Note: Descriptions are shown in the official language in which they were submitted.
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A NON-CORROSIVE TREATMENT TO ENHANCE PRESSURIZED AND NON-
PRESSURIZED PULVERIZED COAL COMBUSTION=
FIELD OF THE INVENTION
The invention pertains to methods and compositions for inhibiting corrosion of
metal
surfaces in contact with a furnace.
BACKGROUND OF THE INVENTION
The use of copper and other metals to enhance furnace operation is well known.
For
example, in accordance with the teachings of U.S. Patent 6,077,325 (Morgan et
al.),
metallic compounds including Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Al, Sn,
and Pb
may be added to pulverized coal that is burned as fuel in a blast furnace or
the like.
Pulverized coal is often used as a substitute for a portion of the coke in the
preparation
of iron involving the reduction of iron oxide with carbon in the blast
furnace. This
substitution purportedly results in less pollution since coke is being
replaced in part,
and since coal is less expensive than coke, economies in the process can be
realized.
In typical blast furnace processes, iron bearing materials including iron ore,
sinter,
scrap, or other iron source along with a fuel, generally coke, and a flux,
limestone, or
dolomite are charged into the blast furnace from the top. The blast furnace
burns part
of the fuel to produce heat for melting the iron ore and the balance of the
fuel is
utilized for reducing the iron and its combination with carbon. The charge in
a typical
furnace, per ton of pig iron produced, is about 1.7 tons of ore or other iron
bearing
materials, 0.5-0.65 tons of coke or other fuel, and about 0.25 tons of
limestone and/or
dolomite. Additionally, from 1.8-2.0 tons of air are blown into the furnace
during the
process.
In practice, iron bearing raw materials (sinter, iron ore, pellets, etc.),
fuel (coke), and
flux (limestone, dolomite, etc.) are charged to the top of the furnace. Heated
air
(blast) is blown into a blast furnace through openings, known as tuyeres, at
the bottom
of the furnace. Tuyere stocks are fitted with injection lances through which
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supplemental fuels (gas, oil, and pulverized coal) are injected. The blast air
burns the
fuel and facilitates the smelting chemistry that produces iron. Combustion
gases from
the blast furnace are scrubbed to remove particulate and other noxious gases
before
being burned in stoves which are used to preheat blast air or in other
applications,
e.g., coke ovens, boilers, etc.
As referred to above, when pulverized coal is substituted for a portion of the
coke,
metals such as those disclosed in the '325 patent may be used as combustion
catalysts
or aids. These are of benefit since they provide the ability to use lower rank
coals in
the furnace and allow for greater coke replacement by the pulverized coal.
Additionally, they help to minimize "coal cloud" and reduce LOT. Lowered slag
content, reduced particulate emissions, and higher quality iron are also
potential
benefits that may be attributed to the use of these catalysts or aids.
Copper-based catalysts or combustion aids have become especially popular.
However, attendant problems of corrosion have appeared as a result. The
problem
arises from the corrosion that the product generates on mild steel surfaces
that are
present in the furnace system in which the combustion catalyst/aid is applied.
(As
used herein, "furnace" and "furnace systems" refer to ovens, boilers, blast
furnaces, or
any enclosure in which a fuel is combusted.)
As a consequence of this corrosion of metallic parts and components of a
furnace
system, the furnace equipment itself can fail, leading to process down time
and costly
replacement.
SUMMARY OF THE INVENTION
We have developed a technology that inhibits corrosion in furnace systems and
allows
use of metallic based combustion catalysts/aids, especially those employing Cu
as the
active component. In one aspect of the invention, the corrosion inhibiting
treatment
of the invention is blended with a copper combustion catalyst/aid to form a
protective
film on the mild steel surface in contact with the furnace combustion
products.
