CA2516491A1 - A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion - Google Patents
A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion Download PDFInfo
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- CA2516491A1 CA2516491A1 CA002516491A CA2516491A CA2516491A1 CA 2516491 A1 CA2516491 A1 CA 2516491A1 CA 002516491 A CA002516491 A CA 002516491A CA 2516491 A CA2516491 A CA 2516491A CA 2516491 A1 CA2516491 A1 CA 2516491A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L5/00—Solid fuels
- C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
- C10L5/34—Other details of the shaped fuels, e.g. briquettes
- C10L5/36—Shape
- C10L5/366—Powders
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/001—Injecting additional fuel or reducing agents
- C21B5/003—Injection of pulverulent coal
- C21B5/004—Injection of slurries
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- Liquid Carbonaceous Fuels (AREA)
Abstract
Methods and compositions for inhibiting corrosion of metal surfaces in a furnace system are disclosed. In one aspect of the invention, pulverized coal is burned as fuel in the presence of a copper ion catalyst/combustion aid.
Corrosion is inhibited in these systems by the use of a blend of primary aminoalcohol such as 2-aminoethanol, tertiary aminoalcohol such as triethanol amine, and boric acid or water soluble salt form of the acid.
Corrosion is inhibited in these systems by the use of a blend of primary aminoalcohol such as 2-aminoethanol, tertiary aminoalcohol such as triethanol amine, and boric acid or water soluble salt form of the acid.
Description
A NON-CORROSIVE TREATMENT TO ENHANCE PRESSURIZED AND NON-PRESSURIZED PULVERIZED COAL COMBUSTION
FIELD OF THE INVENTION
The invention pertains to methods and compositions fox 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, lVlo, 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, lmown as tuyeres, at the bottom of the furnace. . Tuyere stocks are fitted with injection lances through which 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 LOI. 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.
FIELD OF THE INVENTION
The invention pertains to methods and compositions fox 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, lVlo, 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, lmown as tuyeres, at the bottom of the furnace. . Tuyere stocks are fitted with injection lances through which 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 LOI. 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.
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 4,45,006 and 4,224,1i~0 herein incorporated by reference.) 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 ml -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/coriibustion aid, a copper ion source may also be incorporated into the aqueous solution that is to be sprayed over the coal.
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 4,45,006 and 4,224,1i~0 herein incorporated by reference.) 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 ml -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/coriibustion aid, a copper ion source may also be incorporated into the aqueous solution that is to be sprayed over the coal.
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 components) 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.
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 components) 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.
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.
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 stoclc 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 Cuz+ in (4.84%) was maintained for each new stock formulation prepared. The percentage of 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 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 iri every stock solution tested below)/
1.6%
alkylpolyglucoside surfactant (Triton BG-10).
Corrosion Inhibitor Blend (CIB)=2-aminoethanol, triethanolamine, and boric acid (Maxhib 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.
Example Composition of Stock Corrosion % Reduction Solution of Tested (by % weight) Rate (mpy) Corrosion Rate on Low Carbon (relative to Steel CBCE) Control CBCE (4.84% Cu) [CONTROL]935 - NA
C-1 Similar to CBCE but with25 97 the 4.84% Cu coming from ~Copper(II)-D-Gluconate instead of CuS045H20 C-2 CBCE with an added 1 959 0 % Sodium Gluconate C-3 CBCE with an added 6.7% 974 0 Sodium Gluconate C-4 CBCE with an added 9% 1000 0 Sodium Gluconate C-5 . Similar to the CBCE but 968 0 with 1 %
of the Cu coming form .
Copper(II)-D-Gluconate & the other 3.84% Cu coming from CuS04 5H20 C-6 CBCE but with the pH 964 0 raised .1 unit with NH40H
C-7- Similar to the CBCE but 955 0 with 1 %
of the Cu coming from Copper(II)-D-Gluconate & the other 3.84% Cu coming from CuS045I-I20. In addition 0.1%
Zinc was added.
C-8 Similar to the CBCE but 466 50 with 1%
of the Cu coming from Copper (II)-D-Gluconate & the . other 3.84% Cu coming from CuS045Hz0. In addition, pH
was raised one-half unit with NH40H.
