by-product as raw material.
[0113] According to the present invention, the composition (C), after mixing the compound
(SSB), as detailed above, with the at least one first additive, as detailed above,
and with the at least one second additive, as detailed above, further comprises fluorine,
expressed as CaF
2, in an amount equal to or less than 10.0 wt. %, relative to the total dry weight
of the composition (C).
[0114] The inventors have thus found that the composition (C) of the present invention,
can be safely used as raw material in a steel making process and that the yield of
said process is improved and the need of further additives during the process is reduced.
[0115] It is further understood that the definition of dry weight, as described above for
the compound (SSB), equally applies for the composition (C).
[0116] Preferably, said composition (C) comprises equal to or less than 8.0 wt. %, equal
to or less than 7.0 wt. %, preferably equal to or less than 6.0 wt. %, more preferably
equal to or less than 5.0 wt. %, even more preferably equal to or less than 4.0 wt.
%, most preferably equal to or less than 3.0 wt. %, most preferably equal to or less
than 2.0 wt. %, of fluorine, expressed as CaF
2, relative to the total dry weight of the composition (C).
[0117] It is further understood that the lower limit of fluorine, expressed as CaF
2, in the composition (C) is advantageously equal to or more than 0.0 wt. % or equal
to or more than 0.2 wt. %, preferably equal to or more than 0.5 wt. %, preferably
equal to or more than 0.7 wt. %, more preferably equal to or more than 1.0 wt. %,
even more preferably equal to or more than 1.5 wt. %, most preferably equal to or
more than 2.0 wt. %, relative to the total dry weight of the composition (C).
[0118] In an embodiment of the composition of the present invention, fluorine, expressed
as CaF
2,, as detailed above, is advantageously present in the composition (C) in an amount
from 0.0 wt. % to 10.0 wt. %, preferably from 0.2 wt. % to 8.0 wt. %, preferably from
0.5 wt. % to 7.0 wt. %, more preferably from 0.7 wt. % to 6.0 wt. %, more preferably
from 1.0 wt. % to 5.0 wt. % or from 1.5 wt. % to 5.0 wt. % or from 2.0 wt. % to 5.0
wt. %, relative to the total dry weight of the composition (C).
[0119] Preferably, the composition (C) is in the form of a solid composition. For the purpose
of the present invention, the term "solid composition" is intended to refer to a composition
in the form of powders, fibers, dusts, tablets, pellets, aggregates, compacts or briquettes
or a granular form such as granules or crumbs,.
[0120] Preferably, said composition (C), is in a form selected from the group consisting
of powders, aggregates, briquettes or mixtures of two or more thereof. Preferably,
said composition (C) is in a form selected from the group consisting of aggregates,
briquettes or mixtures of two or more thereof.
Method for manufacturing the composition (C)
[0121] The methods to manufacture composition (C) are also an aspect of the present invention.
[0122] It is further understood that all definitions and preferences, as described above,
equally apply for all further embodiments, as described below.
[0123] The composition (C) of the present invention can be prepared by a variety of methods
known in the art.
[0124] In one embodiment of the present invention, the method for the manufacturing of the
composition (C), as detailed above, comprises mixing of
(a) at least one compound (SSB), as detailed above,
(b) at least one first additive, as detailed above and
(c) optionally at least one second additive, as detailed above.
[0125] The inventors have further found that the composition (C) prepared according to the
invention is particularly suitable for use as raw material in a steel making process.
[0126] It is understood that the skilled person in the art will carry out said mixing according
to general practice such as notably using optimal times, speeds, weights, volumes
and batch quantities.
[0127] Furthermore, it is understood that any order of mixing of the various components
as comprised in the composition (C), as detailed above, is acceptable.
[0128] When appropriate, the first additive, as detailed above and the second additive,
as detailed above, can be pre-mixed to form a premix prior to the mixing with the
compound (SSB), or the first additive and the second additive can be separately mixed
with the compound (SSB).
[0129] When the first additive and the second additive are separately mixed with the compound
(SSB), the first additive and the second additive can be mixed simultaneously, or,
if desired, the second additive can be mixed after the first additive.
[0130] It is further understood that the various components as comprised in the composition
(C), as detailed above may be introduced in the form of a powder or dust, however,
it may also be present in a compressed form such as tablets, pellets or granules to
manufacture the composition (C).
