US2911292A - Reducing the corrosivity of vanadiumcontaining oils - Google Patents
Reducing the corrosivity of vanadiumcontaining oils Download PDFInfo
- Publication number
- US2911292A US2911292A US198476A US19847650A US2911292A US 2911292 A US2911292 A US 2911292A US 198476 A US198476 A US 198476A US 19847650 A US19847650 A US 19847650A US 2911292 A US2911292 A US 2911292A
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- US
- United States
- Prior art keywords
- nickel
- oil
- vanadium
- vanadate
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/1814—Chelates
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1828—Salts thereof
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds
-
- 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
Definitions
- Residual fuel oils contain very small amounts of metals such. as vanadium, calcium, iron,-nickel, molybdenum, sodium, etc. Some of these elements are introduced during the refining of the oils. Others are present in the original crude either in fine suspension or in the form of soluble organic compounds. When the oil is burned in industrial installations these metals are transformed into oxides which are generally partly blown out of the stacks and partly remain as flue dust. When this fiue dust contains vanadium and is deposited on the surface of the boiler tubes or the fire brick walls, corrosion and/or slagging results. The extent of this corrosion and slagging is a function of the melting point of the dust and its content of free vanadium pentoxide remaining in excess depending on the metal content of the oil.
- metals such. as vanadium, calcium, iron,-nickel, molybdenum, sodium, etc.
- This oxide melts at 690 C. and is extremely corrosive, attacking every metal, even platinum and silica when in the molten state. Furthermore, vanadium pentoxide, due to its relatively low melting point will be projected in droplets which will remain liquid (particularly in small installations with restricted-size combustion chambers) and will collect additional dust particles.
- oil soluble metal compounds which are suitable are the metal derivatives of acids such as naphthenic acids and fatty acids, phenolates, salts of alkylated phenol sulfides such as di-isobutyl phenol'sulfide, salicylates, salts of thiophosphorus acid esters such as dilauryl, thiophosphoric acid, chelates such as the metal derivatives of compounds having difunctional groups, for example diamine and diketo compounds of the type of pentane-dione.
- acids such as naphthenic acids and fatty acids
- phenolates salts of alkylated phenol sulfides such as di-isobutyl phenol'sulfide
- salicylates salts of thiophosphorus acid esters such as dilauryl, thiophosphoric acid
- chelates such as the metal derivatives of compounds having difunctional groups, for example diamine and diketo compounds of the type of pentane-dione.
- the metal compounds may be added to the oil at any time prior to combustion and in approximately the stoichiometric proportions necessary to form the corresponding meta vanadate. The exact amount depends upon the metal but may easily be calculated from the .0l% for nickel, calculated as the metal.
- vanadium pentoxide present in the oil which is usually from 0.0001 to 0.05%. This amounts tofbetween 0.00001 and 0.005% for aluminum, between 0.00002 and 0.01% for iron, and between 0.00002 and The. actual amount of metal compound added will also depend upon the presence of naturally occurring nickel or ironisalts in' .the oil. If these are appreciable, the amount'added to combine with the vanadium would be correspondingly less. f
- addition agents of the present invention maybe added toany fuel oil, 'they are-especially adapted for use in conjunction with'residual or bunker fuels.
- Example 1 The vanadates of aluminum, nickel, iron and magnesium were prepared and the melting point of each was obtained with the following results:
- Example 2 A sample of a Venezuela fuel oil ash containing 25% vanadium was found to have a melting point between 1500 and 1550 F. Sufficient anhydrous sodium sulfate was added to this ash to make the sodium content about 11%. The melting point of this material was found to be between 1200 and 1300 F. Sufficient nickel oxide (19.4%) was added to combine with the vanadium present and the melting point was found to have increased to between 1850 and 1950 F.
- a fuel composition comprising a major amount of a residual fuel oil yielding a corrosive vanadium containing ash upon combustion, and a minor amount, sufficient to retard the corrosiveness of said ash of an oilsoluble metal compound selected from the group consisting of the oil-soluble compounds of iron, aluminum, and nickel, said fuel oil composition in the absence of said metal compound normally yielding a corrosive vanadium containing ash upon combustion.
