US2882237A - Method for oxidizing carbonaceous deposits - Google Patents
Method for oxidizing carbonaceous deposits Download PDFInfo
- Publication number
- US2882237A US2882237A US587959A US58795956A US2882237A US 2882237 A US2882237 A US 2882237A US 587959 A US587959 A US 587959A US 58795956 A US58795956 A US 58795956A US 2882237 A US2882237 A US 2882237A
- Authority
- US
- United States
- Prior art keywords
- weight percent
- deposits
- hydrogen peroxide
- tubes
- carbonaceous deposits
- 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
Links
- 238000000034 method Methods 0.000 title claims description 9
- 230000001590 oxidative effect Effects 0.000 title description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 238000004939 coking Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
- B08B9/027—Cleaning the internal surfaces; Removal of blockages
- B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B43/00—Preventing or removing incrustations
- C10B43/02—Removing incrustations
- C10B43/08—Removing incrustations with liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B43/00—Preventing or removing incrustations
- C10B43/02—Removing incrustations
- C10B43/10—Removing incrustations by burning out
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J3/00—Removing solid residues from passages or chambers beyond the fire, e.g. from flues by soot blowers
- F23J3/02—Cleaning furnace tubes; Cleaning flues or chimneys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
Definitions
- This invention relates to a method of cleaning objects bearing carbonaceous deposits.
- the activated oxidizing solution is applied to the carbonaceous deposits and maintained in the liquid phase in contact therewith until the deposits are, for the most part, oxidized to form fluid substances.
- the reaction is highly exothermic and the deposits are usually completely converted into gaseous or colorless, water-soluble products.
- the method may be applied at room or ambient temperatures.
- the activated oxodizing solution is admitted slowly to fill the tubes, preferably from the bottom, leaving the higher ends of the tubes open to permit generated gas to escape freely.
- a shield or apron to prevent spillage and a fume hood are useful at the higher ends.
- the composition of the activated oxidizing solution is advantageously adjusted to complete the treatment in about four to twenty minutes.
- Higher temperatures, higher concentrations of hydrogen peroxide and, within limits, higher concentrations of ammonia result in more rapid oxidations; conversely the oxidation is retarded by the contrary changes.
- oxidation is too rapid excessive foaming results; this can lead to spattering and, when applied to confined places such as tubes, to undesirable blow-off of fluid and/or build-up of pressure.
- solutions containing over 30 weight percent of hydrogen peroxide are advantageously avoided, and concentrations under 27 weight percent are preferred. Excessively low concentrations lead to disproportionately slow oxidation rates.
- the method can be applied to any surface which is not excessively corroded by hydrogen peroxide; excellent results were obtained on glass and aluminum objects hearing carbon deposits. Because of the high corrosion re sulting from the treatment, it is usually not suitable for removing carbon deposits from heavy metals, such as lead, copper and brass, save in the unusual case where corrosion is not detrimental.
- Example I A solution consisting of two volumes of 30 weight percent H 0 and one volume of concentrated ammonium hydroxide (having a final composition 20 weight percent H 0 and 19.3 weight percent NH OH) was applied at room temperature to the surface of a sheet of aluminum having a carbonaceous deposit thereon resulting from the coking of jet engine lubricating oils. The solution covered the deposit for ten minutes, during which time carbon dioxide was liberated, accompanied with mild foaming and a temperature rise. At the end of the period the solution was clear and was removed, leaving a clean aluminum surface.
- Example 11 Tests on other aqueous hydrogen peroxide solutions following the deposits and procedure of Example I, indicate the efiects of varying the concentrations. Their eifects are shown in tabular form below:
- the method of removing carbonaceous resinous or gummy deposits resulting from the coking of hydrocarbons from the inner surfaces of tubes which comprises flowing through said tubes a solution consisting essentially of water, hydrogen peroxide in amount between 12 and 27 weight percent and ammonium hydroxide in amount between 3 and 32 weight percent.
