U.S. patent number 3,807,557 [Application Number 05/279,903] was granted by the patent office on 1974-04-30 for flotation of pyrite from coal.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the. Invention is credited to Kenneth J. Miller.
United States Patent |
3,807,557 |
Miller |
April 30, 1974 |
FLOTATION OF PYRITE FROM COAL
Abstract
Pyrite is removed from coal by means of a two-stage froth
flotation process. In the first stage, coarse pyrite is removed as
underflow in a conventional froth flotation operation. In the
second stage, the froth product from the first stage is subjected
to froth flotation using a coal flotation depressant and a pyrite
flotation collector, thereby removing a substantial proportion of
fine pyrite.
Inventors: |
Miller; Kenneth J. (Floreffe,
PA) |
Assignee: |
The United States of America as
represented by the Secretary of the (Washington, DC)
|
Family
ID: |
23070834 |
Appl.
No.: |
05/279,903 |
Filed: |
August 11, 1972 |
Current U.S.
Class: |
209/166;
209/167 |
Current CPC
Class: |
B03D
1/02 (20130101) |
Current International
Class: |
B03D
1/00 (20060101); B03D 1/02 (20060101); B03d
001/02 () |
Field of
Search: |
;209/166,107 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Bull. of Mines Tech. Progress Report, Feb. 1972, TPR51 (Miller
& Baker) pp. 1-7; Chem. Abst. 73, 1970, 122, 223c pp. 106,
107..
|
Primary Examiner: Halper; Robert
Attorney, Agent or Firm: Brown; William S.
Claims
I claim:
1. A two-stage process for removal of pyrite from coal comprising
the steps of (1) forming an aqueous pulp of the coal in a finely
divided state, and frothing the pulp to collect the coal in the
froth and leave a residual pulp containing course pyrite and (2)
removing and repulping the froth product from step (1),
conditioning the pulp with a coal flotation depressant and a pyrite
flotation collector, and frothing the pulp to collect a substantial
portion of fine pyrite in the froth and leave a residual pulp
containing a product coal of low pyritic sulfur content.
2. The process of claim 1 in which the depressant employed in stage
2 is an organic colloid.
3. The process of claim 2 in which the depressant is a
carbohydrate.
4. The process of claim 2 in which the depressant is quebracho
extract.
5. The process of claim 1 in which the collector employed in stage
2 is a xanthate.
6. The process of claim 5 in which the xanthate is potassium amyl
xanthate.
Description
Sulfur content of bituminous coals ranges from less than 1 percent
to as much as 6 percent or more. Pyritic sulfur, i.e., sulfur in
the form of pyrite or marcasite, essentially FeS.sub.2, generally
makes up about 40 to 80 percent of the total sulfur present, with
the balance being chiefly organic sulfur compounds. The pyritic
sulfur is present in macroscopic and microscopic forms, the
macroscopic form occurring chiefly as veins, lenses or beds,
nodules, or pyritized plant tissue. The microscopic pyrite occurs
as finely disseminated globules, veinlets, or euhedral crystals as
small as 1 or 2 microns.
Air pollution as a result of burning high-sulfur coals has come
under increasing public scrutiny and efficient means for processing
coals to lower their sulfur content are, therefore, of increasing
importance. Obviously, the sulfur content of some coals could be
significantly reduced if most of the pyrite were physically removed
during coal preparation. However, because coal must be crushed to a
fine size in order to liberate pyrite, such a separation is
extremely difficult with conventional coal preparation techniques.
Specific gravity separation methods are ineffective because of the
extreme fineness of some of the crushed material, and conventional
froth flotation suffers from the tendency for the fine-size pyrite
to float with the coal.
