US2902511A - Oil additive and process for its preparation - Google Patents
Oil additive and process for its preparation Download PDFInfo
- Publication number
- US2902511A US2902511A US610396A US61039656A US2902511A US 2902511 A US2902511 A US 2902511A US 610396 A US610396 A US 610396A US 61039656 A US61039656 A US 61039656A US 2902511 A US2902511 A US 2902511A
- Authority
- US
- United States
- Prior art keywords
- alkali metal
- sulfonate
- alkaline earth
- salt
- pounds
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/62—Sulfonated fats, oils or waxes of undetermined constitution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
Definitions
- alkaline earth metal alkylaryl sulfonates and particularly alkaline earth metal petroleum or mahogany sulfonates, may be prepared and loaded with extremely high alkaline reserve in essentially a single operation.
- an alkali metal petroleum sulfonate otherwise known as a mahogany sulfonate, is heated with an aqueous solution of an alkaline earth metal halide and an aqueous solution of either an alkali metal carbonate or an alkali metal borate to simultaneously form the alkaline earth metal petroleum sulfonate and load it with increased alkalinity.
- the alkali metal petroleum sulfonate otherwise known as a mahogany sulfonate
- alkaline earth metal halide functions to provide the alkaline earth content of the sulfonate and the alkali metal salt, specifically the carbonate or the borate, is used to provide the alkaline reserve-bearing compound.
- the reaction between these reagents and the alkali metal sulfonate forms a connecting bridge of alkaline reserve radicals between the alkaline earth sulfonate groups that are formed.
- the alkali metal sulfonate such as theordinary sodium mahogany sulfonate of com merce
- an alkaline earth metal halide such as the halides of calcium, mang'anese, strontium, or barium
- an alkali metal carbonate or. an alkali metal borate an alkali metal carbonate or. an alkali metal borate.
- the resulting product or complex has up to three times or more as much alkaline earth metal content as that of a neutral alkaline earth metal mahogany sulfonate. This value is expressed as having a loading value of 3-1, being three times that of the neutral sulfonate.
- a suitable alkaline earth metal halide is calcium chloride because of its availability, inexpensiveness, and gen: erally satisfactory results.
- the aqueous solution of the alkaline earth metal halide and the aqueous solution of either alkali metal carbonate or borate are added preferably simultaneously in separate batches to the alkali metal petroleum sulfonate, preferably diluted with a neutral oil while agitating the sulfonate and while the sul- 5 fonate and oil mixture is at a temperature between about 180-210 F.
- the heat is continued at a temperature that is above about 200 F. until substantially all of the water has been driven off.
- the heating temperature is preferably above 0 about 240 F.
- alkaline earth metal halide and alkali metal carbonate or borate used to react with the sodium sulfonate' is preferably from 2-5 times the amount of the sulfonate on an equivalent weight basis.
- the metal ratio is 2 to 1 and one mol of CaCO as' alkaline reserve .is available. However, for a safety factor in heavy duty oils, it is preferred to use a 3 to 2 mol ratio:
- Example 1 1428 pounds of sodium sulfonate of about 3.5%
- sodium content are blended with 1428 pounds of a lubricating oil stock such as l00@100 neutral in a kettle of suitable size equipped with means of heating and stirring. The mixture is then heated.
- a lubricating oil stock such as l00@100 neutral
- a good example of the latter class is the alkali metal borate such as borax.
- Example 2 1428 pounds of sodium sulfonate (Na content approximately 3.5%) and 1428 pounds of the above neutral lubricating stock are blended with heating and stirring in a blending kettle.
- ISO- F an aqueous solution of 763 pounds borax in sufiicient water to effect complete solution and an aqueous solution of 333 pounds anhydrous CaCl in 1,000 pounds of water are added simultaneously and separately in the same manner as in Example 1 with the exception that no CO is employed. Heating and stirring are continued to expel water exactly as in Example 1 and the resultant product is filtered.
- This product has the formula Ca(SO R) 2CaB O- and is a bright viscous dark-colored oil-soluble compound.
- the oxidation inhibitor thathas heretofore been added as a separate ingredient maybe introduced .byincorporating a dithiophosphate in the sulfonate molecule itself.
- Example 3 V 1428 pounds of sodium sulfonate (-Na content about 3.5% and 1428 pounds neutralllubricatin'g stock were blended as in the other examples.
- 55S pounds anhydrous CaCl were dissolved in 1,000 pounds water.
- 222.3 pounds'P S were added slowly to a Solution off159 pounds anhydrous Na CO in 75 0pounds water at boiling temperature. A.vigo;rous reaction ensued, with a'result ant dark brownish green solution.
- 265 pounds anhydrous Na CO were dissolved in 7 50 pound's water.
- the mass is heated with constant agitation to 380 400 F. to remove the water, then filtered.
- the additives of this invention may be added to any of the ordinary petroleum lubricating oils by primarily heating and stirring the mixture of oil and additive until the additive is dissolved.
- the amount of additive employed may be any amount up to about 20% by weight of the oil. A satisfactory amount has been found to be about 5%. All percentages expressed herein are by weight.