- the method of removing carbonaceous resinous or gummy deposits resulting from the coking of hydrocarbons from objects which comprises oxidizing said deposits by covering the part of the object bearing said deposit with an aqueous solution of between 6 and 30 weight percent hydrogen peroxide and between 1 and 40 weight percent of ammonium hydroxide.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
2,882,237 Patented Apr. 14, 1959 METHOD FOR OXIDIZING CARBONACEOUS DEPOSITS Clarence Lynn Mahoney, Berkeley, Calif., assignor to Shell Development Company, New York, N.Y., a corporation of Delaware No Drawing. Application May 29, 1956 Serial No. 587,959
2 Claims. (Cl. 252-186) This invention relates to a method of cleaning objects bearing carbonaceous deposits.
carbonaceous deposits which contain resinous or gummy materials and result from the coking of hydrocarbons are often difficult to remove by ordinary means, being too tenaceous to be effectively dislodged by detergents and situated on inaccessible or irregularly shaped surfaces so as to defy scraping. Thus, difficulties occur in removing deposits from the inner surfaces of heat exchanger tubes used in the petroleum industry and in molds used, for example, for rubber goods. Oxygenliberating compounds such as hydrogen peroxide have been used heretofore to clean internal combustion engines, molds, and the like, but under conditions which caused no substantial oxidation thereof at ordinary temperatures.
Now in accordance with this invention, it was found that hydrogen peroxide in aqueous solution is activated and readily oxidizes the carbonaceous deposits When ammonia is admixed thereto. In most instances the aqueous solutions used contain from 6 to 30 weight percent hydrogen peroxide and ammonia yielding from 1 to 40 weight percent of ammonia hydroxide. The rate of oxidation is best controlled and the operation is safer, as described below, When the hydrogen peroxide content is between 12 and 27 weight percent and the ammonium hydroxide content between 3 and 32 weight percent.
In the practice of the invention, the activated oxidizing solution is applied to the carbonaceous deposits and maintained in the liquid phase in contact therewith until the deposits are, for the most part, oxidized to form fluid substances. The reaction is highly exothermic and the deposits are usually completely converted into gaseous or colorless, water-soluble products. The method may be applied at room or ambient temperatures.
As applied to the cleaning of tubes, such as aluminum heat exchange tubes, the activated oxodizing solution is admitted slowly to fill the tubes, preferably from the bottom, leaving the higher ends of the tubes open to permit generated gas to escape freely. A shield or apron to prevent spillage and a fume hood are useful at the higher ends.
The composition of the activated oxidizing solution is advantageously adjusted to complete the treatment in about four to twenty minutes. Higher temperatures, higher concentrations of hydrogen peroxide and, within limits, higher concentrations of ammonia result in more rapid oxidations; conversely the oxidation is retarded by the contrary changes. When oxidation is too rapid excessive foaming results; this can lead to spattering and, when applied to confined places such as tubes, to undesirable blow-off of fluid and/or build-up of pressure. Also, to avoid the hazard of forming explosive peroxides, solutions containing over 30 weight percent of hydrogen peroxide are advantageously avoided, and concentrations under 27 weight percent are preferred. Excessively low concentrations lead to disproportionately slow oxidation rates.
The method can be applied to any surface which is not excessively corroded by hydrogen peroxide; excellent results were obtained on glass and aluminum objects hearing carbon deposits. Because of the high corrosion re sulting from the treatment, it is usually not suitable for removing carbon deposits from heavy metals, such as lead, copper and brass, save in the unusual case where corrosion is not detrimental.
Example I A solution consisting of two volumes of 30 weight percent H 0 and one volume of concentrated ammonium hydroxide (having a final composition 20 weight percent H 0 and 19.3 weight percent NH OH) was applied at room temperature to the surface of a sheet of aluminum having a carbonaceous deposit thereon resulting from the coking of jet engine lubricating oils. The solution covered the deposit for ten minutes, during which time carbon dioxide was liberated, accompanied with mild foaming and a temperature rise. At the end of the period the solution was clear and was removed, leaving a clean aluminum surface.
