WO2002016659A1 - Ferrous metal particle briquettes and method of making and using them - Google Patents

Ferrous metal particle briquettes and method of making and using them Download PDF

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Publication number
WO2002016659A1
WO2002016659A1 PCT/US2001/026358 US0126358W WO0216659A1 WO 2002016659 A1 WO2002016659 A1 WO 2002016659A1 US 0126358 W US0126358 W US 0126358W WO 0216659 A1 WO0216659 A1 WO 0216659A1
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WO
WIPO (PCT)
Prior art keywords
ferrous metal
briquettes
silicate
metal particles
acid esters
Prior art date
Application number
PCT/US2001/026358
Other languages
French (fr)
Inventor
Thomas A. Cobett
Original Assignee
Solvent Systems International
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvent Systems International filed Critical Solvent Systems International
Priority to AU2001285236A priority Critical patent/AU2001285236A1/en
Publication of WO2002016659A1 publication Critical patent/WO2002016659A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/248Binding; Briquetting ; Granulating of metal scrap or alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • C22B1/242Binding; Briquetting ; Granulating with binders
    • C22B1/243Binding; Briquetting ; Granulating with binders inorganic
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • ferrous metal materials iron and steel
  • the ferrous metal has significant value if it can be re-melted by
  • the present invention is directed to ferrous metal masses or briquettes
  • the ferrous metal masses (iron and steel) comprise a mixture of at least 80%
  • ferrous metal particles by weight ferrous metal particles and preferably over 90% by weight ferrous metal
  • particles are included. They also include an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into an alkali metal silicate. Forming the particles into
  • ferrous metal particles In carrying out the method of the present invention, ferrous metal particles
  • the mixture should be at least 80%, and preferably at least 90%, 80% by
  • ferrous metal with the balance being an alkali alkaline metal silicate and other inorganic impurities, such as silica sand.
  • the ferrous metal particles are recovered from ferrous metal processing,
  • particles may range in size from fine powders to coarse, grains. Particles in the
  • alkali metal silicates may be used in the practice of the invention, including sodium
  • silicate potassium silicate, and lithium silicate.
  • sodium silicate is
  • one or more silicates may be combined in the mixture.
  • silicate should be used in the form of an aqueous solution containing from about 20%
  • the alkali metal silicate may be
  • Curing of the briquettes is believed to proceed by causing the alkali metal
  • silicate solution to form a gel, which contracts and forces the water out of the
  • the moisture in the alkaline metal silicate solution is
  • the gelling of the silicate be accelerated by adding an
  • an accelerant for example, the following materials can be used as curing accelerants for this purpose: calcium silicate, aluminates such as
  • acetic acid esters such as ethylene glycol diacetate, ethylene
  • glycol monoacetate glycerol triacetate
  • glycerol diacetate glycerol
  • carbon dioxide gas into the mixture is another method of accelerating the curing
  • Heating is yet another way to accelerate the curing, and may be used
  • briquettes may be hardened by simply permitting them to dehydrate until hardened.
  • briquettes may be of any practical size convenient for melting in the particular furnace
  • the silicate forms a glassy coating on the ferrous metal particles, preventing the
  • the melting point of the metal particles fines is controlled by their chemistry.
  • Such briquettes will melt at a temperature of at least about 2400°F, and up to about
  • Example 1 is intended to teach one of ordinary skill how to make and use the invention. These examples are not intended to limit the invention or its protection in any way. Example 1
  • a briquette in accordance with the present invention was prepared by
  • Si0 2 to about 1.0 part Na 2 O could be used and indeed, weight ratios of as low as 2.0
  • the materials were mixed for three minutes and compacted by hand into a
  • plastic form to increase the density of the briquette.
  • the form was inverted onto a
  • composition of the iron was verified as being acceptable Class 30 gray iron, which is
  • the partially cured shapes were allowed to dehydrate, forming briquettes in
  • Example 2 exposed to weather, as in Example 2.
  • the shapes were also melted into an iron bath, as in
  • Example 1 The same results achieved in Examples 1 and 2 were achieved in this example.

Abstract

Ferrous metal briquettes made from ferrous metal particles and an alkaline metal silicate, for adding to ferrous metal melts to recycle the particles.