C-9 Similar to the CBCE but 175 81 with 1 %
of the Cu coming from (Product was not Copper(II)-D-Gluconate stable.) & the other 3.84% Cu coming from CuS045H20. In addition, pH
was raised one unit with KOH.
C-10 Similar to the CBCE but 212 77 with 1%
of the Cu coming from (Product was not Copper(II)-D-Gluconate & the stable.) other 3.84% Cu coming from CuSO45H20. In addition, pH
was raised one unit with NaOH.
C-11 Similar to the CBCE but 174 81 with 1 %
of the Cu coming from Copper(II)-D-Gluconate (Product was & the not stable.) other 3.34% Cu coming from CuS045H20. In addition, pH
was raised one unit with NaOH.
C-12 Similar to the CBCE but 147 84 with 1%
of the Cu coming from (Product was not Copper(II)-D-Gluconate & the stable.) other 3.84% Cu coming from CuSO45H20. In addition, pH
was raised one unit with NH40H.
C-13 Similar to the CBCE but 900 4 with 1.35% allcylpolyglucoside surfactant (Triton BG-10) instead of 1.6%, and 0.25% alkoxylated mercaptan (Burco THE
added as well.
C-14 Similar to the CBCE but 957 0 with 1.35% alkylpolyglucoside surfactant (Triton BG-10) instead of 1.6%, and 1.5% alkoxylated mercaptan (Burco THE added as well.
C-15 Similar to the CBCE but 838 10 with 1.6% alkylpolyglucoside surfactant (Triton BG-10) replaced by 1.6% alkoxylated amine.
C-16 Similar to the CBCE but 787 16 with 1.6% alkylpolyglucoside surfactant (Triton BG-10) replaced by 1..6% alkoxylated amine.
C-17 Similar to the CBCE but 808 14 with 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 852 9 with 1.6% allcylpolyglucoside surfactant (Triton BG-10) replaced by 1.6% of a quaternary aryl ammonium chloride (Dodicor 2565).
C-19 Similar to the CBCE but 998 0 the 1.6%
alkylpolyglucoside surfactant (Triton BG-10) was not added.
Instead, 1 % boric acid & 1 EDTA were added.
C-20 Similar to the CBCE but 913 2 the 1.6%
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 543 42 the 1.6%
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 576 38 the 1.6%
alkylpolyglucoside surfactant (Tritoil BG-10) was not added.
Instead, 10% quaternary aryl ammonium chloride (Dodicor 2565) was added.
C-23 Similar to the CBCE but 875 6 the 1.6%
alkylpolyglucoside surfactant (Triton BG-10) was replaced by 1.6% of a quaternary aryl ammonium chloride (Dodicor 2565). In addition, pH
was raised one unit w/NH40H.
C-24 Similar to the CBCE but 832 11 with the 1.6% alkylpolyglucoside surfactant (Triton BG-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 CuS04SH20.
The pH was raised one unit w/NH40H
as well.
C-25 Similar to the CBCE but 692 26 with the 1.6% alkylpolyglucoside surfactant (Triton BG-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 CuS04SH20. The pH was raised one unit with NaOH as well.
Example Similar to the CBCE but 222 76 with the 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 4.84% Cu (from 19% copper sulfate pentahydrate).
Example Similar to the CBCE but 213 77 with the 2 1.6% allcylpolyglucoside surfactant (Triton .BG-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 223 76 with the 3 1.6% allcylpolyglucoside 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 230 75 with the 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 181 81 with the 1.6% alkylpolyglucoside surfactant (Triton BG-10) not 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 541 42 with the 6 1.6% allcylpolyglucoside 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 200 79 with the 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 1'46 84 with the 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%
Cu came from copper sulfate pentahydrate to make up the 4.84% total Cu amount.
C-27 Similar to the CBCE but 820 12 with the 1.6% . allcylpolyglucoside surfactant' (Triton BG-10) replaced by 1.6% modified complex amine (Deterge 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 775 17 with the 1.6% allcylpolyglucoside 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
(Control for 11-day test) Undiluted Blend Tested for 781 84 11 ' Days vs.
