U.S. patent number 3,607,326 [Application Number 04/885,640] was granted by the patent office on 1971-09-21 for mineral grinding aids.
This patent grant is currently assigned to W. R. Grace & Co.. Invention is credited to Frank G. Serafin.
United States Patent |
3,607,326 |
Serafin |
September 21, 1971 |
MINERAL GRINDING AIDS
Abstract
Solid inorganic compounds such as naturally occuring inorganic
mineral compounds and Portland cement are interground with certain
amine salts of aryl hydroxy compounds (e.g. triethanolamine
phenoxide) to enhance the efficiency of the grinding operation.
Inventors: |
Serafin; Frank G. (Peabody,
MA) |
Assignee: |
W. R. Grace & Co.
(Cambridge, MA)
|
Family
ID: |
25387377 |
Appl.
No.: |
04/885,640 |
Filed: |
December 16, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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556589 |
Jun 10, 1966 |
|
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|
Current U.S.
Class: |
106/727; 106/794;
106/460; 241/16; 106/781; 106/801; 252/384 |
Current CPC
Class: |
C04B
28/04 (20130101); B02C 23/06 (20130101); C04B
24/122 (20130101); C04B 28/04 (20130101); C04B
14/00 (20130101); C04B 14/30 (20130101); C04B
24/122 (20130101); C04B 2103/52 (20130101) |
Current International
Class: |
C04B
28/00 (20060101); C04B 24/00 (20060101); C04B
28/04 (20060101); C04B 24/12 (20060101); B02C
23/06 (20060101); B02C 23/00 (20060101); C04b
007/54 () |
Field of
Search: |
;106/90,102,314
;241/15,16,22 ;252/384 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levow; Tobias E.
Assistant Examiner: Scott; W. T.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
556,589, filed June 10, 1966 and now abandoned. This invention
relates to grinding minerals and more particularly to the use of an
additive for improving the grinding efficiency and pack set
characteristics of minerals.
Claims
What is claimed is:
1. A composition consisting essentially of a solid, inorganic
compound selected from the group consisting of naturally occuring
mineral compounds, Portland cement clinker, magnesia and beryllium
oxide, and intimately admixed therewith, about 0.001 to 1% weight,
based on the weight of said solid compound, of an additive,
consisting of a salt of an amine selected from the group consisting
of morpholine and an alkanolamine wherein the alkanol group
contains about 1-5 carbon atoms and an aryl hydroxy compound
wherein the aryl radical is selected from the group consisting of
phenyl, naphthyl and substituted phenyl and maphthyl wherein the
substituent is selected from the group consisting of nitro, halo,
alkyl of 1-5 carbon atoms, aryl, amino and alkoxy of 1-5 carbon
atoms.
2. The composition as defined in claim 1 wherein said additive is
triethanolammonium phenoxide.
3. The composition of claim 1 wherein said solid inorganic compound
is selected from the group consisting of phosphate rock, iron ore,
bauxite, clay, gypsum, limestone, silica, Portland cement clinker,
magnesia and beryllium oxide.
4. The composition of claim 1 wherein said solid material is
magnesia.
5. The composition of claim 1 wherein said solid material is
amorphous silica.
6. The composition of claim 1 wherein said solid material is
taconite.
7. The method which comprises intergrinding a solid, inorganic
compound selected from the group consisting of naturally occuring
mineral compounds, Portland cement clinker, magnesia and beryllium
oxide, an amount of an additive consisting of a salt of an amine
selected from the group consisting of morpholine and an alkandamine
wherein the alkanol group contains about one to five carbon atoms
and an aryl hydroxy compound wherein the aryl radical is selected
from the group consisting of phenyl, naphthyl and substituted
phenyl and naphthyl wherein the substituent is selected from the
group consisting of nitro, halo, alkyl of 1-5 carbon atoms, aryl,
amino and alkoxy of 1-5 carbon atoms, the amount of said additive
being sufficient to enhance the efficiency of the grinding
operation.
8. The method of claim 7 wherein said amount is about 0.001 to 1
percent by weight, based on the weight of the solid compound.
9. The method of claim 7 wherein the solid inorganic compound is
Portland cement and said additive is triethanolammonium
phenoxide.
10. A composition consisting essentially of Portland cement, and,
intimately admixed therewith, about 0.001 to 1 percent by weight,
based on the weight of said Portland cement, of an additive
consisting of a salt of an amine selected from the group consisting
of morpholine and triethanolamine and an aryl hydroxy compound
wherein the aryl radical is selected from the group consisting of
phenyl, naphthyl and substituted phenyl and naphthyl wherein the
substituent is selected from the group consisting of nitro, halo,
alkyl of 1-5 carbon atoms, aryl, amino and alkoxy of 1-5 carbon
atoms.
11. The composition as defined in claim 10 wherein said amine
comprises a mixture of morpholine and triethanolamine and said aryl
hydroxy compound is phenol.
12. The composition as defined in claim 10 wherein said additive is
triethanolammonium phenoxide.
13. The composition as defined in claim 10 wherein the amount of
additive employed is about 0.004 to 0.04 percent by weight, based
on the weight of said Portland cement.