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The corrosion inhibiting treatment comprises a blend of a primary aminoalcohol
(i. e.,
having primary amino function) and boric acid or water soluble salt or the
acid. A
tertiary aminoalcohol (i. e., having a tertiary amine function) may also be
present in
the blend. The blend is preferably sprayed onto the pulverized coal in aqueous
solution form prior to injection of the coal into the furnace. Alternatively,
the
treatment may be applied in spray form anywhere in the furnace system
including the
so-called "fireside" or "cold" ends of the furnace. (See U. S. Patents
4,458,606 and
4,224,180.)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Metal surfaces, such as mild steel surfaces, of a furnace system are
effectively treated
in accordance with the invention by a corrosion inhibiting treatment
comprising a
blend of a primary aminoalcohol and boric acid or water soluble salt form
thereof.
Additionally, the corrosion inhibiting treatment may comprise a tertiary
aminoalcohol.
Preferably, the primary aminoalcohol is 2-aminoethanol and the tertiary
aminoalcohol
is triethanolamine. The invention has proven to be successful, especially in
furnace
systems in which pulverized coal is burned as fuel in the presence of a copper
catalyst/combustion aid.
The corrosion inhibiting treatment is most preferably provided in the form of
an
aqueous solution. By the phrase" aqueous solution" as used herein, we mean to
encompass not only true chemical solutions, but also dispersions, mixtures,
and
suspensions. The solution may be sprayed directly over the pulverized coal in
an
amount of about 100 ml to 1 L of aqueous solution per ton of coal. More
preferably,
the dosage rate is from about 300 m1-1L of aqueous solution per ton pulverized
coal.
Preferably, the corrosion inhibiting treatment comprises both the 2-
aminoethanol and
triethanolamine component. In addition, conventional corrosion inhibitors,
such as
water-soluble gluconic acid salts, preferably sodium gluconate, may be
incorporated
into the corrosion inhibiting treatment. When the pulverized coal is to be
burned in
the presence of copper as a catalyst/combustion aid, a copper ion source may
also be
incorporated into the aqueous solution that is to be sprayed over the coal.
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The invention is also directed to corrosion inhibiting treatment compositions
that are
adapted for application or spraying onto the fuel in the form of an aqueous
solution.
In these compositions, the 2-aminoethanol, triethanolamine, and boric acid or
salt
thereof components may be present in the aqueous solution in the amount of
about 1-
wt%. Sodium gluconate may also be present in the aqueous solution in an amount
of about 1-15 wt%. In those instances in which a copper ion source is also
present in
the aqueous solution, the copper ion source may be present in such an amount
as to
provide Cu++ in an amount of 1-20 wt%.
The synergistic blend of 2-aminoethanol, triethanolamine, and borate is not
water
soluble in the presence of copper. However, when this blend is mixed with the
known
mild steel corrosion inhibitor, sodium gluconate, the gluconate/"blend"
mixture has a
high solubility in water even in the presence of copper.
Exemplary compositions in accordance with the invention include:
aminoalcohol component(s) and boric acid or salt 1-10 wt%
sodium gluconate 1-15 wt%
copper (as Cu++)* 0-20 wt%
water remainder
More preferably, the compositions include
aminoalcohol blend of 2-aminoethanol and 1-10 wt%
triethanolamine with boric acid or salt
sodium gluconate 1-15 wt%
copper (as Cu)* 1-20 wt%
*Copper compound adapted to provide requisite amount of
Cu++ ion in aqueous solution.
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Based upon preliminary results, it is preferred to provide the copper ion
source,
sodium gluconate, 2-aminoethanol, triethanolamine, and boric acid or water
soluble
salt in a single aqueous solution for spray application over the pulverized
coal.
Exemplary copper ion sources are copper sulfate pentahydrate and copper II-D-
gluconate.
The product which is presently preferred for commercial use comprises .about
3%
actives of a blend of 2-aminoethanol, triethanolamine, and boric acid, along
with 4%
active sodium gluconate, and 19% actives of copper sulfate pentahydrate along
with
sufficient water to equal 100% of the total weight of the formulation.
EXAMPLES
The invention will be further described in conjunction with the following
examples
which should be viewed as being illustrative of the invention and should not
be
construed to limit the invention.