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 o the 4.84% Cu (from 19% copper sulfate pentahydrate).
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 % Reduction Rate of Solution Tested (by (mpy) on Low Corrosion Rate wt%) Carbon Steel (relative to EP9587) Control EP9587 [CONTROL] . 935 NA
C-29 EP9587 W/4.84% Cu 25 97 from Copper(II)-D-Gluconate instead of CuS0 5H (Increase in 0 raw material cost higher than 20%.) C-30 EP9587 1% Sodium 959 0 Gluconate.
C-31 EP9587 6.7% Sodium 974 0 is 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 CuS045H20.
C-34 EP9587 & pH raised 964 0 1 unit w/ NH40H.
C-35 EP9587 w/ 1% Cu .from955 0 Copper(II)-D-Gluconate &
3.84% from CuS045H20 w/
0.1 % zinc.
C-36 EP9587 w/ 1% Cu from 466 50 Copper(II)-D-Gluconate &
3.84% from CuS045H20 &
pH raised one half unit w/
NH40H.
C-37 EP9587 w/ 1% Cu from 175 81 Copper(II)-D-Gluconate &
(Product was' not 3.84% from CuS045H2O
&
stable.) pH raised one unit w/ KOH.
C-38 EP9587 w/ 1% Cu from 212 77 Copper(II)-D-Gluconate &
84% from CuS0 (Product was 5H not 0 &
.
a stable.) pH raised one unit with NAOH.
C-39 EP9587 w/ 1.5% Cu from174 81 Copper(II)-D-Gluconate &
34% from CuS0 (Product was 0 w1 not SH
.
stable.) pH raised one unit with NaOH.
C-40 EP9587 w/ 1 % Cu from 147 84 Copper(II)-D-Gluconate ~
3.84% from CuS045H
0 & (Product was not stable.) pH raised one unit w/NH4OH.
C-41 EP9587 wl 1.35% Triton900 ' 4 BG-10 & 0.25% Burlco TME.
C-42 EP9587 wf 0.1 % Triton95? 0 BG-10 & I.5% Burko THE
C-43 EP958,7 w/ Triton BG-10838 10 replaced by alkoxylated amine.
C-44 EP9587 w/ Triton BG-10787 I6 replaced by allcoxylated amine.
C-45 EP9587 w/ Triton BG-10808 14 replaced by Maxhib PA 315.
C-46 EP9587 wl Triton BG-10852 9 replaced by Dodicor 2565.
t7 C-47 EP9587 wl Triton BG-10998 0 replaced by 1% Boric Acid & EDTA.
C-48 EP9587 w/ Triton BG-10913 2 replaced by Maxhib PA 315.
C-49 EP9587 w/ Triton BG-10543 42 replaced by 5% Dodicor 2565.
C-50 EP9587 w/ Triton BG-10576 38 replaced by 10% Dodicor 2565.
C-51 EP9587 w/ Triton BG-10875 6 replaced by Dodicor 2565 &
pH raised one unit w/
NH40H.
C-52 Triton BG-10 replaced832 11 by Dodicor 2565 ~ 1 %
.Cu from Copper(II)-D-Gluconate &
3.84% from CuS045H2O
and pH raised one -unit w/
NaOH.
Example Triton BG-10 replaced692 26 by Maxhib PA 315 & 1 % Cu from Copper(II)-D-Gluconate & 3.84%
from CuSO4SH20 and pH raised one unit w/ NaOH.
Example Triton BG-10 replaced222 76 by 11 2.27% Maxhib AB 400 &
6.7% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced213 77 by 12 2.3% Maxhib AB . 400 , &
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.
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 stoclc 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 Cuz+ in (4.84%) was maintained for each new stock formulation prepared. The percentage of 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 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 iri every stock solution tested below)/
1.6%
alkylpolyglucoside surfactant (Triton BG-10).
Corrosion Inhibitor Blend (CIB)=2-aminoethanol, triethanolamine, and boric acid (Maxhib 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.