- a liquid fuel composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadiu-m and an oil-soluble metal compound selected from the group consisting of the oil-soluble compounds of iron,
- metal compound being present in the amount required to react substantially stoichiometrically with the vanadium upon combustion of the fuel oil to form a meta vanadate of the metal.
- composition as defined in claim 5 in which the amount of aluminum compound added, calculated as aluminum is between 0.00001 and 0.005% of the residual fuel.
- a liquid fuel oil composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadium to which is added a substantially stoichiometrie amount of an oil-soluble nickel salt of a high molecular weight fatty acid which-will react with the vanadium pentoxide to form a vanadate of the metal melting above 1600 F.
- a liquid fuel oil composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadium to. which. is added a substantially stoichiometric amount of an oil-soluble nickel napththenate which will react with the vanadium pentoxide to form a vanadate of the metal melting above 1600 F.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
United.S atesParehto,"
" 2,911,292 Patented Nov. 3, .1959
.7 fuel oils containing vanadium to produce, when burned,
an ash which will corrode boiler tubes and boiler tube supports and cause slagging offire bricks.
Residual fuel oils contain very small amounts of metals such. as vanadium, calcium, iron,-nickel, molybdenum, sodium, etc. Some of these elements are introduced during the refining of the oils. Others are present in the original crude either in fine suspension or in the form of soluble organic compounds. When the oil is burned in industrial installations these metals are transformed into oxides which are generally partly blown out of the stacks and partly remain as flue dust. When this fiue dust contains vanadium and is deposited on the surface of the boiler tubes or the fire brick walls, corrosion and/or slagging results. The extent of this corrosion and slagging is a function of the melting point of the dust and its content of free vanadium pentoxide remaining in excess depending on the metal content of the oil. This oxide melts at 690 C. and is extremely corrosive, attacking every metal, even platinum and silica when in the molten state. Furthermore, vanadium pentoxide, due to its relatively low melting point will be projected in droplets which will remain liquid (particularly in small installations with restricted-size combustion chambers) and will collect additional dust particles.
It has now been found that the corrosive effect of this vanadium pentoxide may be eliminated or at least greatly reduced by the addition to the oil, prior to burning, of an oil soluble metal compound which will combine with the vanadium pentoxide and form a vanadate of suflicient- 1y high melting point that it will not be melted during the combustion of the oil. The minimum melting point which such a vanadate should possess is above 1600 F. since the temperature reached in the combusion of fuel oil does not quite reach that high. The only vanadates which have been found to possess fusion points as high as 1600 F. are iron, nickel and aluminum meta vanadates. The nickel and aluminum vanadates are particularly efiicient since both have melting points above 2000" F. However, the use of nickel is preferred since the addition of aluminum salts may cause gelling of the fuel oil. 7
Among the oil soluble metal compounds which are suitable are the metal derivatives of acids such as naphthenic acids and fatty acids, phenolates, salts of alkylated phenol sulfides such as di-isobutyl phenol'sulfide, salicylates, salts of thiophosphorus acid esters such as dilauryl, thiophosphoric acid, chelates such as the metal derivatives of compounds having difunctional groups, for example diamine and diketo compounds of the type of pentane-dione.
The metal compounds may be added to the oil at any time prior to combustion and in approximately the stoichiometric proportions necessary to form the corresponding meta vanadate. The exact amount depends upon the metal but may easily be calculated from the .0l% for nickel, calculated as the metal.
amount of vanadium pentoxide present in the oil which is usually from 0.0001 to 0.05%. This amounts tofbetween 0.00001 and 0.005% for aluminum, between 0.00002 and 0.01% for iron, and between 0.00002 and The. actual amount of metal compound added will also depend upon the presence of naturally occurring nickel or ironisalts in' .the oil. If these are appreciable, the amount'added to combine with the vanadium would be correspondingly less. f
Although .the addition agents of the present invention maybe added toany fuel oil, 'they are-especially adapted for use in conjunction with'residual or bunker fuels.
These fuels have gravities in the range from 1r fto 15 1 API and furol'viscosities at 122 F. in the range from 25 seconds to 300 seconds. From what has been'said, therefore, in a specific embodiment of the inventionzythe nickel derivativeof naphthenic acid may'be employed in a'vanadium-containing residual fuel inan amountisuch that the nickel willv be present in the fuel in a proportion sufficient to 'form'nickel meta vanadate -wi t-h;, the vanadium.