EXAMPLE 1
Bottle Test Method for Corrosion Rate Comparison =
Experimental Procedure
All corrosion tests were carried out using a bottle test method with mild
steel
coupons. The coupons were cleaned with tri-sodium phosphate and pumice before
and after exposure to the produce solution. Isopropyl alcohol was used to
rinse the
coupons after cleaning. Each low carbon steel coupon was immersed in a 1% (by
weight) copper solution prepared form the indicated stock solution for 24
hours.
(Only exceptions are the last two entries in the data table below which
involved
immersion of the mild steel coupons into the undiluted stock solution.) Total
test
solution weight was 100 grams. Each test was conducted at 30 C in a water bath
shaking at 40 rpm. Corrosion rates were determined by the amount of weight
loss that
occurred in 24 hours. All formulations tested were run in duplicate, so the
corrosion
rates shown represent the average of the two. The level of copper (as Cu2+ in
EP9587
(4.84%) was maintained for each new stock formulation prepared. The percentage
of
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surfactant and water and the source of copper ion were the variables
manipulated. All
blends were prepared based on the weight % of each component. In addition, an
11-
day test using undiluted stock solutions was carried out with the better of
the two
corrosion blends.
Experimental Results
Copper Based Combustion Enhancer (CBCE)=19% copper sulfate pentahydrate
(which is 4.84% Cu2+, the level found in every stock solution tested below)/
1.6%
alkylpolyglucoside surfactant (TritonTm BG-1 0).
Corrosion Inhibitor Blend (CIB)=2-aminoethanol, triethanolamine, and boric
acid
(MaxhibTm AB-400) ¨ available from Chemax, Rutgers Organics Corporation,
Greenville, SC 29606.
Data Table 1 below shows the above listed as CBCE and CIB with the appropriate
concentrations used.
TABLE 1
Example Composition of Stock Solution Corrosion % Reduction of
Tested (by % weight) Rate (mpy) on Corrosion Rate
Low Carbon (relative to
Steel CBCE)
Control CBCE (4.84% Cu) [CONTROL] 935 NA
C-1 Similar to CBCE but with the 25 97
4.84% Cu coming from
Copper(II)-D-Gluconate instead
of CUS04.5H20
C-2 CBCE with an added 1 % Sodium 959 0
Gluconate
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C-3 CBCE with an added 6.7% 974 0
Sodium Gluconate
C-4 CBCE with an added 9% Sodium 1000 0
Gluconate
C-5 Similar to the CBCE but with 1% 968 0
of the Cu coming form
Copper(II)-D-Gluconate & the
other 3.84% Cu coming from
CuSO4=5H20
C-6 CBCE but with the pH raised 1 964 0
unit with NH4OH
C-7 Similar to the CBCE but with 1% 955 0
of the Cu coming from
Copper(II)-D-Gluconate & the
other 3.84% Cu coming from
CuSO4.5H20. In addition 0.1%
Zinc was added.
C-8 Similar to the CBCE but with 1% 466 50
of the Cu coming from Copper
(II)-D-Gluconate & the other
3.84% Cu coming from
CuSO4.5H20. In addition, pH
was raised one-half unit with
NH4OH.
C-9 Similar to the CBCE but with 1% 175 81
of the Cu coming from
(Product was not
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Copper(II)-D-Gluconate & the stable.)
other 3.84% Cu coming from
CuSO4.5H20. In addition, pH
was raised one unit with KOH.
C-10 Similar to the CBCE but with 1% 212 77
of the Cu coming from
(Product was not
Copper(II)-D-Gluconate & the
stable.)
other 3.84% Cu coming from
CuSO4.5H20. In addition, pH
was raised one unit with NaOH.
C-11 Similar to the CBCE but with 1% 174 81
of the Cu coming from
(Product was not
Copper(II)-D-Gluconate & the
stable.)
other 3.34% Cu coming from
CuSO4.5H20. In addition, pH
was raised one unit with NaOH.