Description

5543-00002
FERROUS METAL PARTICLE BRIQUETTES AND METHOD OF MAKING AND USING THEM
This application is a continuation of U.S. Patent Application Serial No.
09/575,226 filed May 22, 2000 and entitled BRIQUETTING OF FERROUS METAL
PARTICLES WITH AN ALKALI METAL SILICATE FOR RECOVERY BY MELTING.
BACKGROUND OF THE INVENTION
Many methods of processing ferrous metal materials (iron and steel), such as
crushing, grinding, cutting, polishing, machining, screening and melting ferrous metal
parts, produce large amounts of fine ferrous metal particles. It is desirable to recover and
reprocess these particles. The ferrous metal has significant value if it can be re-melted by
a foundry, smelter or steel making operation. It is also environmentally preferable to melt
existing metal scrap instead of extracting new metal from the earth as ore.
Unfortunately, particles of ferrous metals will oxidize (rust) rapidly at ambient
temperature, particularly in humid weather. When such ferrous particles are added
to a hot melting furnace, they are likely to be oxidized so rapidly that they will burn
before melting. Additionally, fine, light particles of ferrous metal are often blown out
of the melt bath and into the atmosphere by heat convection or by the air blast from
a cupola furnace. Finally, the iron in such iron oxide particles that do not burn and
are not blown away are nevertheless difficult or inefficient to recover by melting, and
often end up being lost into the slag produced as a byproduct of the melting
process. Thus, most of the ferrous metal particles produced in ferrous metal
processing are so problematic to recycle, that they are regarded as practically non- recyclable. They therefore are often placed in landfills and lost forever. A method of
forming these fine ferrous metal particles into compacted masses or briquettes that
resist oxidation and can be simply and efficiently re-melted in foundries, smelters or
steel making operations, would constitute an important improvement in the current
state of the art.
SUMMARY OF THE INVENTION
The present invention is directed to ferrous metal masses or briquettes
bonded by a glassy binder coating and to a method of making those masses and
using them in recycling ferrous metal particles.
The ferrous metal masses (iron and steel) comprise a mixture of at least 80%
by weight ferrous metal particles and preferably over 90% by weight ferrous metal
particles. They also include an alkali metal silicate. Forming the particles into
briquettes makes it possible to conveniently and efficiently recycle the particles by
adding them to a ferrous metal melt.
DETAILED DESCRIPTION OF THE INVENTION
In carrying out the method of the present invention, ferrous metal particles
and an alkali metal silicate solution liquid alkaline metal silicate are mixed together in
any convenient manner, and shaped into masses or briquettes, preferably
compacted, and caused to cure or harden by gelation and/or dehydration. After
curing, the mixture should be at least 80%, and preferably at least 90%, 80% by
weight of ferrous metal with the balance being an alkali alkaline metal silicate and other inorganic impurities, such as silica sand.
The ferrous metal particles are recovered from ferrous metal processing,
including crushing, grinding, cutting, polishing, and machining operations. The
particles may range in size from fine powders to coarse, grains. Particles in the
range of about 100 mesh to about 10 mesh are preferred. However, larger and smaller
particles can also be utilized. It is desirable to ensure that the ferrous metal particles
are kept free from rust prior to being combined with the silicate. Various liquid alkaline
alkali metal silicates may be used in the practice of the invention, including sodium
silicate, potassium silicate, and lithium silicate. Among these, sodium silicate is
preferred. Additionally, one or more silicates may be combined in the mixture. The
silicate should be used in the form of an aqueous solution containing from about 20%
to 50% by weight solids preferably 35% to 45% by weight solids, and most preferably
about 38% by weight solids, with the balance water. Where the ferrous metal particles
are provided in a form which already includes water, the alkali metal silicate may be
provided, in whole or in part, in dry form so that the already present water supplies
some or all of the water in the alkali metal solution.
Curing of the briquettes is believed to proceed by causing the alkali metal
silicate solution to form a gel, which contracts and forces the water out of the
ferrous metal/silicate mixture, thusthereby hardening the final product. Thus, during
the curing of the briquettes, the moisture in the alkaline metal silicate solution is
given up to the atmosphere.
Also, it is preferred that the gelling of the silicate be accelerated by adding an
appropriate amount of an accelerant. For example, the following materials can be used as curing accelerants for this purpose: calcium silicate, aluminates such as
calcium aluminate, sodium aluminate, magnesium aluminate, potassium aluminate
and lithium aluminate; acetic acid esters such as ethylene glycol diacetate, ethylene
glycol monoacetate, glycerol triacetate, glycerol diacetate, and glycerol
monoacetate; carbonic acid esters such as ethylene carbonate and propylene
carbonate; formic acid esters such as methyl formate and ethyl formate; lactic acid
esters; adipic acid esters; glutaric acid esters and succinic acid esters. Injecting
carbon dioxide gas into the mixture is another method of accelerating the curing
process. Heating is yet another way to accelerate the curing, and may be used
either alone or in combination with any of the other accelerants. Indeed, any known
method used to cause the curing of the alkali metal silicates solutions may be
utilized to harden the ferrous metal particles fines into convenient shapes.
In the absence of the addition of accelerants or the use of heating, the
briquettes may be hardened by simply permitting them to dehydrate until hardened.
The mixture of ferrous metal particles and liquid alkaline alkali metal silicate
solution is compacted into appropriately sized forms corresponding to the size and
shape of the mass desired before allowing the mixture to cure, either slowly at ambient temperature, or more rapidly by adding accelerants as described above. The
briquettes may be of any practical size convenient for melting in the particular furnace
being used. For example, briquettes of about 2" x 2" x 2" up to 10" x 10" x 10" in size