Example Composition of Stock Corrosion % Reduction Solution of Tested (by % weight) Rate (mpy) Corrosion Rate on Low Carbon (relative to Steel CBCE) Control CBCE (4.84% Cu) [CONTROL]935 - NA
C-1 Similar to CBCE but with25 97 the 4.84% Cu coming from ~Copper(II)-D-Gluconate instead of CuS045H20 C-2 CBCE with an added 1 959 0 % Sodium Gluconate C-3 CBCE with an added 6.7% 974 0 Sodium Gluconate C-4 CBCE with an added 9% 1000 0 Sodium Gluconate C-5 . Similar to the CBCE but 968 0 with 1 %
of the Cu coming form .
Copper(II)-D-Gluconate & the other 3.84% Cu coming from CuS04 5H20 C-6 CBCE but with the pH 964 0 raised .1 unit with NH40H
C-7- Similar to the CBCE but 955 0 with 1 %
of the Cu coming from Copper(II)-D-Gluconate & the other 3.84% Cu coming from CuS045I-I20. In addition 0.1%
Zinc was added.
C-8 Similar to the CBCE but 466 50 with 1%
of the Cu coming from Copper (II)-D-Gluconate & the . other 3.84% Cu coming from CuS045Hz0. In addition, pH
was raised one-half unit with NH40H.
C-9 Similar to the CBCE but 175 81 with 1 %
of the Cu coming from (Product was not Copper(II)-D-Gluconate stable.) & the other 3.84% Cu coming from CuS045H20. In addition, pH
was raised one unit with KOH.
C-10 Similar to the CBCE but 212 77 with 1%
of the Cu coming from (Product was not Copper(II)-D-Gluconate & the stable.) other 3.84% Cu coming from CuSO45H20. In addition, pH
was raised one unit with NaOH.
C-11 Similar to the CBCE but 174 81 with 1 %
of the Cu coming from Copper(II)-D-Gluconate (Product was & the not stable.) other 3.34% Cu coming from CuS045H20. In addition, pH
was raised one unit with NaOH.
C-12 Similar to the CBCE but 147 84 with 1%
of the Cu coming from (Product was not Copper(II)-D-Gluconate & the stable.) other 3.84% Cu coming from CuSO45H20. In addition, pH
was raised one unit with NH40H.
C-13 Similar to the CBCE but 900 4 with 1.35% allcylpolyglucoside surfactant (Triton BG-10) instead of 1.6%, and 0.25% alkoxylated mercaptan (Burco THE
added as well.
C-14 Similar to the CBCE but 957 0 with 1.35% alkylpolyglucoside surfactant (Triton BG-10) instead of 1.6%, and 1.5% alkoxylated mercaptan (Burco THE added as well.
C-15 Similar to the CBCE but 838 10 with 1.6% alkylpolyglucoside surfactant (Triton BG-10) replaced by 1.6% alkoxylated amine.
C-16 Similar to the CBCE but 787 16 with 1.6% alkylpolyglucoside surfactant (Triton BG-10) replaced by 1..6% alkoxylated amine.
C-17 Similar to the CBCE but 808 14 with 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 852 9 with 1.6% allcylpolyglucoside surfactant (Triton BG-10) replaced by 1.6% of a quaternary aryl ammonium chloride (Dodicor 2565).
C-19 Similar to the CBCE but 998 0 the 1.6%
alkylpolyglucoside surfactant (Triton BG-10) was not added.
Instead, 1 % boric acid & 1 EDTA were added.
C-20 Similar to the CBCE but 913 2 the 1.6%
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 543 42 the 1.6%
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 576 38 the 1.6%
alkylpolyglucoside surfactant (Tritoil BG-10) was not added.
Instead, 10% quaternary aryl ammonium chloride (Dodicor 2565) was added.
C-23 Similar to the CBCE but 875 6 the 1.6%
alkylpolyglucoside surfactant (Triton BG-10) was replaced by 1.6% of a quaternary aryl ammonium chloride (Dodicor 2565). In addition, pH
was raised one unit w/NH40H.
C-24 Similar to the CBCE but 832 11 with the 1.6% alkylpolyglucoside surfactant (Triton BG-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 CuS04SH20.
The pH was raised one unit w/NH40H
as well.
C-25 Similar to the CBCE but 692 26 with the 1.6% alkylpolyglucoside surfactant (Triton BG-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 CuS04SH20. The pH was raised one unit with NaOH as well.