C-12 Similar to the CBCE but with 1% 147 84
of the Cu coming from
= (Product was not
Copper(II)-D-Gluconate & the
stable.)
other 3.84% Cu coming from
CuSO4.5H20. In addition, pH
was raised one unit with NH4OH.
C-13 Similar to the CBCE but with 900 4
= 1.35% alkylpolyglucoside
surfactant (Triton BG-10) instead
of 1.6%, and 0.25% alkoxylated
mercaptan (Burco TME added as
= well.
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C-14 Similar to the CBCE but with 957 0
1.35% alkylpolyglucoside
surfactant (Triton BG-10)
instead of 1.6%, and 1.5%
alkoxylated mercaptan (Burco
TME added as well.
C-15 Similar to the CBCE but with 838 10
1.6% alkylpolyglucoside
surfactant (Triton BG-10)
replaced by 1.6% alkoxylated
amine.
C-16 Similar to the CBCE but with 787 16
1.6% alkylpolyglucoside
surfactant (Triton BG-10)
replaced by 1.6% alkoxylated
amine.
C-17 Similar to the CBCE but with 808 14
1.6% alkylpolyglucoside
surfactant (Triton BG-10)
replaced by 1.6% proprietary
surfactant blend with propargyl
alcohol (Maxhib PA 315).
C-18 Similar to the CBCE but with 852 9
1.6% alkylpolyglucoside
surfactant (Triton B G-10)
replaced by 1.6% of a
quaternary aryl ammonium
chloride (DodicorTm 2565).
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C-19 Similar to the CBCE but the 1.6% 998 0
alkylpolyglucoside surfactant
(Triton BG-10) was not added.
Instead, 1% boric acid & 1%
EDTA were added.
C-20 Similar to the CBCE but the 1.6% 913 2
alkylpolyglucoside surfactant
(Triton BG-10) was not added.
Instead 5% proprietary surfactant
blend with propargyl alcohol
(Maxhib PA 315) was added.
C-21 Similar to the CBCE but the 1.6% 543 42
alkylpolyglucoside surfactant
(Triton BG-10) was not added.
Instead, 5% quaternary aryl
ammonium chloride (Dodicor
2565 was added.
C-22 Similar to the CBCE but the 1.6% 576 38
alkylpolyglucoside surfactant
(Triton BG-10) was not added.
Instead, 10% quaternary aryl
ammonium chloride (Dodicor
2565) was added.
= C-23 Similar to the CBCE but
the 1.6% 875 6
alkylpolyglucoside surfactant
(Triton BG-10) was replaced by
1.6% of a quaternary aryl
ammonium chloride (Dodicor
2565). In addition, pH was raised
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one unit w/NH4OH.
C-24 Similar to the CBCE but with the 832 11
1.6% alkylpolyglucoside
surfactant (Triton B G-10)
replaced by 1.6% of a quaternary
aryl ammonium chloride
(Dodicor 2565). In addition, 1%
of the Cu was from Copper(II)-D-
Gluconate & the other 3.84%
came from CuSO4.5H20. The
pH was raised one unit w/NH4OH
as well.
C-25 Similar to the CBCE but with the 692 26
1.6% alkylpolyglucoside
surfactant (Triton B G-10)
replaced by 1.6% of a proprietary
surfactant blend with propargyl
alcohol (Maxhib PA 315). In
addition, 1% of the Cu was from
Copper(II)-D-Gluconate & the
other 3.84% came from
CuSO4.5H20. The pH was
raised one unit with NaOH as
well.
Example Similar to the CBCE but with the 222 76
1 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 2.27% CIB
(Maxhib AB 400) & 6.7% sodium
gluconate were added to the
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4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 213 77
2 1.6% alkylpolyglucoside
surfactant (Triton I3G-10) not
added. Instead, 2.3% CIB
(Maxhib AB 400) & 5.4% sodium
gluconate were added to the
4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 223 76
3 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 2.8% CIB
(Maxhib AB 400) & 4.3% sodium
gluconate were added to the
4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 230 75
4 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 3.0% CIB,
(Maxhib AB 400) & 4.0% sodium
gluconate were added to the
4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 181 81
1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
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added. Instead, 3.0% CIB
(Maxhib AB 400) & 5.0% sodium
gluconate were added to the
4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 541 42
6 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 3.5% CIB
(Maxhib AB 400) & 4.2% sodium
gluconate were added to the
4.84% Cu (from 19% copper
sulfate pentahydrate).