have been made and used in accordance with the invention in induction furnaces and
in an iron foundry cupola. Briquettes less than about 2" x 2" x 2" in size are less
desirable because of the danger that they will be blown out of the melt bath. Surprisingly, although one would expect the exposed ferrous metal particles
to rust on the surface of the final briquette produced, this does not occur. Rather,
the silicate forms a glassy coating on the ferrous metal particles, preventing the
briquettes from rusting, even under humid conditions. Furthermore, porosity of the
briquette would also be expected which would produce rusting that works its way
through the briquette, weakening the briquette and reducing its reuse value. Again,
surprisingly, this is not found not to be the case.
The melting point of the metal particles fines is controlled by their chemistry.
When the briquettes are added to a hot melting furnace maintained at a
temperature sufficiently high to cause melting of the metal particles fines, the entire
briquette breaks up, releasing the iron into the melt, while the silicates float up to
the surface to become part of the slag. For example, it has been found that many
such briquettes will melt at a temperature of at least about 2400°F, and up to about
3000°F. This occurs with little or no loss of metal due to high temperature
oxidation, and certainly no blow out of fine metal particles. Indeed, it is believed
that the glassy coating of the ferrous metal particles by the silicate continues to
remain in place at the high melting temperatures, until after the ferrous metal
particles melt into the furnace bath, whereupon the sodium silicate becomes a part
of the slag floating on top of the molten metal.
The following examples are intended to be illustrative of the present invention
and to teach one of ordinary skill how to make and use the invention. These examples are not intended to limit the invention or its protection in any way. Example 1
A briquette in accordance with the present invention was prepared by
combining 90% by weight of ferrous metal particles produced by grinding iron
castings with 10% by weight of a solution of aqueous sodium silicate containing
42% by weight solids, which had a weight ratio of about 3.22 parts Si0 to about
1.0 part Na2O. In other tests, it was found that a weight ratio of about 2.4 parts
Si02 to about 1.0 part Na2O could be used and indeed, weight ratios of as low as 2.0
to 1.0, and as high as 4.0 to 1.0, will produce satisfactory briquettes. Acceptable
solids contents of the aqueous sodium silicate solutions ranged from as low as about
20% to as high as 50%.
The materials were mixed for three minutes and compacted by hand into a
plastic form to increase the density of the briquette. The form was inverted onto a
plate and the resulting briquette carefully removed from the form. The briquette was
allowed to dehydrate for 72 hours.
Several of the briquettes were placed outdoors in an unprotected area. A
small pile of unbonded or free ferrous metal particles was placed next to the
briquettes. After 90 days of weathering, including rain, snow, ice and sunlight, the
briquettes exhibited no oxidation. The small pile of unbonded particles was
completely covered with bright orange rust. Example 2
Five pounds of briquettes prepared as explained in Example 1, were placed on
top of six pounds of liquid Class 30 gray iron that had been melted to a temperature
of 2700°F., in a small electric induction furnace. The briquettes, which floated on the surface, gradually melted into the existing molten iron. The floating of the
briquettes ensured insured that any moisture present in the glassy coating within the
interstices of the mass would evaporate and escape without entering the melt.
After removal of the slag on the surface of the molten metal, the iron was
poured into an ingot mold and permitted to cool. After cooling, the ingot was
weighed and found to be just slightly less than 11 pounds. This indicates nearly
complete recovery of metal from the 5 pounds of briquettes. Additionally, the
composition of the iron was verified as being acceptable Class 30 gray iron, which is
a standard iron composition with 30,000 p.s.i. tensile strength.
Example 3
A mixture of ferrous metal particles and sodium silicate solution was made as
explained in Example 1. This mixture was compacted into plastic forms and carbon
dioxide gas was injected at a pressure of 15 p.s.i., using a small lance. After 10
seconds of gassing, the partially cured mixture was easily removed from the form.
The partially cured shapes were allowed to dehydrate, forming briquettes in
accordance with the invention, and then were exposed to weather as in Example 1.
They were also melted in an iron bath, as in Example 2. In all cases, the results
were the same as in Examples 1 and 2.
Example 4
In this example, a mixture of 89.2% by weight of fine ferrous metal particles
generated by grinding iron castings, was combined with 10% by weight aqueous sodium
silicate and 0.8% by weight of an accelerant, ethylene glycol diacetate. The materials were
mixed for 3 minutes, and compacted by hand into a plastic form. After 15 minutes, a partially cured shape was easily removed from the form. The partially cured shape was
allowed to dehydrate to form briquettes in accordance with the present invention and
exposed to weather, as in Example 2. The shapes were also melted into an iron bath, as in
Example 1. The same results achieved in Examples 1 and 2 were achieved in this example.
Example 5
In this example, 10% by weight of the liquid sodium silicate was combined with
86% by weight of iron metal particles generated by grinding iron castings and 4.0% by
weight sodium aluminate, which was added as an accelerant. The materials were mixed
for 3 minutes and compacted by hand into a plastic form. After fifteen minutes, the
mixture was easily removed from the form. These partially cured shapes were allowed to
dehydrate, forming briquettes in accordance with the present invention. They were
exposed to weather and melted into an iron bath, as in Examples 1 and 2, producing
results commensurate with those Examples.
While the present invention is described above in connection with preferred or
illustrative embodiments, these embodiments are not intended to be exhaustive or
limiting of the invention. Rather, the invention is intended to cover all alternatives,
modifications, and equivalents included within its spirit and scope, as defined by the
appended claims.