It has now been found, according to the present invention, that
these problems can be largely overcome by means of a process in
which the coal, in a finely-divided form in an aqueous pulp, is
initially subjected to froth flotation to float the coal and remove
most of the coarse, or essentially free, pyrite as underflow, along
with the other nonfloatable refuse such as clay and shale. The
froth product from this first step of the process is then repulped
with fresh water and froth flotation, using a coal flotation
depressant and a pyrite flotation collector, is employed to float a
substantial portion of the remaining fine-size pyrite, while
removing the coal product as underflow.
The feed material in the process of the invention may be any coal
containing a substantial proportion of pyritic sulfur. This will
usually be a bituminous coal having a pyritic sulfur content as
discussed above. It is employed in a finely divided form, i.e., in
a particle size of less than about 35 mesh (500 microns). Suitable
particle size reduction may be readily achieved by conventional
techniques such as grinding, pulverizing etc.
The initial stage of the process consists of conventional froth
flotation of the finely divided coal from an aqueous pulp
consisting of about 8 to 15 percent coal. This pulp is prepared by
conventional means comprising addition of the coal to water in a
flotation cell, or prior to addition to the cell, followed by
thorough dispersion, as by mechanical stirring means. The pH of the
pulp is not critical but will usually be about 4.5 to 8.5. A
conventional frother may also be added to the dispersion in an
amount of about zero to 0.001 percent by weight. It has, however,
been found that optimum results are obtained in the process of the
invention when the amount of frother employed is held to near the
minimum amount required to float the coal. Suitable frothers
include those commonly used in the froth flotation of coal and
other minerals, e.g., pine oil and aliphatic alcohols such as
methyl isobutyl carbinol (MIBC) and 2-ethylisohexanol.
Flotation of the coal is then accomplished by aeration at a flow
rate of about 0.3 to 1.2 cubic feet of air per minute per gallon of
slurry, generally for a period of about 1 to 3 minutes.
Subsequently or simultaneously, the resulting froth product is
separated by conventional means such as froth scrapers or
paddles.
In the second stage of the process, this froth product is repulped
in the flotation cell with fresh water to form a pulp having about
6 to 14 percent solids content. The pH of this pulp should be from
about 4.5 to about 8.0, since values substantially above or below
this range may have an adverse effect on the pyritic sulfur content
of the second stage froth concentrate refuse. This pulp is then
subjected to froth flotation, employing a coal flotation depressant
and a pyrite flotation collector in order to float a substantial
proportion of the fine-size pyrite, with the desired coal product
remaining as underflow.
Preferably the second-stage pulp is initially conditioned with the
coal flotation depressant by maintaining about 0.002 to 0.007
percent by weight of the depressant dispersed in the pulp for a
period of about 5 seconds to 1 minute. The depressant consists of
an organic colloid. This material may consist of a carbohydrate
such as dextrin or modified, i.e., the so-called soluble, starches,
such as modified corn or potato starch.
The organic colloid depressant may also consist of a proteinaceous
material such as glue, gelatin, albumin, casein or whey.
It may also consist of complex polyhydroxy carboxylic acids and
glucocides of high molecular weight such as quebracho extract,
tannin or saponin.
About 0.001 to 0.005 weight percent of pyrite flotation collector
is then added and the mixture again conditioned for a period of
about 5 seconds to 1 minute. The collector consists of a xanthate,
of the formula RO-C-SM, where R is an alkyl radical of at least
about 3 carbon atoms and M is a metal such as potassium or sodium.
Generally, the effectiveness of the compound increases with the
number of carbon atoms in R, potassium amyl xanthate being a
preferred compound. However, other xanthates such as sodium
isobutyl xanthate and sodium isopropyl xanthate are also
effective.
A frother such as those disclosed above is then added in similar
amount, and the pulp is aerated in the same manner as in the first
flotation stage.
The froth is again removed, as in the first stage, and the coal
product recovered from the remaining slurry by means of
conventional procedures such as vacuum filtration or
centrifugation.