14. The method which comprises intergrinding Portland cement with
about 0.001 to 1 percent by weight, based on the weight of said
Portland cement, of an additive consisting of a salt of an amine
selected from the group consisting of morpholine and
triethanolamine and an aryl hydroxy compound wherein the aryl
radical is selected from the group consisting of phenyl, naphthyl
and substituted phenyl and naphthyl wherein the substituent is
selected from the group consisting of nitro, halo, alkyl of 1-5
carbon atoms, aryl, amino and alkoxy of 1-5 carbon atoms.
15. The method as defined in claim 14 wherein said additive is
triethanolammonium phenoxide.
16. The method as defined in claim 14 wherein the amount of the
additive is about 0.004 to 0.04% by weight, based on the weight of
said Portland cement.
Description
In the processing of minerals, a grinding operation is generally
employed either in the unprocessed or semiprocessed state to reduce
the particular mineral to relatively small particle size. It is
desirable in this grinding step to have as efficient an operation
as possible; that is, to reduce the particular mineral to the
desired particular size at a relatively rapid rate.
A grinding aid is frequently employed in such a grinding operation
to assist in the grinding of the minerals either by increasing the
rate of production or by increasing the fineness of the particles
at the same rate of production without having adverse effects on
any of the properties of the ground product.
Cleavage of the particles during grinding of the minerals exposes
fresh or nacent surfaces which have high energy. The surface forces
of the ground particles persist for some time after grinding and
lead to compaction or pack set and/or poor fluidity if they are not
reduced. Mineral particles when compacted by vibration, e.g., when
transported in a hopper car often become semirigid and will not
flow until considerable mechanical effort has been applied to break
up the compaction. Therefore, it is desirable that a material be
employed to reduce the above-described adhesion of the
particles.
The term "pack set" as used herein is intended to refer to the
agglomeration or adhesion of particles by, for example, storing or
transporting in bulk. Adhesion results from surface forces, the
majority of which are believed to be created during the grinding of
the minerals. "Pack set index" is a relative term which indicates
numerically how prone a particular material is to start flowing
after it is stored or transported in bulk. "Pack set index ratio"
is the relative pack set index of the untreated sample compared to
the treated sample. This ratio is used to permit comparison between
different samples of the mineral.
Pack set index is determined in the following manner:
One hundred grams of the mineral is placed in a 250 millilitor
Erhlenmeyer flask set on top of a variable vibrator. The flask
containing the mineral is vibrated 15 seconds after which it is
removed from the vibrator and set into a jig with the axis of the
flask lying horizontally. The flask is then rotated around its axis
until the mineral which is compacted in the bottom of the flask
collapses. The flask is twisted at 180.degree. angles at
approximately 100 twists per minute. The number of 180.degree.
twists required for the mineral sample to collapse establishes the
pack set index. Thus the greater the energy required to break up
the bed, the higher will be the pack set index.
A novel additive has now been found which will function as a
grinding aid and a pack set inhibitor for minerals. The novel
additive of the present invention is an amine salt of an aryl
hydroxy compound. Such additives are the reaction product of an
aryl hydroxy compound, e.g., phenol, with an amine. In preparing
the novel additives of the present invention, one or more aryl
hydroxy compounds are mixed with one or more amines. The starting
materials may be pure chemicals or materials containing impurities.
The methods of preparing the additives are known to the art.
Preferably, equimolar parts of the amine and aryl hydroxy compound
are employed.
The term "aryl" as used herein is intended to refer to phenyl or
naphthyl radical. It should be understood that one or more of the
hydrogen atoms on the aryl radical may be replaced by a nitro;
halogen, preferably chlorine; alkyl, preferably to a 1- to 5-carbon
group, more preferably methyl; aryl, preferably of one to three
aromatic rings, amino and alkoxy preferably a one to five carbon
alkoxy group.
The amines employed in the present invention include mono-; di-and
trialkanol amines and morpholine. The alkanol group or groups in
the mono-, di- and trialkanol amines each contain about one to five
carbon atoms. Illustrative of such alkanolamines are
monethanolamine, diethanolamine, dipropanolamine, dibutanolamine,
triethanolamine, tripropanolamine, etc., as well as mixtures
thereof. Obviously the aforementioned amines employed in the
invention can contain substituent groups which do not deleteriously
affect the reaction of the amine with the aryl hydroxy compound or
the desired effects of the additive of the invention on minerals
mentioned herein. Exemplary of such nondeleterious substituted
amines are N-methyl-morpholine and 4-(2-aminoethoxy)
ethylmorpholine. Trialkanolamines, for example, triethanolamine,
are especially preferred for use in forming the additive of the
invention.
The additive is interground with the mineral in the grinding mill
to provide increased grinding efficiency as well as other
advantageous results, e.g., inhibiting pack set of bulk stored
materials. It has also been found that the novel additive of the
present invention serves to provide fluidity to the ground minerals
when they are being transported by conveying systems, particularly
to pneumatic air systems.