Example Similar to the CBCE but with the 200 79
7 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 2% CIB (Maxhib
AB 400) was added. In addition,
1% Cu came from Copper(II)-D-
Gluconate & 3.84% Cu came
from copper sulfate pentahydrate
to make up the 4.84% total Cu
amount.
=
Example Similar to the CBCE but with the 146 84
8 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 2.5% CIB
(Maxhib AB 400) was added. In
addition, 1% Cu came from
Copper(II)-D-Gluconate & 3.84%
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Cu came from copper sulfate
pentahydrate to make up the
4.84% total Cu amount.
C-27 Similar to the CBCE but with 820 12
the 1.6% alkylpolyglucoside
surfactant (Triton B G-10)
replaced by 1.6% modified
complex amine (DetergeTM AT-
100). In addition, 1 % Cu came
from Copper(II)-D-Gluconate &
3.84% Cu came from copper
sulfate pentahydrate to make up
the 4.84% total Cu amount.
C-28 Similar to the CBCE but with 775 17
the 1.6% alkylpolyglucoside
surfactant (Triton BG-10) not
added. Instead, 3% modified
complex amine (Deterge AT-
100) was added. In addition,
1% Cu came from Copper(II)-
D-Gluconate & 3.84% Cu came
from copper sulfate
pentahydrate. The pH was
raised one unit with NaOH as
well.
11-Day Bottle Test Using Undiluted Stock Solutions
Example 9 Undiluted CBCE tested for 11 days 4961 NA
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(Control for 11-day test)
Undiluted Blend Tested for 11 Days vs. 781 84
CBCE. In this case, the CBCE prepared
did not have the 1.6% alkylpolyglucoside
surfactant (Triton BG-10). Instead, 3.0%
CIB(Maxhib AB 400) & 4.0% sodium
gluconate were added to the 4.84% Cu
(from 19% copper sulfate pentahydrate).
EXAMPLE 2
The procedures reported in Example 1 were again performed in conjunction with
comparative treatments and treatments in accordance with the invention.
Results are
shown in Table 2.
Example Composition of Stock Corrosion Rate % Reduction of
Solution Tested (by wt%) (mpy) on Low Corrosion Rate
Carbon Steel (relative to
EP9587)
Control EP9587 [CONTROL] 935 NA
C-29 EP9587 W/4.84% Cu from 25 97
Copper(II)-D-Gluconate
(Increase in raw
instead of CuSO4=5H20
material cost
higher than 20%.)
C-30 EP9587 1% Sodium 959 0
Gluconate.
C-31 EP9587 6.7% Sodium 974 0
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Gluconate.
C-32 EP9587 9% Sodium 1000 0
Gluconate.
C-33 EP9587 1% Cu from 968 0
Copper(II)-D-Gluconate &
3.84% Cu from
CuS0405H20.
C-34 EP9587 & pH raised 1 unit 964 0
w/ NRIOH.
C-35 EP9587 w/ 1% Cu from 955 0
Copper(II)-D-Gluconate &
3.84% from CuSO4=5H20 w/
0.1% zinc.
C-36 EP9587 w/ 1% Cu from 466 50
Copper(II)-D-Gluconate &
3.84% from CuSO4=5H20 &
pH raised one half unit w/
NH4OH.
C-37 EP9587 w/ 1% Cu from 175 81
Copper(II)-D-Gluconate &
3.84% from CuSO4=5H20 & (Product was not
stable.)
pH raised one unit w/ KOH.