The invention will be more specifically illustrated by the
following examples. In these examples, flotation tests were
conducted in a standard laboratory rotor-stator flotation cell of
the subaeration type. The impeller speed was set at 1,800
revolutions per minute, and the aeration rate was 0.33 cubic feet
of air per minute. For the first stage of each test, 200 grams or
400 grams of minus 35 mesh bituminous coal was mixed in the cell
with 2,300 milliliters of tap water, and the slurry was conditioned
for 15 minutes to insure thorough wetting of the material. The 8 or
15 percent solids slurries had a pH ranging from about 5 to about
8.
The first stage of the process was a standard flotation procedure
with minimum frother during which much of the coarse, or
essentially free, pyrite was removed as underflow with the other
nonfloatable refuse. The froth product from the first stage was
then repulped in the floatation cell with 2,300 milliliters of
fresh water, and the slurry was treated with a coal floatation
depressant. After a brief conditioning time, about 1 minute, the
pyrite flotation collector was added. After another brief
conditioning period, the frother was added, the air applied, and
the froth product collected for 1 to 3 minutes.
Feed compositions, reagents and the results are given, in tabular
form in the following examples. Tailings 1 in these examples is the
underflow refuse from the first stage, tailings 2 the froth
concentrate refuse in the second stage, and clean coal is the
underflow product from the second stage. Hercules RT1712 is a trade
name for pine oil, available from Hercules Powder Co. Aero Zanthate
350 is a trade name for potassium amyl xanthate, available from
American Cyanamid Co. Aero Depressant 633 is a trade name for a
carbohydrate colloid flotation depressant, available from American
Cyanamid Co. The feed material in Examples 1 to 17 consisted of
coal from the Lower Freeport coal bed in Cambria County, Pa., while
those in Examples 18, 19 and 20 consisted of coal from the Lower
Kittanning coal bed in Armstrong County, Pa., the Middle Kittanning
bed in Lawrence County, Pa., and the Pittsburgh bed in Green
County, Pa., respectively.
Example 1 shows the results obtained with no xanthate collector.
Obviously, no selective pyrite flotation occurred. Examples 2
through 8, however, show the effect of increased amounts of
xanthate in the second stage. The depressant dosage also had to be
increased to avoid floating the coal, but this did not adversely
affect pyrite flotation. The clean coal products in Examples 2
through 8, which amounted to 50 to 60 percent of the feed,
contained only 0.29 to 0.56 percent pyritic sulfur, whereas the
tailings 2 product contained 3.83 to 7.71 percent. That is,
although tailings 2 represented only 3.4 to 10.7 percent of the
feed product, it contained 45 to 75 percent of the pyrite available
in the second stage. These results clearly demonstrate the
selectivity of the process.
Examples 2 through 8 were run at reduced pH with HCl, but this step
was not essential with this coal. Examples 9 and 10 show only
slight adverse effect as a result of eliminating some, and then all
of the HCl.
Examples 11 and 12 show that quebracho depresses the coal in the
second stage as well as does the Aero Depressant 633. Example 13
shows results with modified cornstarch,which was also effective.
And examples 14 and 15 show that methylisobutyl carbinol is as
effective as pine oil as the frothing agent.
Examples 16 and 17 show results with the lower molecular weight
xanthate collectors, sodium isobutyl xanthate and sodium isopropyl
xanthate. Potassium ethyl xanthate was also tested, but it was not
effective at concentrations below about 2 lb/ton of coal. These
results indicate that the amyl xanthate is the most powerful
collector, while the butyl, propyl, and ethyl xanthates are
gradually less effective.
Examples 18, 19, and 20 show results with three additional coal
samples to demonstrate the broad application of the process.