[0131] Generally said mixing, as detailed above, may be carried out by using a variety of
mixing means known in the art. Non-limiting examples of such mixing means are for
example mechanical mixing such as traditional mixers and blenders, high intensity
mixers and electric stirrers, said mixers, blenders and stirrers which can be equipped
with at least one dispersion disk. A high sheer force can be applied during the mixing
in order to improve the homogeneity of the composition (C).
[0132] Preferably, said mixing is carried out until a homogeneous mixture is obtained.
[0133] Advantageously, the composition (C) may be further converted into a pellet form,
tablet form, briquette form, compact form, aggregate form or granular form, or mixtures
thereof. Such conversion methods are known in the art.
[0134] In a preferred embodiment, said composition (C), after mixing, is then subjected
to a shaping step. In general during this shaping step, a shape is given to the composition
(C). Various shaping process are known in the art and non-limiting examples of such
a shaping process are pelletizing, compacting, slip casting, aggregating, extrusion.
Preferably, the shaping process is a compacting process. Non-limiting examples of
compacting processes are cold isostatic pressing, tabletting, briquetting, roll compaction.
After the shaping process, the shaped composition (C) can take various forms such
as compacts, tablets, briquettes, pellets, extrudates.
[0135] Preferably, according to the invention, the shaped composition (C) takes the form
of briquettes or aggregates.
[0136] The premix of the first additive, as detailed above, and the second additive, as
detailed above, is another aspect of the present invention.
[0137] It is further understood that all definitions and preferences, as described above,
equally apply for the premix.
[0138] The use of the composition (C), as detailed above, as raw material in a steel making
process is another aspect of the invention.
[0139] It is further understood that all definitions and preferences, as described above,
equally apply for the use of the composition (C) as raw material in a steel making
process.
EXAMPLES
[0140] The invention will be now described in more details with reference to the following
examples, whose purpose is merely illustrative and not intended to limit the scope
of the invention.
Test methods
Measurements of free water
[0141] The measurements of free water were performed by subjecting the sample to a heating
step at 80 °C until a constant weight of the sample subjected to said measurement
was reached.
Measurements of fluorine
[0142] The amount of fluorine was measured after the measurement of free water, described
above. Fluorine was thus measured on a "dry sample", after the evaporation of the
free water, as detailed above.
[0143] The measurements of fluorine were performed by using wavelength dispersive X-ray
fluorescence spectrometer device from Malvern Panalytical Zetium.
Measurements of the reactivity
[0144] The quicklime reactivity was evaluated with the European reactivity on slaking test,
EN 459-2: Building lime - Part 2: Tests methods. The reactivity t
60, was determined as the time needed to reach 60 °C when 150 g of quicklime was added
to 600 cm
3 of water.
Measurements of the LOI (Loss on ignition)
[0145] The LOI, in order to determine the amount of bound water and carbonate in the invention,
was obtained using thermogravimetric analysis (TGA) performed by gradually raising
the temperature of a sample of the composition, at a rate of 5°C/min from room temperature
to at least 950°C (or to constant mass) in a furnace under a flow of nitrogen, as
its weight was measured on an analytical scale. The weight of the sample was plotted
against temperature to observe thermal transitions/decompositions that occur upon
raising temperature. The hydrated compound(s) comprised in the composition of the
invention decompose(s) between 350°C and 550°C by releasing water (then called "bound
water"). The mass loss occurring between 350°C and 550°C corresponds therefore to
the amount of "bound water" (expressed as H
2O) according to the invention. The carbonate compound(s) comprised in the composition
of the invention decompose(s) between 550°C and 950°C (or constant mass) by releasing
CO
2. The mass loss occurring between 550°C and 950°C (or constant mass) corresponds therefore
to the amount of total carbonate (expressed as CO
2) according to the invention.
Measurements of the mechanical resistance of the agglomerated composition
[0146] The compressive strength was measured by applying a progressively increasing load
(or force) on a solid sample until fracture. The maximum force applied before fracture
was recorded and used as an indicator of the mechanical resistance. The measurement
was performed using a laboratory press Mecmesin OmniTest.
Example 1 (E1)
[0147] Example 1 was realized using the raw materials having the composition and properties
as described in tables 1-3.