. In order to more fully illustrate the present invention, the following examples are given:
Example 1 The vanadates of aluminum, nickel, iron and magnesium were prepared and the melting point of each was obtained with the following results:
Compound: Melting point, F. Aluminum vanadate 2100 Ferric vanadate l6l5l630 Nickel vanadate 2000+ Magnesium vanadate 1290-1330 The nickel vanadate was analyzed and found to contain 39.2% vanadium and 25.2% nickel. The vanadium content corresponds very closely to the theoretical for nickel meta vanadate (Ni(VO but the nickel content is 10% too high, due probably to occluded salts. Since the vanadium pentoxide content of fuel oil varies from 0.0001 to 0.05%, the addition of 0.00002 to 0.01% nickel will be necessary to form the theoretical amount of nickel meta vanadate.
Example 2 A sample of a Venezuela fuel oil ash containing 25% vanadium was found to have a melting point between 1500 and 1550 F. Sufficient anhydrous sodium sulfate was added to this ash to make the sodium content about 11%. The melting point of this material was found to be between 1200 and 1300 F. Sufficient nickel oxide (19.4%) was added to combine with the vanadium present and the melting point was found to have increased to between 1850 and 1950 F.
The nature of the present invention having been thus fully set forth and specific examples of the same given, what is claimed as new and useful and desired to be secured by Letters Patent is:
1. A fuel composition comprising a major amount of a residual fuel oil yielding a corrosive vanadium containing ash upon combustion, and a minor amount, sufficient to retard the corrosiveness of said ash of an oilsoluble metal compound selected from the group consisting of the oil-soluble compounds of iron, aluminum, and nickel, said fuel oil composition in the absence of said metal compound normally yielding a corrosive vanadium containing ash upon combustion.
2. A liquid fuel composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadiu-m and an oil-soluble metal compound selected from the group consisting of the oil-soluble compounds of iron,
aluminum and nickel, said metal compound being present in the amount required to react substantially stoichiometrically with the vanadium upon combustion of the fuel oil to form a meta vanadate of the metal.
3. Composition as defined inclaim 2 in which the metal compound is an oil-soluble nickel compound.
4. Composition as defined in claim 2 in which the metal compound is an oil-soluble iron compound.
5. Composition as defined in claim 2 in which the metal compound is an oil-soluble aluminum compound.
6. Composition as defined in claim 3 in which the amount of nickel compound added, calculated as nickel,
is between 0400002 and 0.01% of the residual fuel.
' 7. Composition as defined in claim 4in. which the amount of iron compound added, calculated as iron, is between 0.00002 and 0.01% of the residual fuel.
8. Composition as defined in claim 5 in which the amount of aluminum compound added, calculated as aluminum is between 0.00001 and 0.005% of the residual fuel.
9. A liquid fuel oil composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadium to which is added a substantially stoichiometrie amount of an oil-soluble nickel salt of a high molecular weight fatty acid which-will react with the vanadium pentoxide to form a vanadate of the metal melting above 1600 F.
10. A liquid fuel oil composition adapted to be burned at substantially atmospheric pressure without corroding the equipment comprising a residual fuel oil containing vanadium to. which. is added a substantially stoichiometric amount of an oil-soluble nickel napththenate which will react with the vanadium pentoxide to form a vanadate of the metal melting above 1600 F.
References Cited in the file of this patent v V UNITED STATES PATENTS 2,230,642 Fischer et al. Feb. 4, 1941 2,301,795 Proell a Nov. 10, 1942 2,338,578 Downing Jan. 4, 1944 2,560,542 Bartleson. July 17,1951
FOREIGN PATENTS 445,506 Great Britain .4. Apr. 14, 1936 496,692 Great Britain Dec. 5, 1938 OTHER REFERENCES Dunstan et al.: The Science of Petroleum, Oxford Univ. Press, New York, N.Y., 1.93 8-, vol. 2, page 1053.