Example Similar to the CBCE but 222 76 with the 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 4.84% Cu (from 19% copper sulfate pentahydrate).
Example Similar to the CBCE but 213 77 with the 2 1.6% allcylpolyglucoside surfactant (Triton .BG-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 223 76 with the 3 1.6% allcylpolyglucoside 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 230 75 with the 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 181 81 with the 1.6% alkylpolyglucoside surfactant (Triton BG-10) not 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 541 42 with the 6 1.6% allcylpolyglucoside 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 200 79 with the 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 1'46 84 with the 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%
Cu came from copper sulfate pentahydrate to make up the 4.84% total Cu amount.
C-27 Similar to the CBCE but 820 12 with the 1.6% . allcylpolyglucoside surfactant' (Triton BG-10) replaced by 1.6% modified complex amine (Deterge 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 775 17 with the 1.6% allcylpolyglucoside 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
(Control for 11-day test) Undiluted Blend Tested for 781 84 11 ' Days vs.
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 o the 4.84% Cu (from 19% copper sulfate pentahydrate).
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 % Reduction Rate of Solution Tested (by (mpy) on Low Corrosion Rate wt%) Carbon Steel (relative to EP9587) Control EP9587 [CONTROL] . 935 NA
C-29 EP9587 W/4.84% Cu 25 97 from Copper(II)-D-Gluconate instead of CuS0 5H (Increase in 0 raw material cost higher than 20%.) C-30 EP9587 1% Sodium 959 0 Gluconate.
C-31 EP9587 6.7% Sodium 974 0 is 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 CuS045H20.
C-34 EP9587 & pH raised 964 0 1 unit w/ NH40H.
C-35 EP9587 w/ 1% Cu .from955 0 Copper(II)-D-Gluconate &
3.84% from CuS045H20 w/
0.1 % zinc.
C-36 EP9587 w/ 1% Cu from 466 50 Copper(II)-D-Gluconate &
3.84% from CuS045H20 &
pH raised one half unit w/
NH40H.
C-37 EP9587 w/ 1% Cu from 175 81 Copper(II)-D-Gluconate &
(Product was' not 3.84% from CuS045H2O
&
stable.) pH raised one unit w/ KOH.
C-38 EP9587 w/ 1% Cu from 212 77 Copper(II)-D-Gluconate &
84% from CuS0 (Product was 5H not 0 &
.
a stable.) pH raised one unit with NAOH.
C-39 EP9587 w/ 1.5% Cu from174 81 Copper(II)-D-Gluconate &
34% from CuS0 (Product was 0 w1 not SH
.
stable.) pH raised one unit with NaOH.
C-40 EP9587 w/ 1 % Cu from 147 84 Copper(II)-D-Gluconate ~
3.84% from CuS045H
0 & (Product was not stable.) pH raised one unit w/NH4OH.
C-41 EP9587 wl 1.35% Triton900 ' 4 BG-10 & 0.25% Burlco TME.
C-42 EP9587 wf 0.1 % Triton95? 0 BG-10 & I.5% Burko THE
C-43 EP958,7 w/ Triton BG-10838 10 replaced by alkoxylated amine.
C-44 EP9587 w/ Triton BG-10787 I6 replaced by allcoxylated amine.
C-45 EP9587 w/ Triton BG-10808 14 replaced by Maxhib PA 315.
C-46 EP9587 wl Triton BG-10852 9 replaced by Dodicor 2565.
t7 C-47 EP9587 wl Triton BG-10998 0 replaced by 1% Boric Acid & EDTA.
C-48 EP9587 w/ Triton BG-10913 2 replaced by Maxhib PA 315.
C-49 EP9587 w/ Triton BG-10543 42 replaced by 5% Dodicor 2565.
C-50 EP9587 w/ Triton BG-10576 38 replaced by 10% Dodicor 2565.
C-51 EP9587 w/ Triton BG-10875 6 replaced by Dodicor 2565 &
pH raised one unit w/
NH40H.
C-52 Triton BG-10 replaced832 11 by Dodicor 2565 ~ 1 %
.Cu from Copper(II)-D-Gluconate &
3.84% from CuS045H2O
and pH raised one -unit w/
NaOH.