EXAMPLE 1
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 31.3 2.21 1.78 Tailings 1 36.1 68.2 3.47 3.31 Tailings 2
2.7 9.5 1.15 0.56 Clean coal 61.2 10.5 1.52 0.93
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Hercules RT 1712 0.1 Final pH=5.6
EXAMPLE 2
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 31.7 2.22 1.79 Tailings 1 36.8 67.5 3.31 3.21 Tailings 2
7.7 11.5 4.50 3.83 Clean coal 55.5 10.8 1.18 0.56
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Aero Xanthate 350 0.2 Hercules RT1712 0.1 Final
pH=6.2
EXAMPLE 3
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 34.3 2.38 1.91 Tailings 1 43.1 65.7 3.58 3.46 Tailings 2
6.0 12.0 4.63 4.24 Clean coal 50.9 10.3 1.10 0.32
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Aero Xanthate 350 0.3 Hercules RT1712 0.1 Final
pH=5.7
EXAMPLE 4
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 25.2 2.12 1.77 Tailings 1 34.1 57.2 3.52 3.52 Tailings 2
5.8 12.1 5.63 5.23 Clean coal 60.1 8.4 0.99 0.45
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Aero Xanthate 350 0.3 Hercules RT1712 0.1 Final
pH=5.7
EXAMPLE 5
Analyses, percent Product Weight Ash sulfur sulfur Feed 100.0 32.2
2.29 1.92 Tailings 1 36.6 70.1 3.43 3.42 Tailings 2 4.7 15.5 7.66
6.91 Clean coal 58.5 9.9 1.12 0.56 Reagents Pounds per ton of coal
Hydrochloric acid 0.9 Aero Depressant 633 0.7 Aero Xanthate 350 0.5
Hercules RT1712 0.05 Final pH=6.2
EXAMPLE 6
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 31.2 2.23 1.79 Tailings 1 36.3 68.1 3.49 3.29 Tailings 2
3.4 17.8 8.47 7.71 Clean coal 60.3 9.7 1.12 0.56 Reagents Pounds
per ton of coal Hydrochloric acid 0.9 Aero Depressant 633 1.0 Aero
Xanthate 350 0.5 Hercules RT1712 0.05 Final pH=6.2
EXAMPLE 7
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 32.1 2.28 1.85 Tailings 1 37.6 68.1 3.40 3.34 Tailings 2
10.7 11.6 4.71 4.13 Clean Coal 51.7 10.1 0.96 0.29
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.7 Aero Xanthate 350 0.5 Hercules RT1712 0.1 Final
pH=6.2
EXAMPLE 8
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 32.2 2.30 1.84 Tailings 1 34.6 73.3 3.55 3.34 Tailings 2
8.7 14.4 5.96 5.57 Clean coal 56.7 10.0 0.97 0.35
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 1.0 Aero Xanthate 350 0.5 Hercules RT1712 0.1 Final
pH=6.4
EXAMPLE 9
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 26.8 2.24 1.91 Tailings 1 41.7 52.1 3.53 3.46 Tailings 2
4.9 11.7 5.18 4.55 Clean coal 53.4 8.5 0.97 0.45
Reagents Pounds per ton of coal Hydrochloric acid 0.6 Aero
Depressant 633 0.5 Aero Xanthate 350 0.3 Hercules RT1712 0.1 Final
pH=6.4
EXAMPLE 10
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 25.8 2.29 1.86 Tailings 1 35.4 57.0 3.72 3.43 Tailings 2
9.8 9.7 3.99 3.44 Clean coal 54.8 8.6 1.07 0.56 Reagents Pounds per
ton of coal Aero Depressant 633 0.5 Aero Xanthate 350 0.3 Hercules
RT1712 0.1 Final pH=8.1
EXAMPLE 11
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 25.3 2.19 1.78 Tailings 1 33.4 58.7 3.48 3.48 Tailings 2
6.0 11.5 5.30 4.65 Clean coal 60.0 8.3 1.17 0.56
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Quebracho 0.5