Claims (1)
1. A FUEL COMPOSITION COMPRISING A MAJOR AMOUNT A RESIDUAL FUEL OIL YIELDING A CORROSIVE VANADIUM CONTAINING ASH UPON COMBUSTION, AND A MINOR AMOUNT, SUFFICIENT TO RETARD THE CORROSIVENESS OF SAID ASH OF AN OILSOLUBLE METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE OIL-SOLUBLE COMPOUNDS OF IRON ALUMINUM, AND NICKEL, SAID FUEL OIL COMPOSITION IN THE ABSENCE OF SAID METAL COMPOUND NORMALLY YIELDING A CORROSIVE VANADIUM CONTAINING AS UPON COMBUSTION.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US198476A US2911292A (en) | 1950-11-30 | 1950-11-30 | Reducing the corrosivity of vanadiumcontaining oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US198476A US2911292A (en) | 1950-11-30 | 1950-11-30 | Reducing the corrosivity of vanadiumcontaining oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2911292A true US2911292A (en) | 1959-11-03 |
Family
ID=22733542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US198476A Expired - Lifetime US2911292A (en) | 1950-11-30 | 1950-11-30 | Reducing the corrosivity of vanadiumcontaining oils |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2911292A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3078665A (en) * | 1960-08-03 | 1963-02-26 | Gulf Research Development Co | Vanadium containing residual fuels modified with iron, c o b a l t or nickel and alkali metal compounds |
| US3114710A (en) * | 1960-02-10 | 1963-12-17 | Shell Oil Co | Thickened hydrocarbon compositions |
| US3177233A (en) * | 1963-08-30 | 1965-04-06 | Shell Oil Co | Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid |
| US4170447A (en) * | 1977-01-11 | 1979-10-09 | Exxon Research & Engineering Co. | Method of separating solid particulate |
| US20030159338A1 (en) * | 2000-06-19 | 2003-08-28 | Michel Moliere | Use of nickel compounds as vanadium corrosion inhibitors |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB445506A (en) * | 1934-08-06 | 1936-04-14 | Bataafsche Petroleum | A process for burning oil |
| GB496692A (en) * | 1936-07-27 | 1938-12-05 | Bbc Brown Boveri & Cie | Improved method of firing oil fired furnaces |
| US2230642A (en) * | 1938-08-13 | 1941-02-04 | Standard Oil Dev Co | Fuel oil |
| US2301795A (en) * | 1941-06-16 | 1942-11-10 | Standard Oil Co | Stabilizer for oils |
| US2338578A (en) * | 1941-06-21 | 1944-01-04 | Du Pont | Heating fuel oil |
| US2560542A (en) * | 1947-06-07 | 1951-07-17 | Standard Oil Co | Clean-burning carbonaceous compositions |
-
1950
- 1950-11-30 US US198476A patent/US2911292A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB445506A (en) * | 1934-08-06 | 1936-04-14 | Bataafsche Petroleum | A process for burning oil |
| GB496692A (en) * | 1936-07-27 | 1938-12-05 | Bbc Brown Boveri & Cie | Improved method of firing oil fired furnaces |
| US2230642A (en) * | 1938-08-13 | 1941-02-04 | Standard Oil Dev Co | Fuel oil |
| US2301795A (en) * | 1941-06-16 | 1942-11-10 | Standard Oil Co | Stabilizer for oils |
| US2338578A (en) * | 1941-06-21 | 1944-01-04 | Du Pont | Heating fuel oil |
| US2560542A (en) * | 1947-06-07 | 1951-07-17 | Standard Oil Co | Clean-burning carbonaceous compositions |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3114710A (en) * | 1960-02-10 | 1963-12-17 | Shell Oil Co | Thickened hydrocarbon compositions |
| US3078665A (en) * | 1960-08-03 | 1963-02-26 | Gulf Research Development Co | Vanadium containing residual fuels modified with iron, c o b a l t or nickel and alkali metal compounds |
| US3177233A (en) * | 1963-08-30 | 1965-04-06 | Shell Oil Co | Oil-soluble polyvalent metal salts of alkyl mercaptomethyl phosphonic acid |
| US4170447A (en) * | 1977-01-11 | 1979-10-09 | Exxon Research & Engineering Co. | Method of separating solid particulate |
| US20030159338A1 (en) * | 2000-06-19 | 2003-08-28 | Michel Moliere | Use of nickel compounds as vanadium corrosion inhibitors |
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