Claims

CLAIMSWhat I claim is:
1. A method for making ferrous metal masses with a glassy coating comprising:
mixing ferrous metal fines particles and an aqueous alkali metal silicate
solution;
shaping the mixture into briquettes remove air pockets; and
permitting the briquettes to cure.
2. The method of claim 1 in which the briquettes are compacted to increase
their density.
3. The method of claim 1 in which the ferrous metal particles are supplied in an
amount sufficient to provide the cured briquettes with over 80% by weight ferrous
metal.
4. The method of claim 1 in which the ferrous metal particles are supplied in an
amount sufficient to provide the cured briquettes with at least 90% by weight ferrous
metal.
5. The method of claim 1 in which the ferrous metal particles range in size from fine to coarse.
6. The method of claim 1 in which the ferrous metal particles are from about 10
to about 100 mesh in size.
7. The method of claim 1 in which the ferrous metal particles are recovered from
a ferrous metal processing operation chosen from the group consisting of crushing, grinding, cutting, polishing and machining.
8. The method of claim 1 in which the ferrous metal particles are free from rust
before being mixed with the alkali metal silicate solution.
9. The method of claim 1 in which the alkali metal silicate is chosen from the
group consisting of sodium silicate, potassium silicate, and lithium silicate.
10. The method of claim 9 in which the alkali metal silicate is sodium silicate.
11. The method of claim 10 in which the sodium silicate is in the form of an
aqueous solution having SiO2 and Na2O in a ratio from about 2.0 to 1.0 to about 4.0
to 2.0.
12. The method of claim 10 in which the sodium silicate is in the form of an
aqueous solution having SiO2 and Na2O in a weight ratio of about 3.22 to 1.0.
13. The method of claim 10 in which the sodium silicate is in the form of an
aqueous solution having SiO2 and Na2O in a weight ratio of about 2.4 to 1.0.
14. The method of claim 1 in which the alkali metal silicate is supplied in the form
of an aqueous solution having from about 20% to about 50% by weight solids.
15. The method of claim 1 in which the alkali metal silicate is supplied in the form
of an aqueous solution having about 38% by weight solids.
16. The method of claim 1 in which the gelling of the alkali metal silicate is
accelerated by adding an appropriate amount of a curing accelerant.
17. The method of claim 16 in which the curing accelerant is chosen from the
group consisting of calcium silicate, aluminates, acetic acid esters, carbonic acid
esters, formic acid esters, lactic acid esters, adipic acid esters, succinic acid esters,
glutaric acid esters and acidic gases.
18. The method of claim 17 where the aluminates include calcium aluminate,
sodium aluminate, magnesium aluminate, potassium aluminate or lithium aluminate;
the acetic acid esters include ethylene glycol monoacetate, glycerol triacetate,
glycerol diacetate, or glycerol monoacetate; the carbonic acid esters include ethylene
carbonate or propylene carbonate; the formic acid esters include methyl formate and
ethyl formate, and the acidic gases include carbon dioxide.
19. The method of claim 1 in which the curing of the briquettes is accelerated by
heating.
20. The method of claim 1 in which the briquettes range in size from 2" x 2" x 2"
to about 10" x 10" x 10" in size.
21. The method of claim 1 in which the briquettes are at least about 2" x 2" x 2" in size.
22. A method of recycling ferrous metal particles by first making ferrous metal
masses with a glassy coating by mixing ferrous metal particles and an alkali metal
silicate solution, shaping the mixture into briquettes, permitting the briquettes to cure,
storing the briquettes as desired, and then adding the briquettes to a ferrous metal
melt maintained at a temperature sufficiently high to melt the ferrous metal particles.
23. The method of claim 22 in which the ferrous metal melt is maintained at a
temperature of about 2400°F to about 3000°F.
24. The method of claim 22 in which the briquettes have at least 80% by weight ferrous metal.
25. The method of claim 22 in which the ferrous metal particles range in size from about 10 to about 100 mesh in size.
26. The method of claim 22 in which the alkali metal silicate is chosen from the
group consisting of sodium silicate, potassium silicate, and lithium silicate.
27. The method of claim 1 in which the ferrous metal particles are recovered from
a ferrous metal processing operation chosen from the group consisting of crushing,
grinding, cutting, polishing, machining, screening and melting.
28. A ferrous metal briquette made by mixing ferrous metal particles and an alkali
metal silicate solution, shaping the mixture into briquettes, and permitting the
briquette to cure.
29. The method of claim 1 where the ferrous metal particles are provided in a
form which already includes water, and the alkali metal silicate is provided, in whole
or in part, in dry form so that the already present water supplies some or all of the
water in the alkali metal silicate solution.
PCT/US2001/026358 2000-08-23 2001-08-23 Ferrous metal particle briquettes and method of making and using them WO2002016659A1 (en)

