AU2004213746B2

AU2004213746B2 - A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion

Info

Publication number: AU2004213746B2
Application number: AU2004213746A
Authority: AU
Inventors: Nicholas Robert Blandford; Libardo A. Perez
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2003-02-19
Filing date: 2004-01-26
Publication date: 2009-05-07
Anticipated expiration: 2024-01-26
Also published as: BRPI0407655A; WO2004074548A1; CA2516491C; US20090253085A1; US20070033864A1; JP2006518419A; CN1764741A; CN100351430C; CA2516491A1; KR101138658B1; JP4440919B2; EP1597413A1; US20040159184A1; KR20050102123A; AU2004213746A1

Description

WO 2004/074548 PCT/US2004/002051 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 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. 5 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 10 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, 15 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.) 20 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. The discussion of documents, acts, materials, devices, articles and the like is included in this 25 specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. 30 Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof. 2 W \S EW\752235 RLE)\Response to Ist rcpom 752235 Sp i 310309.doc 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 5 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 10 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 from prior to injection of the coal into the furnace. Alternatively, the treatment may be applied in spray from anywhere in the furnace system including the so-called "fireside" or "cold" end of the furnace. 15 (See U.S. Patents 4,458,006 and 4,224,180 herein incorporated by reference.) In one aspect, the present invention provides 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 a primary aminoalcohol 20 having a primary amine functionality and boric acid or water soluble salt of said boric acid. In another aspect, the present invention provides 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 25 treatment, said treatment comprising 2-aminoethanol, triethanolamine and boric acid or water salt thereof. In a further aspect, the present invention provides corrosion inhibiting composition comprising an aqueous solution comprising: 30 (a) 2-aminoethanol; (b) triethanolamine; and (c) boric acid or water soluble salt form. 3 W \SEW\752235 (RLE)\Rcsponse to Ist repct\752235 Speci 310309 doc DETAILED DESCRIPTION OF THE PRFERRED 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 5 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. 10 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 IL of aqueous 15 solution per ton of coal. More preferably, the dosage rate is from about 300 ml-I L 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 20 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. 3a W.\SEW\2752235 5 o Is rcpmt\ 7 5 22 3 5 Spci 3 10309doc WO 2004/074548 PCT/US2004/002051 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 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. 4 WO 2004/074548 PCT/US2004/002051 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 Cu 2 + in EP9587 (4.84%) was maintained for each new stock formulation prepared. The percentage of 5 WO 2004/074548 PCT/US2004/002051 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 2+ (which is 4.84% Cu , 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 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 CuSO 4 *5H 2 0 C-2 CBCE with an added 1% Sodium 959 0 Gluconate 6 WO 2004/074548 PCT/US2004/002051 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 CuSO 4 e5H 2 0 C-6 CBCE but with the pH raised 1 964 0 unit with NH 4 0H 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 CuSO 4 -5H 2 0. 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 CuSO 4 -5H 2 0. In addition, pH was raised one-half unit with

NH

4 0H. C-9 Similar to the CBCE but with 1% 175 81 of the Cu coming from (Product was not 7 WO 2004/074548 PCT/US2004/002051 Copper(II)-D-Gluconate & the stable.) other 3.84% Cu coming from CuSO 4 -5H 2 0. 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 Copper(II)-D-Gluconate & the (Product was not other 3.84% Cu coming from stable.) CuSO 4 -5H 2 0. In addition, pH was raised one unit with NaOH. C-1I Similar to the CBCE but with 1% 174 81 of the Cu coming from Copper(II)-D-Gluconate & the (Product was not other 3.34% Cu coming from stable.) CuSO 4 -511 2 0. 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 Copper(II)-D-Gluconate & the (Product was not other 3.84% Cu coming from stable.) CuSO 4 -5H 2 0. In addition, pH was raised one unit with NH 4 0H. 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. 8 WO 2004/074548 PCT/US2004/002051 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 BG-10) replaced by 1.6% of a quaternary aryl ammonium chloride (Dodicor 2565). 9 WO 2004/074548 PCT/US2004/002051 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 10 WO 2004/074548 PCT/US2004/002051 one unit w/NH 4 0H. C-24 Similar to the CBCE but with the 832 11 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 CuSO 4 e5H 2 0. The pH was raised one unit w/NH 4 0H as well. C-25 Similar to the CBCE but with the 692 26 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 CuSO 4 -5H 2 0. 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 11 WO 2004/074548 PCT/US2004/002051 4.84% Cu (from 19% copper sulfate pentahydrate). Example Similar to the CBCE but with the 213 77 2 1.6% alkylpolyglucoside 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 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 5 1.6% alkylpolyglucoside surfactant (Triton BG-10) not 12 WO 2004/074548 PCT/US2004/002051 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% 13 WO 2004/074548 PCT/US2004/002051 Cu came from copper sulfate pentahydrate to make up the 4.84% total Cu amount. C-27 Similar to the CBCE but with the 820 12 1.6% alkylpolyglucoside 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 with the 775 17 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 14 WO 2004/074548 PCT/US2004/002051 (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 instead of CuSO 4 -5H 2 0 (Increase in raw material cost higher than 20%.) C-30 EP9587 1% Sodium 959 0 Gluconate. C-31 EP9587 6.7% Sodium 974 0 15 WO 2004/074548 PCT/US2004/002051 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 CuSO 4 -5H 2 0. C-34 EP9587 & pH raised 1 unit 964 0 w/ NH 4 0H. C-35 EP9587 w/ 1% Cu from 955 0 Copper(II)-D-Gluconate & 3.84% from CuSO 4 -5H 2 0 w/ 0.1% zinc. C-36 EP9587 w/ 1% Cu from 466 50 Copper(II)-D-Gluconate & 3.84% from CuSO 4 -5H 2 0 & pH raised one half unit w/