Example Triton BG-10 replaced692 26 by Maxhib PA 315 & 1 % Cu from Copper(II)-D-Gluconate & 3.84%
from CuSO4SH20 and pH raised one unit w/ NaOH.
Example Triton BG-10 replaced222 76 by 11 2.27% Maxhib AB 400 &
6.7% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced213 77 by 12 2.3% Maxhib AB . 400 , &
5.4% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced223 ~ 76 by 13 2:8% Maxhib AB 400 &
4.3% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced23 75 by 14 3.0% Maxhib AB 400' &.
4.0% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced181 81 by 15 3.0% Maxhib AB 400 &
5.0% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced541 42 by 16 3.5% Maxhib AB 400 &
4.2% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 .replaced200 79 by 17 2% Maxhib AB 400 &
1%
Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
Example Triton BG-10 replaced146 84 by 18 2.5 % Maxhib AB 400 & ' 1 Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
C-53 Triton BG-10 replaced820 12 by Deterge AT-100 & 1%
Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
C-54 Triton BG-10 replaced775 17 by 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 tested4961 NA
for 11 days (Control for 11-day test).
Example Undiluted Blend Tested781 84 for 19 11 days vs. EP9587:
Triton BG-10 replaced by 3.0%
Maxhib AB400 & 4.0%
sodium gluconate and 19%
copper sulfate pentahydrate.
Example Triton BG-10 replaced223 ~ 76 by 13 2:8% Maxhib AB 400 &
4.3% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced23 75 by 14 3.0% Maxhib AB 400' &.
4.0% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced181 81 by 15 3.0% Maxhib AB 400 &
5.0% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 replaced541 42 by 16 3.5% Maxhib AB 400 &
4.2% sodium gluconate and 19% copper sulfate pentahydrate.
Example Triton BG-10 .replaced200 79 by 17 2% Maxhib AB 400 &
1%
Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
Example Triton BG-10 replaced146 84 by 18 2.5 % Maxhib AB 400 & ' 1 Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
C-53 Triton BG-10 replaced820 12 by Deterge AT-100 & 1%
Cu from Copper(II)-D-Gluconate & 3.84%
from copper sulfate pentahydrate.
C-54 Triton BG-10 replaced775 17 by 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 tested4961 NA
for 11 days (Control for 11-day test).
Example Undiluted Blend Tested781 84 for 19 11 days vs. EP9587:
Triton BG-10 replaced by 3.0%
Maxhib AB400 & 4.0%
sodium gluconate and 19%
copper sulfate pentahydrate.
Claims (24)
1. A method of inhibiting corrosion of metal surfaces in a furnace wherein coal is burned as a fuel, said method comprising burning said coal in the presence of a corrosion inhibiting treatment comprising an aminoalcohol.
2. A method as recited in claim 1 wherein said corrosion inhibiting treatment further comprises boric acid or water soluble salt of aid boric acid.
3. A method as recited in claim 2 wherein said coal is pulverized and said treatment is applied in the form of an aqueous solution over said pulverized coal.
4. A method as recited in claim 2 wherein said treatment is sprayed in aqueous solution form into said furnace.
5. A method as recited in claim 2 wherein said aminoalcohol comprises a primary aminoalcohol having a primary amine functionality.
6. A method as recited in claim 5 wherein said aminoalcohol further comprises a tertiary aminoalcohol having tertiary amine functionality.
7. A method as recited in claim 5 wherein said aminoalcohol further comprises 2-aminoethanol.
8. A method as recited in claim 6 wherein said tertiary aminoalcohol is triethanolamine.
9. A method as recited in claim 8 wherein said coal is burned in the, presence of copper.
10. A method as recited in claim 3 wherein said aqueous solution is sprayed over said pulverized coal in an amount of about 100 ml-1L of said aqueous solution per ton of said pulverized coal.
11. A method as recited in claim 10 wherein said aqueous solution is sprayed over said pulverized coal in an amount of about 300 ml - 1L per ton of said pulverized coal.
