Title of Invention

"A NON-CORROSIVE TREATMENT TO ENHANCE PRESSURIZED AND NON-PRESSURIZED PULVERIZED COAL COMBUSTION"

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.
Full Text 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 Jess 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 bums 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

supplemental fuels (gas, oil, and pulverized coal) are injected. The blast air bums 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 paniculate 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 4,458,006 and 4,224,1 SO 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/combustion 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 1-10 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 coppersion 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 l-15wt%
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 l-15wt%
copper (as Cu++)* l-20wt%
*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.
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

surfactant and water and the source of coppersion were the yariables 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% Or4, the level found in 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.
TABLE 1
(Table Removed)
11-Day Bottle Test Using Undiluted Stock Solutions
(Table Removed)
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.
(Table Removed)











We Claim:
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. a corrosion inhibiting treatment using a corrosion inhibiting
composition comprising an aminoalcohol and boric acid or water
soluble salt of said boric acid; and
b. copper
2. A method as claimed in claim 1 wherein said coal is pulverized and said composition is applied in the form of an aqueous solution over said pulverized coal.
3. A method as claimed in claim 1 wherein said composition is sprayed in aqueous solution form into said furnace.
4. A method as claimed in claim 1 wherein said aminoalcohol comprises a primary aminoalcohol having a primary amine functionality.
5. A method as claimed in claim 4 wherein said aminoalcohol comprises a tertiary aminoalcohol having tertiary amine functionality.
6. A method as claimed in claim 4 wherein said aminoalcohol comprises 2-aminoethanol.
7. A method as claimed in claim 5 wherein said tertiary aminoalcohol is triethanolamine.
8. A method as claimed in claim 2 wherein said aqueous solution is sprayed over said pulverized coal in an amount of 100 ml-lL per ton of said aqueous solution per ton of said pulverized coal.
9. A method as claimed in claim 8 wherein said aqueous solution is sprayed over said pulverized coal in an amount of 300 ml-lL per ton of said pulverized coal.
10. A method as claimed in claim 6 and 7 wherein said 2-aminoethanol, triethanolamine, and boric acid or salt thereof are present in combination in aqueous solution in an amount of between 1-10 wt%.
11. A method as claimed in claim 10 wherein said aqueous solution further comprises sodium gluconate, said sodium gluconate being present in said aqueous solution in an amount of between l-10wt%.
12. A method as claimed in claim 2 wherein 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 burning said coal in the presence of a corrosion inhibiting composition, said composition comprising 2-aminoethanol, triethanolamine and boric acid or water soluble thereof.
13. A method as claimed in claim 12 wherein said copper and said corrosion inhibiting composition are both sprayed onto said coal in the form of a single aqueous solution.
14. A method as claimed in claim 12 wherein said corrosion inhibiting composition comprises gluconic acid or water soluble salt thereof.
15. A method as claimed in claim 14 wherein said corrosion inhibiting composition further comprises sodium gluconate.
16. A method as claimed in claim 15 wherein said 2-aminoethanol, triethanolamine and boric acid or salt thereof are present in combination in said aqueous solution in an amount of 1-10 wt%, said sodium gluconate being present in said aqueous solution in an amount of 1-15 wt% and wherein said copper is present in said aqueous solution as Cu++ in an amount of 1-20 wt%, and wherein 100 ml-lL of said aqueous solution is sprayed onto said pulverized coal.
17. Corrosion inhibiting composition as claimed in claim 1 comprising an aqueous solution comprising: (a) 2-aminoethanol; (b) triethanolamine; and (c) boric acid or water soluble salt form.
18. Corrosion inhibiting composition as claimed in claim 17 wherein the composition further comprises (d) sodium gluconate.
19. Corrosion inhibiting composition as claimed in claim 18 wherein the composition comprises a copper ion source.
20. Corrosion inhibiting composition as claimed in claim 19 wherein said copper ion source is copper sulfate pentahydrate or copper (II)-D Gluconate.
21. Corrosion inhibiting composition as claimed in claim 19 wherein said (a), (b) and (c), in combination, are present in said aqueous solution in an amount of 1-10 wt%, said (d) is present in said aqueous solution in an amount of 1-15 wt% and wherein said copper ion source (e) is present in an amount sufficient to provide from 1-20 wt% of Cu++ in said aqueous solution.

Documents:

3969-DELNP-2005-Abstract-(24-01-2011).pdf

3969-delnp-2005-abstract.pdf

3969-delnp-2005-assignment.pdf

3969-DELNP-2005-Claims (11-11-2009).pdf

3969-delnp-2005-Claims-(03-12-2010).pdf

3969-DELNP-2005-Claims-(24-01-2011).pdf

3969-delnp-2005-claims.pdf

3969-DELNP-2005-Correspondence-Others (11-11-2009).pdf

3969-delnp-2005-Correspondence-Others-(03-12-2010).pdf

3969-DELNP-2005-Correspondence-Others-(24-01-2011).pdf

3969-delnp-2005-correspondence-others.pdf

3969-delnp-2005-description (complete).pdf

3969-delnp-2005-form-1.pdf

3969-delnp-2005-form-18.pdf

3969-delnp-2005-form-2.pdf

3969-DELNP-2005-Form-3 (11-11-2009).pdf

3969-delnp-2005-form-3.pdf

3969-delnp-2005-form-5.pdf

3969-DELNP-2005-GPA (11-11-2009).pdf

3969-delnp-2005-pct-101.pdf

3969-delnp-2005-pct-210.pdf

3969-delnp-2005-pct-237.pdf

3969-delnp-2005-pct-304.pdf

3969-delnp-2005-pct-311.pdf


Patent Number 246172
Indian Patent Application Number 3969/DELNP/2005
PG Journal Number 08/2011
Publication Date 25-Feb-2011
Grant Date 18-Feb-2011
Date of Filing 05-Sep-2005
Name of Patentee GENERAL ELECTRIC COMPANY
Applicant Address ONE RIVER ROAD, SCHENECTADY, NEW YORK 12345, USA.
Inventors:
# Inventor's Name Inventor's Address
1 BLANDFORD NICHOLAS ROBERT 115 THUNDER CIRCLE, BENSALEM, PA 19020, USA.
2 PEREZ LIBARDO A. 114 JULIET ROAD, MORRISVILLE, PA 19067, USA.
PCT International Classification Number C23F 11/02
PCT International Application Number PCT/US2004/002051
PCT International Filing date 2004-01-26
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/368,823 2003-02-19 U.S.A.