WO2004074548A1 - 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
- Publication number
- WO2004074548A1 WO2004074548A1 PCT/US2004/002051 US2004002051W WO2004074548A1 WO 2004074548 A1 WO2004074548 A1 WO 2004074548A1 US 2004002051 W US2004002051 W US 2004002051W WO 2004074548 A1 WO2004074548 A1 WO 2004074548A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- recited
- aqueous solution
- copper
- amount
- coal
- Prior art date
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention pertains to methods and compositions for inhibiting corrosion of metal surfaces in contact with a furnace.
- 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.
- iron bearing raw materials sinter, iron ore, pellets, etc.
- fuel coke
- flux limestone, dolomite, etc.
- Heated air blast
- 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.
- 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.)
- 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
- the blend is preferably sprayed onto the pulverized coal in aqueous solution form prior to injection of the coal into the furnace.
- 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 4,224,180 herein incorporated by reference.)
- 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.
- the corrosion inhibiting treatment may comprise a tertiary aminoalcohol.
- 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.
- aqueous solution 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 -IL of aqueous solution per ton pulverized coal.
- the corrosion inhibiting treatment comprises both the 2-aminoethanol and triethanolamine component.
- conventional corrosion inhibitors such as water-soluble gluconic acid salts, preferably sodium gluconate, may be incorporated into the corrosion inhibiting treatment.
- 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.
- 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%.
- 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.
- 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.
- compositions in accordance with the invention include:
- aminoalcohol component(s) and boric acid or salt 1-10 wt% aminoalcohol component(s) and boric acid or salt 1-10 wt%
- compositions include
- 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.
- the level of copper (as Cu 2+ in EP9587 (4.84%o) 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 11- day test using undiluted stock solutions was carried out with the better of the two corrosion blends.
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Detergent Compositions (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006503005A JP4440919B2 (en) | 2003-02-19 | 2004-01-26 | Non-corrosive treatment to improve pressurized and unpressurized pulverized coal combustion |
KR1020057015191A KR101138658B1 (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
AU2004213746A AU2004213746B2 (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
EP04705247A EP1597413A1 (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
BRPI0407655-9A BRPI0407655A (en) | 2003-02-19 | 2004-01-26 | non-corrosive treatment to improve combustion of pressurized and non-pressurized pulverized coal |
CA2516491A CA2516491C (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/368,823 US20040159184A1 (en) | 2003-02-19 | 2003-02-19 | Non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
US10/368,823 | 2003-02-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004074548A1 true WO2004074548A1 (en) | 2004-09-02 |
Family
ID=32850212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/002051 WO2004074548A1 (en) | 2003-02-19 | 2004-01-26 | A non-corrosive treatment to enhance pressurized and non-pressurized pulverized coal combustion |
Country Status (9)
Country | Link |
---|---|
US (3) | US20040159184A1 (en) |
EP (1) | EP1597413A1 (en) |
JP (1) | JP4440919B2 (en) |
KR (1) | KR101138658B1 (en) |
CN (1) | CN100351430C (en) |
AU (1) | AU2004213746B2 (en) |
BR (1) | BRPI0407655A (en) |
CA (1) | CA2516491C (en) |
WO (1) | WO2004074548A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101838810B (en) * | 2010-05-18 | 2012-03-14 | 深圳市堃琦鑫华科技有限公司 | Easily degraded water-soluble molten metal oxidation resisting reducing agent |
TWI704233B (en) * | 2018-10-02 | 2020-09-11 | 孫文彬 | Preparation method and system of combustion-supporting agent |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3406042A (en) * | 1965-12-14 | 1968-10-15 | Cons Edison Co New York Inc | Process for corrosion control |
US4101293A (en) * | 1977-03-30 | 1978-07-18 | Reichhold Chemicals, Inc. | Stabilizing emulsifiers |
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 |
US4224180A (en) * | 1979-10-30 | 1980-09-23 | Betz Laboratories, Inc. | Cold end additive compositions |
US4462830A (en) * | 1983-08-04 | 1984-07-31 | Nalco Chemical Company | Corrosion inhibited copper nitrate solutions |
WO1999035215A2 (en) * | 1998-01-12 | 1999-07-15 | Deborah Wenzel | An additive composition also used as a fuel composition comprising water soluble alcohols |
Family Cites Families (16)
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US2836566A (en) * | 1954-01-27 | 1958-05-27 | Detrex Chem Ind | Cleaning composition and method |
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 |
US4458606A (en) * | 1982-04-01 | 1984-07-10 | Betz Laboratories, Inc. | Method of conditioning fireside fouling deposits using large particle size amorphous silica |
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 |
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 BR BRPI0407655-9A patent/BRPI0407655A/en not_active Application Discontinuation
- 2004-01-26 CN CNB2004800079997A patent/CN100351430C/en not_active Expired - Fee Related
- 2004-01-26 KR KR1020057015191A patent/KR101138658B1/en not_active IP Right Cessation
- 2004-01-26 EP EP04705247A patent/EP1597413A1/en not_active Withdrawn
- 2004-01-26 JP JP2006503005A patent/JP4440919B2/en not_active Expired - Fee Related
- 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 WO PCT/US2004/002051 patent/WO2004074548A1/en not_active Application Discontinuation
-
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
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US4224180A (en) * | 1979-10-30 | 1980-09-23 | Betz Laboratories, Inc. | Cold end additive compositions |
US4462830A (en) * | 1983-08-04 | 1984-07-31 | Nalco Chemical Company | Corrosion inhibited copper nitrate solutions |
WO1999035215A2 (en) * | 1998-01-12 | 1999-07-15 | Deborah Wenzel | An additive composition also used as a fuel composition comprising water soluble alcohols |
Also Published As
Publication number | Publication date |
---|---|
US20090253085A1 (en) | 2009-10-08 |
US20070033864A1 (en) | 2007-02-15 |
EP1597413A1 (en) | 2005-11-23 |
CA2516491A1 (en) | 2004-09-02 |
US20040159184A1 (en) | 2004-08-19 |
KR101138658B1 (en) | 2012-04-19 |
AU2004213746A1 (en) | 2004-09-02 |
JP2006518419A (en) | 2006-08-10 |
AU2004213746B2 (en) | 2009-05-07 |
KR20050102123A (en) | 2005-10-25 |
CN100351430C (en) | 2007-11-28 |
JP4440919B2 (en) | 2010-03-24 |
CN1764741A (en) | 2006-04-26 |
CA2516491C (en) | 2013-07-09 |
BRPI0407655A (en) | 2006-02-21 |
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