The term "mineral" as used herein is intended to refer to solid
inorganic compounds including naturally occurring inorganic mineral
compounds such as phosphate rock; iron ore, for example taconite;
bauxite; clay; gypsum; amorphous silica and limestone; as well as
such materials derived from naturally occurring mineral compounds
as Portland cement clinker; beryllium oxide and magnesia. The
naturally occurring mineral compounds can be more efficiently
ground according to the invention either as recovered in their
natural state or at some point in their processing.
The grinding aids of the present invention are particularly
preferred for used with cement, particularly Portland cement.
Portland cement represents a class of hydraulic cement and is
comprised essentially of two calcium silicates and a lesser amount
of calcium aluminate. These cements are produced by heating an
intimate mixture of finely divided calcareous material (limestone)
and argillaceous material (clay) to form a clinker. The clinker is
ground with the addition of about 2 percent gypsum, or some other
form of calcium sulfate, to obtain the desired setting qualities in
the finished cement. It is to the clinker that the novel additive
of this invention is preferably added to increase grinding
efficiency and to inhibit subsequent pack set in the finished
cement. The additive of the invention was also found to ideally
enhance the compressive strength of concrete made from Portland
cement interground therewith.
The additives of the present invention are employed in either dry
or liquid form. For convenience, the additive is in water solution
to permit accurate metering into the mill stream. In instances
where the additive is not very soluble in water, it can be utilized
in liquid form by emulsifying with a suitable wetting agent, for
example, sodium dodecyl benzene sulfonate. The addition is
accomplished either prior to the grinding or the additive is
introduced into the grinding mill simultaneously with the mineral.
If the additive is employed merely for the reduction of pack set or
for fluidizing purposes, it is added at any convenient point in the
processing.
The additive is employed effectively over a relatively wide range.
The preferred range is about 0.001 to 1 percent based on the weight
of the mineral, i.e., the weight of additive solids based on the
weight of the mineral solids (herein referred to as solids on
solids). In a particularly preferred embodiment, the amount of
additive employed is about 0.004 to 0.04 percent. Higher levels are
employed if grinding to a relatively high surface area and the
amount of additive is limited solely by the desired surface area
and the degree of fluidity desired.
EXAMPLE I
In the following table, the efficiency of triethanolamonium
phenoxide, prepared by mixing equimolar parts of triethanolamine
and phenol, as a grinding aid is reported. The data was collected
on Type I Portland cement ground in a laboratory steel ball mill
for 3403 revolutions at 210.degree. F.
amount of Additive Blain surface % Increase C% solids on solids)
Area, Cm..sup.2 /g. over blank
__________________________________________________________________________
0.01 3114 4.21 0.02 3128 5.20 0.03 3121 4.45 0.04 3134 5.41 0.06
3134 4.89 0.08 3184 7.09
__________________________________________________________________________
A novel grinding aid was prepared by mixing 34 parts by weight of a
50--50 mixture of phenol and cresol with 65.9 parts by weight of a
50--50 mixture of morpholine and triethanolamine. The grinding
efficiency was determined on Type I Portland cement ground in a
laboratory mill for 4941 revolutions at 230.degree. F. At a level
of 0.012 percent based on the weight of the cement, an increase in
Blain Surface Area of 6.75 percent over a blank was found.
EXAMPLE II
A sample of magnesia was interground with 0.010 percent by weight
of triethanolammonium phenoxide in a laboratory steel ball mill.
For comparison, a blank sample containing no phenoxide additive was
also ground. Each sample was ground for 4125 revolutions at
230.degree. F. using a steel to magnesia ratio of 6.5 to 1. The
results were as follows.
---------------------------------------------------------------------------
Amount of Additive Blaine (wt.% additive solids Surface % Increase
Additive on wt. of magnesia) Area, Over Blank Cm..sup.2 /g.
__________________________________________________________________________
Blank -- 5217 -- Triethanol- ammonium Phenoxide 0.010 5644 8.18
__________________________________________________________________________
EXAMPLE III
A sample of amorphous silica was interground with 0.04 percent by
weight of treithanolammonium phenoxide in a laboratory steel ball
mill. For comparison, a blank sample containing no phenoxide
additive was also ground. Each sample was ground for 8855
revolutions at 190.degree. F. using a steel to silica ratio of 6.5
to 1. The results are as follows ##SPC1##
EXAMPLE IV
A sample of taconite was interground with 0.050 percent by weight
of triethanolammonium phenoxide in a laboratory steel ball mill.
For comparison, a blank sample containing no phenoxide additive was
also ground. Each sample was ground for 14,880 revolutions at
220.degree. F. using a steel to taconite ratio of 6.5 to 1. The
results were as follows.
Additive Amount of Additive Blaine (wt.% additive solids Surface
%Increase on wt. of taconite) Area Over Blank (Cm..sup.2 /g.)
__________________________________________________________________________
Blank -- 5702 -- Triethanol- ammonium Phenoxide 0.050 6806 19.4
__________________________________________________________________________
The additive of the present invention is employed preferably as the
sole grinding aid but it should be understood that it can also be
employed with a mixture of one or more grinding aids or in
admixture with other additives.
* * * * *