12. A method as recited in claim 8 wherein said 2-aminoethanol, triethanolamine, and boric acid or salt thereof are present in combination in aqueous solution in an amount of about 1-10 wt%.
13. A method as recited in claim 12 further including sodium gluconate in said aqueous solution, said sodium gluconate being present in said aqueous solution in an amount of between about 1-10 wt%.
14. In a method in which pulverized coal is burned as a fuel in a furnace in the present of copper to enhance the operation of the furnace, the improvement comprising also burning said coal in the presence of a corrosion. inhibiting treatment, said treatment comprising 2-aminoethanol, triethanolamine and boric acid or water soluble thereof.
15. A method as recited in claim 14 wherein said copper and said corrosion inhibiting treatment are both sprayed onto said coal in the form of a single aqueous solution.
16. A method as recited in claim 14 wherein said corrosion inhibiting treatment further comprises gluconic acid or water soluble salt thereof.
17. A method as recited in claim 16 wherein said corrosion inhibiting treatment comprises sodium gluconate.
18. A method as recited in claim 17 wherein said 2-aminoethanol, triethanolamine and boric acid or salt thereof are present in combination in said aqueous solution in an amount of about 1-about 10 wt%, said sodium gluconate being present in said aqueous solution in an amount of about 1-15 wt% and wherein said copper is present in said aqueous solution as Cu++ in an amount of about 1-20 wt%, and wherein about 100 ml -1L of said aqueous solution is sprayed onto said pulverized coal.
19. Corrosion inhibiting composition comprising an aqueous solution comprising:
(a) 2-aminoethanol;
(b) triethanolamine; and (c) boric acid or water soluble salt form.
(a) 2-aminoethanol;
(b) triethanolamine; and (c) boric acid or water soluble salt form.
20. Corrosion inhibiting composition as recited in claim 19 further comprising (d) sodium gluconate.
21. Corrosion inhibiting composition as recited in claim 20 further comprising (e) a copper ion source.
22. Corrosion inhibiting composition as recited in claim 21 wherein said copper ion source is copper sulfate pentahydrate or copper(II)-D Gluconate.
23. Corrosion inhibiting composition as recited in claim 21 wherein said (a), (b) and (c), in combination, are present in said aqueous solution in an amount of about 1-wt%, said (d) is present in said aqueous solution in an amount of about 1-15 wt%
and wherein said copper ion source (e) is present in an amount sufficient to provide from about 1-20 wt% of Cu++ ion in said aqueous solution.
and wherein said copper ion source (e) is present in an amount sufficient to provide from about 1-20 wt% of Cu++ ion in said aqueous solution.
24
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| US10/368,823 | 2003-02-19 | ||
| US10/368,823 US20040159184A1 (en) | 2003-02-19 | 2003-02-19 | Non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
| PCT/US2004/002051 WO2004074548A1 (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
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| US2836566A (en) * | 1954-01-27 | 1958-05-27 | Detrex Chem Ind | Cleaning composition and method |
| US3406042A (en) * | 1965-12-14 | 1968-10-15 | Cons Edison Co New York Inc | Process for corrosion control |
| US4134729A (en) * | 1976-08-12 | 1979-01-16 | Betz Laboratories, Inc. | Aqueous solution of sodium aluminate and N-aminoethyl ethanolamine as a cold end additive |
| US4101293A (en) * | 1977-03-30 | 1978-07-18 | Reichhold Chemicals, Inc. | Stabilizing emulsifiers |
| US4293342A (en) * | 1978-02-09 | 1981-10-06 | American Can Company | Lignosulfonate derivatives |