NH

4 0H. C-37 EP9587 w/ 1% Cu from 175 81 Copper(II)-D-Gluconate & 3.84% from CuSO 4 -5H 2 0 & (Product was not pH raised one unit w/ KOH. stable.) C-38 EP9587 w/ 1% Cu from 212 77 Copper(II)-D-Gluconate & 3.84% from CuSO 4 e5H 2 0 & (Product was not pH raised one unit with stable.) NAOH. 16 WO 2004/074548 PCT/US2004/002051 C-39 EP9587 w/ 1.5% Cu from 174 81 Copper(II)-I)-Gluconate & 3.34% from CuSO 4 e5H 2 0 w/ (Product was not pH raised one unit with stable.) NaOH. C-40 EP9587 w/ 1% Cu from 147 84 Copper(II)-D-Gluconate & 3.84% from CuSO 4 *5H 2 0 & (Product was not pH raised one unit stable.) w/NH 4 0H. 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 10 & 1.5% Burko TME C-43 EP9587 w/ Triton BG-10 838 10 replaced by alkoxylated amme. 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. 17 WO 2004/074548 PCT/US2004/002051 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/

NH

4 0H. C-52 Triton BG-10 replaced by 832 11 Dodicor 2565 & 1% Cu from Copper(II)-D-Gluconate & 3.84% from CuSO 4 e5H 2 0 and pH raised one unit w/ NaOH. Example Triton BG-10 replaced by 692 26 10 Maxhib PA 315 & 1% Cu from Copper(II)-D Gluconate & 3.84% from CuSO 4 -5H 2 0 and pH raised one unit w/ NaOH. 18 WO 2004/074548 PCT/US2004/002051 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 19 WO 2004/074548 PCT/US2004/002051 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). 20 WO 2004/074548 PCT/US2004/002051 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. 21

Claims

2. A method as recited in claim 1 wherein said coal is pulverized and said treatment is applied in the form of an aqueous solution over said pulverized coal. 10
3. A method as recited in claim 1 or 2 wherein said treatment is sprayed in aqueous solution form into said furnace.
4. A method as recited in any one of claims 1-3 wherein said corrosion inhibiting 15 treatment further comprises a tertiary aminoalcohol having tertiary amine functionality.
5. A method as recited in any one of claims 1-4 wherein said corrosion inhibiting treatment further comprises 2-aminoethanol. ?0 6. A method as recited in claim 4 wherein said tertiary aminoalcohol is triethanolamine.
7. A method as recited in claim 6 wherein said coal is burned in the presence of copper.
8. A method as recited in claim 2 wherein said aqueous solution is sprayed over said 25 pulverized coal in an amount of about 100 ml-lL of said aqueous solution per ton of said pulverized coal.
9. A method as recited in claim 8 wherein said aqueous solution is sprayed over said pulverized coal in an amount of about 300 ml-l L per ton of said pulverized coal. 30
10. A method as recited in claim 6 wherein said 2-aminoethanol, triethanolamine, and boric acid or salt thereof are present in combination in aqueous solution in an amount of between about 1-10 wt%. 22 W \SEW\752235 ( RLE)\Rcsponse o I st repot\752235 Oanis 310309dot
11. A method as recited in claim 10 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%. 5 12. 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 salt thereof. 10 13. A method as recited in claim 12 wherein said copper and said corrosion inhibiting treatment are both sprayed onto said coal in the form of a single aqueous solution.
14. A method as recited in claim 12 or 13 wherein said corrosion inhibiting treatment further comprises gluconic acid or water soluble salt thereof. 15
15. A method as recited in claim 14 wherein said corrosion inhibiting treatment comprises sodium gluconate.
16. A method as recited in claim 15 wherein said 2-aminoethanol, triethanolamine and 20 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-IL of said aqueous solution is sprayed onto said pulverized coal. 25 1 7. Corrosion inhibiting composition comprising an aqueous solution comprising: (a) 2-aminoethanol; (b) triethanolamine; and (c) boric acid or water soluble salt form. 30
18. Corrosion inhibiting composition as recited in claim 17 further comprising (d) sodium gluconate. 23 W 'SIW\752235 (RLE)\Rcsponsc to I sM rcpoI752235 CIAis 310309.doc 1 9. Corrosion inhibiting composition as recited in claim 18 further comprising (e) a copper ion source.
20. Corrosion inhibiting composition as recited in claim 19 wherein said copper ion source 5 is copper sulfate pentahydrate or copper(II)-D Gluconate.
21. Corrosion inhibiting composition as recited in claim 19 or 20 wherein said (a), (b) and (c), in combination, are present in said aqueous solution in an amount of about 1-10 wt%, said (d) is present in said aqueous solution in an amount of about 1-15 wt% and wherein said 10 copper ion source (e) is present in an amount sufficient to provide from about 1-20 wt% of Cu** ion in said aqueous solution.
22. A method according to claim 1, substantially as hereinbefore described with reference to any one of the Examples. 15
23. A method according to claim 12, substantially as hereinbefore described with reference to any one of the Examples.
24. Corrosion inhibiting composition according to claiir 17, substantially as hereinbefore 20 described with reference to any one of the Examples. 24 W \SEW\752235 RLEl Resp.ons o Ist rpor\ 7 522 35 C is 310309.doc