Table 1: Steel scale by-product compound (compound SSB)
|
Wt. % |
Free water* |
55.0 |
CaF2** |
36.2 |
Fe2O3** |
30.4 |
Cr** |
5.3 |
Ni** |
4.1 |
Mo** |
0.1 |
* relative to the total weight of the compound SSB |
** relative to the total dry weight of the compound SSB |
Table 2: First additive - composition
|
Amount (wt. %*) |
Na2O |
0.04 |
MgO |
1.55 |
Al2O3 |
0.252 |
SiO2 |
0.745 |
P2O5 |
0.025 |
SO3 |
0.123 |
K2O |
0.046 |
CaO |
92.94 |
Ti |
0.032 |
Fe2O3 |
0.090 |
Zn |
0.005 |
Sr |
0.041 |
H2O (bound water) |
0.9 |
CO2 (carbonate) |
0.7 |
* Relative to the total weight of the first additive |
Table 3: First additive - reactivity
Reactivity |
|
T60 (min) |
1.6 |
T°2' (°c) |
63.2 |
Tmax (°c) |
74.7 |
[0148] The compound SSB, described in table 1, was mixed with a first additive, as detailed
in tables 2 and 3, in an amount providing a weight ratio of calcium oxide to the free
water present in the compound (SSB) of 1.62. The mixing was performed with an Eirich
intensive mixer type R01, at 300 rpm stirrer speed and 42 rpm bowl speed. 1.5 kg of
compound SSB was add to the mixer together with 500g of the first additive, as detailed
in table 1 and 2, and mixed during 30 min. Then, an additional 500g of first additive
was added and mixed during 30 min. Then, an additional 500g of first additive was
added and mixed during 30 min. The resulting composition was sampled after 2h from
the start to measure its free water content which was of 4.7 wt%, relative to the
total weight of the composition. This result shows that the addition of the first
additive allows to obtain a composition having a content of free water less than 5
wt. %, which can thus be used as raw material in a steel making process.
Example 2 (E2)
[0149] Example 2 was realized by mixing the composition obtained in example 1 with a second
additive presenting the composition as detailed in table 4.
Table 4 : Second additive - composition
|
Amount (wt. %*) |
H2O free |
< 0.01 |
MgO |
27.5 |
CaO |
40.0 |
Fe2O3 |
1.8 |
F |
< 0.01 |
SO3 |
1.8 |
SiO2 |
3.0 |
Total LOI (bound water + carbonate) |
26.0 |
*relative to the total weight of the second additive |
[0150] The content of fluorine, expressed as CaF
2, in the composition obtained in example 1 was measured, as detailed above, and was
of 8.8 wt. %, relative to the total dry weight of the composition. Then 216.6g of
the second additive, as detailed in table 4, was added and mixed with 200g sampled
from the composition obtained in example 1.
[0151] The mixing was performed using a WAB Turbula
® mixer for 10 min at 72 rpm. The free water of the resulting composition was of 2.2
wt. %, relative to the total weight of the composition. In this composition, the weight
ratio of the magnesium, expressed as magnesium oxide, to the fluorine, expressed as
CaF
2, was 5.0. This result shows that the addition of the second additive allows to obtain
a composition which can be safely used as raw material in a steel making process.
Comparative Example 3 (CE3)
[0152] The compound SSB, described in table 1, was mixed with a first additive, as detailed
in tables 2 and 3, in an amount providing a weight ratio of calcium oxide to the free
water present in the compound (SSB) of 1.1. The mixing was performed with a fast shear
mixer as described in standard NF P 94-093. 1.5 kg of compound SSB was add to the
mixer together with 500g of the first additive, as detailed in table 1 and 2, and
mixed during 30 min. Then, an additional 500g of first additive was added and mixed
during 30 min.
[0153] The resulting composition was sampled after 1h from the start to measure its free
water content which was of 17.4 wt%, relative to the total weight of the composition.
This result shows that the addition of the first additive in a lower ratio does not
allow to obtain a composition which can be safely used as raw material in a steel
making process.
Table 5 : Results
|
E1 |
E2 |
CE3 |
Free water in composition (C) |
4.7 |
2.2 |
17.4 |
Ratio CaO/Free H2O during the addition of first additive |
1.62 |
1.62 |
1.08 |
Ratio MgO/CaF2 after addition of second additive |
N/A |
5.0 |
N/A |
Example of shaping process
Example 4
[0154] Example 4 was realized using the composition obtained in example 1.
[0155] 15g product was pressed at 94Mpa using a lab-scale tableting device to obtain an
agglomerated composition in the form of a tablet which had a compressive mechanical
strength of 890N. This result shows that the composition of the present can be shaped
and that the resulting shaped product presents good mechanical strength.