| US4208188A (en) * | 1978-03-22 | 1980-06-17 | Signet Corporation | Consolidation of coal slurry |
| US4224180A (en) * | 1979-10-30 | 1980-09-23 | Betz Laboratories, Inc. | Cold end additive compositions |
| US4458606A (en) * | 1982-04-01 | 1984-07-10 | Betz Laboratories, Inc. | Method of conditioning fireside fouling deposits using large particle size amorphous silica |
| US4462830A (en) * | 1983-08-04 | 1984-07-31 | Nalco Chemical Company | Corrosion inhibited copper nitrate solutions |
| US4620672A (en) * | 1985-02-04 | 1986-11-04 | Bechtel International Corporation | Apparatus and method for converting pipeline fine coal slurry to coal water mixture suitable for direct combustion in boilers |
| US4732572A (en) * | 1985-10-03 | 1988-03-22 | Westvaco Corporation | Amine salts of sulfomethylated lignin |
| JPS62241993A (en) * | 1986-04-15 | 1987-10-22 | Mitsui Mining Co Ltd | Coal-methanol slurry and production thereof |
| FR2621175B1 (en) * | 1987-09-29 | 1989-12-01 | Accumulateurs Fixes | ELECTRIC CHEMICAL GENERATOR IMPLEMENTING LITHIUM / OXYHALOGENIDE COUPLES |
| US5391234A (en) * | 1991-08-05 | 1995-02-21 | Henkel Corporation | Cleaning or stripping composition and method |
| JPH07188954A (en) * | 1993-12-28 | 1995-07-25 | Ishizuka Glass Co Ltd | Water-soluble rust inhibitor |
| US6141796A (en) * | 1996-08-01 | 2000-11-07 | Isentropic Systems Ltd. | Use of carbonaceous fuels |
| NZ506262A (en) * | 1998-01-12 | 2003-10-31 | Deborah Wenzel | Composition as an additive to create clear stable solutions and microemulsions with a combustible liquid fuel to improve combustion |
| US6077325A (en) * | 1998-06-09 | 2000-06-20 | Betzdearborn Inc. | Method of adding coal combustion enhancer to blast furnace |
| JP4842420B2 (en) * | 1999-09-28 | 2011-12-21 | トヨタ自動車株式会社 | Cooling liquid, cooling liquid sealing method and cooling system |
| JP3402365B2 (en) | 2000-06-28 | 2003-05-06 | 日本電気株式会社 | Anticorrosive |
| US6670296B2 (en) * | 2001-01-11 | 2003-12-30 | Delphi Technologies, Inc. | Alumina/zeolite lean NOx catalyst |
| US6840318B2 (en) * | 2002-06-20 | 2005-01-11 | Schlumberger Technology Corporation | Method for treating subterranean formation |
-
2003
- 2003-02-19 US US10/368,823 patent/US20040159184A1/en not_active Abandoned
-
2004
- 2004-01-26 EP EP04705247A patent/EP1597413A1/en not_active Withdrawn
- 2004-01-26 BR BRPI0407655-9A patent/BRPI0407655A/en not_active Application Discontinuation
- 2004-01-26 JP JP2006503005A patent/JP4440919B2/en not_active Expired - Fee Related
- 2004-01-26 WO PCT/US2004/002051 patent/WO2004074548A1/en not_active Application Discontinuation
- 2004-01-26 CA CA2516491A patent/CA2516491C/en not_active Expired - Fee Related
- 2004-01-26 AU AU2004213746A patent/AU2004213746B2/en not_active Ceased
- 2004-01-26 KR KR1020057015191A patent/KR101138658B1/en not_active IP Right Cessation
- 2004-01-26 CN CNB2004800079997A patent/CN100351430C/en not_active Expired - Fee Related
-
2006
- 2006-10-17 US US11/581,935 patent/US20070033864A1/en not_active Abandoned
-
2009
- 2009-06-15 US US12/484,654 patent/US20090253085A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP1597413A1 (en) | 2005-11-23 |
| US20040159184A1 (en) | 2004-08-19 |
| BRPI0407655A (en) | 2006-02-21 |
| KR101138658B1 (en) | 2012-04-19 |
| KR20050102123A (en) | 2005-10-25 |
| JP2006518419A (en) | 2006-08-10 |
| AU2004213746A1 (en) | 2004-09-02 |
| CN1764741A (en) | 2006-04-26 |
| US20090253085A1 (en) | 2009-10-08 |
| CA2516491C (en) | 2013-07-09 |
| AU2004213746B2 (en) | 2009-05-07 |
| WO2004074548A1 (en) | 2004-09-02 |
| JP4440919B2 (en) | 2010-03-24 |
| CN100351430C (en) | 2007-11-28 |
| US20070033864A1 (en) | 2007-02-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20150126 |