Aero Xanthate 350 0.3 Hercules RT1712 0.1 Final pH=5.6
EXAMPLE 12
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 26.2 2.26 1.78 Tailings 1 33.1 61.5 3.86 3.86 Tailings 2
7.5 11.8 5.39 4.57 Clean coal 59.4 8.4 0.97 0.27
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Quebracho 0.7
Aero Xanthate 350 0.4 Hercules RT1712 0.1 Final pH=5.6
EXAMPLE 13
Analyses percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 29.1 2.25 1.80 Tailings 1 36.3 65.3 3.63 3.48 Tailings 2
5.4 11.2 3.53 2.86 Clean coal 58.3 8.3 1.27 0.65
Reagents Pounds per ton of coal First stage: Methyl isobutyl
carbinol 0.1 Second stage: Water soluble cornstarch 0.7 Aero
Xanthate 350 0.7 Methylisobutyl carbinol 0.1
EXAMPLE 14
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 25.7 2.25 1.87 Tailings 1 34.6 57.9 3.66 3.66 Tailings 2
6.5 11.5 5.63 4.87 Clean coal 58.9 8.4 1.05 0.48
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Aero Xanthate 350 0.2 Methylisobutyl carbinol
0.1 Final pH=5.5
EXAMPLE 15
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 26.2 2.24 1.81 Tailings 1 34.5 58.5 3.70 3.70 Tailings 2
8.8 11.3 4.78 4.34 Clean coal 56.7 8.8 0.95 0.27
Reagents Pounds per ton of coal Hydrochloric acid 0.9 Aero
Depressant 633 0.5 Aero Xanthate 350 0.3 Methylisobutyl carbinol
0.1 Final pH=5.7
EXAMPLE 16
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 24.9 2.48 1.95 Tailings 1 30.8 61.2 4.45 4.18 Tailings 2
10.4 11.0 4.44 4.07 Clean coal 58.8 8.4 1.10 0.41
Reagents Pounds per ton of coal Hydrochloric acid 0.6 Aero
Depressant 633 0.7 Sodium isobutyl xanthate 0.5 Methylisobutyl
carbinol 0.08 Final pH=7.5
EXAMPLE 17
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 23.4 2.29 1.72 Tailings 1 31.7 55.5 4.01 3.67 Tailings 2
7.5 8.0 1.86 1.16 Clean coal 60.8 8.5 1.44 0.77
Reagents Pounds per ton of feed Aero Depressant 633 0.7 Sodium
isopropyl xanthate 0.5 Methylisobutyl carbinol 0.08 Final
pH=8.1
EXAMPLE 18
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 22.4 2.89 2.43 Tailings 1 20.0 65.8 6.18 6.18 Tailings 2
11.1 17.0 6.56 6.56 Clean coal 68.9 10.7 1.34 0.68
Reagents Pounds per ton of coal First stage: Methylisobutyl
carbinol 0.25 Second stage: Hydrochloric acid 1.1 Aero Depressant
633 1.0 Aero Xanthate 350 0.7 Methylisobutyl carbinol 0.08 Final
pH=7.3
EXAMPLE 19
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 6.8 2.87 2.35 Tailings 1 11.3 31.7 12.30 12.13 Tailings
2 9.9 12.2 7.83 7.23 Clean coal 78.8 2.6 0.89 0.34
Reagents Pounds per ton of coal First stage: Kerosine 0.6
Methylisobutyl carbinol 0.16 Second stage: Aero Depressant 633 1.0
Aero Xanthate 350 0.7 Methylisobutyl carbinol 0.08 Final pH=5.3
EXAMPLE 20
Analyses, percent Total Pyritic Product Weight Ash sulfur sulfur
Feed 100.0 15.3 2.45 1.52 Tailings 1 16.3 56.7 5.68 5.35 Tailings 2
9.1 10.6 4.57 3.62 Clean coal 74.6 6.8 1.48 0.43
Reagents Pounds per ton of coal First stage: Methylisobutyl
carbinol 0.25 Second stage: Hydrochloric acid 1.1 Aero Depressant
633 0.7 Aero Xanthate 350 1.0 Methylisobutyl carbinol 0.08 Final
pH=7.6
* * * * *