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Application Number Priority Date Filing Date Title
US64495800A 2000-08-23 2000-08-23
US09/644,958 2000-08-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541057B2 (en) 2008-12-18 2013-09-24 Invista North America S.A R.L. Cyclohexane oxidation process byproduct derivatives and methods for using the same
CN110787724A (en) * 2019-12-03 2020-02-14 四川致远锂业有限公司 Fine lithium ore granulation process and granulator
CN111350079A (en) * 2018-12-21 2020-06-30 日华化学株式会社 Method for producing leather material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802732A (en) * 1953-12-04 1957-08-13 Frederick J Crolius Slag producing material and metallurgical method employing same to recover metal values from steel
US3973998A (en) * 1975-05-05 1976-08-10 Celanese Coatings & Specialties Company Rinsing solutions for acid cleaned iron and steel surfaces
US4105457A (en) * 1976-05-03 1978-08-08 Midrex Corporation Briquet and method of making same
US4585475A (en) * 1980-06-25 1986-04-29 Inland Steel Company Method for recycling oily mill scale
US5531805A (en) * 1990-02-13 1996-07-02 The Illawarra Technology Corporation Limited Smelting ferrous materials
US6139619A (en) * 1996-02-29 2000-10-31 Borden Chemical, Inc. Binders for cores and molds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2802732A (en) * 1953-12-04 1957-08-13 Frederick J Crolius Slag producing material and metallurgical method employing same to recover metal values from steel
US3973998A (en) * 1975-05-05 1976-08-10 Celanese Coatings & Specialties Company Rinsing solutions for acid cleaned iron and steel surfaces
US4105457A (en) * 1976-05-03 1978-08-08 Midrex Corporation Briquet and method of making same
US4585475A (en) * 1980-06-25 1986-04-29 Inland Steel Company Method for recycling oily mill scale
US5531805A (en) * 1990-02-13 1996-07-02 The Illawarra Technology Corporation Limited Smelting ferrous materials
US6139619A (en) * 1996-02-29 2000-10-31 Borden Chemical, Inc. Binders for cores and molds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541057B2 (en) 2008-12-18 2013-09-24 Invista North America S.A R.L. Cyclohexane oxidation process byproduct derivatives and methods for using the same
CN111350079A (en) * 2018-12-21 2020-06-30 日华化学株式会社 Method for producing leather material
CN110787724A (en) * 2019-12-03 2020-02-14 四川致远锂业有限公司 Fine lithium ore granulation process and granulator

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