= C-38 EP9587 w/ 1% Cu from 212 77
Copper(II)-D-Gluconate &
3.84% from CuSO4=5H20 & (Product was not
stable.)
pH raised one unit with
NAOH.
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C-39 EP9587 w/ 1.5% Cu from 174 81
Copper(I1)-D-Gluconate &
(Product was not
3.34% from CuSO4=5H20 w/
stable.)
pH raised one unit with
NaOH.
C-40 EP9587 w/ 1% Cu from 147 84
Copper(I1)-D-Gluconate &
(Product was not
3.84% from CuSO4=5H20 &
stable.)
pH raised one unit
w/NH4OH.
C-41 EP9587 w/ 1.35% Triton 900 4
BG-10 & 0.25% Burko
TME.
C-42 EP9587 w/ 0.1% Triton BG- 957 0
& 1.5% Burko TME
C-43 EP9587 w/ Triton BG-10 838 10
replaced by alkoxylated
amine.
C-44 EP9587 w/ Triton BG-10 787 16
replaced by alkoxylated
amine.
C-45 EP9587 w/ Triton BG-10 808 14
replaced by Maxhib PA 315.
C-46 EP9587 w/ Triton BG-10 852 9
replaced by Dodicor 2565.
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C-47 EP9587 w/ Triton BG-10 998 0
replaced by 1% Boric Acid
& EDTA.
C-48 EP9587 w/ Triton BG-10 913 2
replaced by Maxhib PA 315.
C-49 EP9587 w/ Triton BG-10 543 42
replaced by 5% Dodicor
2565.
C-50 EP9587 w/ Triton BG-10 576 38
replaced by 10% Dodicor
2565.
C-51 EP9587 w/ Triton BG-10 875 6
replaced by Dodicor 2565 &
pH raised one unit w/
NRIOH.
C-52 Triton BG-10 replaced by 832 11
Dodicor 2565 & 1% Cu from
Copper(II)-D-Gluconate &
3.84% from CuSO4=5H20
and pH raised one unit w/
NaOH.
Example Triton BG-10 replaced by 692 26
Maxhib PA 315 & 1% Cu
from Copper(II)-D-
Gluconate & 3.84% from
CuSO4=5H20 and pH raised
one unit w/ NaOH.
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Example Triton BG-10 replaced by 222 76
11 2.27% Maxhib AB 400 &
6.7% sodium gluconate and
19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 213 77
12 2.3% Maxhib AB 400 &
5.4% sodium gluconate and
19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 223 76
13 2.8% Maxhib AB 400 &
4.3% sodium gluconate and
19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 23 75
14 3.0% Maxhib AB 400 &
4.0% sodium gluconate and
19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 181 81
15 3.0% Maxhib AB 400 &
5.0% sodium gluconate and
19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 541 42
16 3.5% Maxhib AB 400 &
4.2% sodium gluconate and
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19% copper sulfate
pentahydrate.
Example Triton BG-10 replaced by 200 79
17 2% Maxhib AB 400 & 1%
Cu from Copper(II)-D-
Gluconate & 3.84% from
copper sulfate pentahydrate.
Example Triton BG-10 replaced by 146 84
18 2.5% Maxhib AB 400 & 1%
Cu from Copper(II)-D-
Gluconate & 3.84% from
copper sulfate pentahydrate.
C-53 Triton BG-10 replaced by 820 12
Deterge AT-100 & 1% Cu
from Copper(II)-D-
Gluconate & 3.84% from
copper sulfate pentahydrate.
C-54 Triton BG-10 replaced by 775 17
3% Deterge AT-100 & 1%
Cu from Copper(II)-D-
Gluconate & 3.84% from
copper sulfate pentahydrate
& pH raised one unit with
NaOH.
C-55 Undiluted EP9587 tested for 4961 NA
11 days (Control for 11-day
test).
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Example Undiluted Blend Tested for 781 84
19 11 days vs. EP9587: Triton
BG-10 replaced by 3.0%
Maxhib AB400 & 4.0%
sodium gluconate and 19%
copper sulfate pentahydrate.
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