Example 11 Tests on other aqueous hydrogen peroxide solutions following the deposits and procedure of Example I, indicate the efiects of varying the concentrations. Their eifects are shown in tabular form below:
Wt. Wt. Relative Run Percent Percent Other Order of Remarks N 0. H202 HrOH Additives Oxidation Rate 30 0 Essentially no reaction.
20 17% (Acetic 0 Do.
10 38 2 Very slow reaction.
15 3 3 Moderate reaction rate.
15 7 4 Fairly fast: reaction.
20 7 5 Fast reaction.
26 7 6 Very fast reaction.
From the foregoing it is evident that aqueous hydrogen peroxide, neither alone nor when acidified with acetic acid, reacts appreciably with the carbonaceous deposits, but does so when activated with ammonia.
I claim as my invention:
1. The method of removing carbonaceous resinous or gummy deposits resulting from the coking of hydrocarbons from the inner surfaces of tubes which comprises flowing through said tubes a solution consisting essentially of water, hydrogen peroxide in amount between 12 and 27 weight percent and ammonium hydroxide in amount between 3 and 32 weight percent.
2. The method of removing carbonaceous resinous or gummy deposits resulting from the coking of hydrocarbons from objects which comprises oxidizing said deposits by covering the part of the object bearing said deposit with an aqueous solution of between 6 and 30 weight percent hydrogen peroxide and between 1 and 40 weight percent of ammonium hydroxide.
References Cited in the file of this patent UNITED STATES PATENTS 355,523 Harrison Ian. 4, 1887 2,037,119 Comey Apr. 14, 1936 2,465,228 Hein Mar. 22, 1949 FOREIGN PATENTS 133,309 Australia June 23, 1949
Claims (1)
1. THE METHOD OF REMOVING CARBONACEOUS RESINOUS OR GUMMY DEPOSITS RESULTING FROM THE COKING OF HYDROCARBONS FROM THE INNER SURFACE''S OF TUBES WHICH COMPRISES FLOWING THROUGH SAID TUBES A SOLUTION CONSISTING ESSENTIALLY OF WATER, HYDROGEN PEROXIDE IN AMOUNT BETWEEN 12 AND 27 WEIGHT PERCENT AND AMMONIUM HYDROXIDE IN AMOUNT BETWEEN 3. AND 32 WEIGHT PERCENT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US587959A US2882237A (en) | 1956-05-29 | 1956-05-29 | Method for oxidizing carbonaceous deposits |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US587959A US2882237A (en) | 1956-05-29 | 1956-05-29 | Method for oxidizing carbonaceous deposits |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2882237A true US2882237A (en) | 1959-04-14 |
Family
ID=24351882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US587959A Expired - Lifetime US2882237A (en) | 1956-05-29 | 1956-05-29 | Method for oxidizing carbonaceous deposits |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2882237A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3034851A (en) * | 1956-10-01 | 1962-05-15 | Du Pont | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process |
| US3076543A (en) * | 1958-10-03 | 1963-02-05 | Sinclair Refining Co | Ammoniacal ammonium nitrate solution with hydrogen peroxide as corrosion inhibitor |
| US3173874A (en) * | 1961-10-03 | 1965-03-16 | Richard B H Sewell | Process for removal of vanadium deposits |
| US3654940A (en) * | 1970-11-25 | 1972-04-11 | Chemed Corp | Method for removing resinous or rubber deposits with organic peroxides |
| DE2524816A1 (en) * | 1974-06-07 | 1976-01-02 | Sapic | METHOD AND APPARATUS FOR RECOVERING A GRANULAR RESIN-BONDED MATERIAL |
| US4113510A (en) * | 1974-06-07 | 1978-09-12 | Societe D'applications De Procedes Industriels Et Chimiques S.A.P.I.C. | Process for regenerating foundry sand |
| DE2911259A1 (en) * | 1979-03-22 | 1980-10-02 | Shell Ag | Cleaning compsns. for boilers - contg. alkali metal iodate or periodate in alkaline soln. |
| WO1988009368A1 (en) * | 1987-05-19 | 1988-12-01 | Schamschula Gyoergy | Composition and process for cleaning of fire-side parts of firing devices |
| US4847089A (en) * | 1986-07-16 | 1989-07-11 | David N. Kramer | Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same |
| US5045121A (en) * | 1989-06-21 | 1991-09-03 | Gte Products Corporation | Method for removing carbon from cemented tungsten carbide articles |
| US5490947A (en) * | 1993-09-10 | 1996-02-13 | Cioffe; Anthony | Method for cleaning firearms and other metal ordnance |
| US20030106838A1 (en) * | 2001-12-12 | 2003-06-12 | Michael Siskin | Process for increasing yield in coking processes |
| CN107418614A (en) * | 2017-07-24 | 2017-12-01 | 天津大学 | Online decoking method for hydrocarbon fuel tubular cracking furnace |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US355523A (en) * | 1887-01-04 | Rison | ||
| US2037119A (en) * | 1933-07-31 | 1936-04-14 | R H Comey Brooklyn Company Inc | Continuous bleaching process |
| US2465228A (en) * | 1946-05-07 | 1949-03-22 | Westinghouse Electric Corp | Liquid treatment of contact surfaces for copper oxide rectifiers |
-
1956
- 1956-05-29 US US587959A patent/US2882237A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US355523A (en) * | 1887-01-04 | Rison | ||
| US2037119A (en) * | 1933-07-31 | 1936-04-14 | R H Comey Brooklyn Company Inc | Continuous bleaching process |
| US2465228A (en) * | 1946-05-07 | 1949-03-22 | Westinghouse Electric Corp | Liquid treatment of contact surfaces for copper oxide rectifiers |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3034851A (en) * | 1956-10-01 | 1962-05-15 | Du Pont | Hydrogen peroxide-ammonium bicarbonate acidic bleaching composition and process |
| US3076543A (en) * | 1958-10-03 | 1963-02-05 | Sinclair Refining Co | Ammoniacal ammonium nitrate solution with hydrogen peroxide as corrosion inhibitor |
| US3173874A (en) * | 1961-10-03 | 1965-03-16 | Richard B H Sewell | Process for removal of vanadium deposits |
| US3654940A (en) * | 1970-11-25 | 1972-04-11 | Chemed Corp | Method for removing resinous or rubber deposits with organic peroxides |
| DE2524816A1 (en) * | 1974-06-07 | 1976-01-02 | Sapic | METHOD AND APPARATUS FOR RECOVERING A GRANULAR RESIN-BONDED MATERIAL |
| US4113510A (en) * | 1974-06-07 | 1978-09-12 | Societe D'applications De Procedes Industriels Et Chimiques S.A.P.I.C. | Process for regenerating foundry sand |
| DE2911259A1 (en) * | 1979-03-22 | 1980-10-02 | Shell Ag | Cleaning compsns. for boilers - contg. alkali metal iodate or periodate in alkaline soln. |
| US4847089A (en) * | 1986-07-16 | 1989-07-11 | David N. Kramer | Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same |
| WO1988009368A1 (en) * | 1987-05-19 | 1988-12-01 | Schamschula Gyoergy | Composition and process for cleaning of fire-side parts of firing devices |
| US5045121A (en) * | 1989-06-21 | 1991-09-03 | Gte Products Corporation | Method for removing carbon from cemented tungsten carbide articles |
| US5490947A (en) * | 1993-09-10 | 1996-02-13 | Cioffe; Anthony | Method for cleaning firearms and other metal ordnance |
| US20030106838A1 (en) * | 2001-12-12 | 2003-06-12 | Michael Siskin | Process for increasing yield in coking processes |
| US6860985B2 (en) | 2001-12-12 | 2005-03-01 | Exxonmobil Research And Engineering Company | Process for increasing yield in coking processes |
| CN107418614A (en) * | 2017-07-24 | 2017-12-01 | 天津大学 | Online decoking method for hydrocarbon fuel tubular cracking furnace |
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