- a novel method of making an additive for a lubricating oil which comprises: (a) concurrently introducing into a quantity of an alkali metal petroleum sulfonate two separate salt solutions, the first of said salt solutions consisting of an aqueous solution of an alkaline earth metal halide and the second of said salt solutions consisting of an aqueous solution of an alkali metal salt selected from the group consisting of an alkali metal carbonate and an alkali metal borate, (b) admixing said salt solutions with said sulfonate, (c) the molar ratio of the said alkaline earth metal halide to the member selected from the group consisting of alkali metal carbonate and alkali metal borate being (N-l-l): N, where N is the number of mols of the alkali metal salt, (d) heating said admixture of materials sufliciently to maintain a temperature above about 200 F. and for a period of time sufliciently long to drive ofi? all the water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Description
United s a Patent 011. ADDITIVE AND PROCESS FOR ITS PREPARATION Thaddeus W. Culmer, R0binson, 11]., assignor to Hall Stewart No Drawing. Application September 17,1956
Serial N0. 610,396
7 Claims. (Cl. 260-504) I have discovered that alkaline earth metal alkylaryl sulfonates, and particularly alkaline earth metal petroleum or mahogany sulfonates, may be prepared and loaded with extremely high alkaline reserve in essentially a single operation. In this method, an alkali metal petroleum sulfonate, otherwise known as a mahogany sulfonate, is heated with an aqueous solution of an alkaline earth metal halide and an aqueous solution of either an alkali metal carbonate or an alkali metal borate to simultaneously form the alkaline earth metal petroleum sulfonate and load it with increased alkalinity. In this method, the
alkaline earth metal halide functions to provide the alkaline earth content of the sulfonate and the alkali metal salt, specifically the carbonate or the borate, is used to provide the alkaline reserve-bearing compound. The reaction between these reagents and the alkali metal sulfonate forms a connecting bridge of alkaline reserve radicals between the alkaline earth sulfonate groups that are formed. I
' In preparing the oil additive, the alkali metal sulfonate, such as theordinary sodium mahogany sulfonate of com merce, is mixed preferably simultaneously with two separate portions of an aqueous solution of an alkaline earth metal halide, such as the halides of calcium, mang'anese, strontium, or barium, and an aqueous solution of either an alkali metal carbonate or. an alkali metal borate. These twosolutionsare preferably added while the alkali metal petroleum sulfonate is maintained at an elevated temperature, preferably between about 180-210 F. The resulting mixture is then heated at a temperature above about 200 F. until substantially all of the water has been driven off. When this procedure is followed, the resulting product or complex has up to three times or more as much alkaline earth metal content as that of a neutral alkaline earth metal mahogany sulfonate. This value is expressed as having a loading value of 3-1, being three times that of the neutral sulfonate.
. A suitable alkaline earth metal halide is calcium chloride because of its availability, inexpensiveness, and gen: erally satisfactory results. The aqueous solution of the alkaline earth metal halide and the aqueous solution of either alkali metal carbonate or borate are added preferably simultaneously in separate batches to the alkali metal petroleum sulfonate, preferably diluted with a neutral oil while agitating the sulfonate and while the sul- 5 fonate and oil mixture is at a temperature between about 180-210 F. After the addition has been completed, the heat is continued at a temperature that is above about 200 F. until substantially all of the water has been driven off. The heating temperature is preferably above 0 about 240 F. up to a maximum of about 350400 F. The amounts of alkaline earth metal halide and alkali metal carbonate or borate used to react with the sodium sulfonate'is preferably from 2-5 times the amount of the sulfonate on an equivalent weight basis. The mechanics of the various reactions involved are believed to be as follows with calcium chloride being used as an example of the alkaline earth metal halide, sodium carbonate as an example of the alkali metal carbonate, and sodium borate or borax as the alkali metal borate, and the sodium mahogany sulfonate being expressed as NaOSO R: If an excess of CaCl is added to Na CO in solution, momentarily an intermediate com, pound is apparently formed before the resolution to the end product CaCO -for instance: I
2CaCl +Na CO =CaCl CaCO +2NaCl structurally illustrated, this is as follows:
C l-Ca This in turn appears to react with sodium sulfonate in this manner:
CaCl CaCO +2NaOSO R=Ca(OSO R) CaCO '+2NaCl The structural formula is believed to be as follows:
The metal ratio is 2 to 1 and one mol of CaCO as' alkaline reserve .is available. However, for a safety factor in heavy duty oils, it is preferred to use a 3 to 2 mol ratio:
On reaction with 2 mols of sodium sulfonate, the following appears to take place:
CaCl 2CaCO +2NaOSO R=CaOSO R2CaCO -l-2NaCl The structure of this compound is as follow: 5
be obvious that higher metal ratios may be secured by increasing the CaCl and Na CO quantities, limited only by the stability of the carbonate-calcium chain. Thus it is apparent that when the metal ratio is to be increased, a molar excess of the alkaline earth metal halide (A.E.M.H.) should be maintained over the other two ingredients; namely, the alkali metal carbonate or borate .(AMC-B) and the alkali metal petroleum sulfonate (AMPS). Expressed as a formula where N equals the molar proportions, N similarly indicates as N the metal reserve, thus:
N(AEMH) (N-l) (AMC-B) +(N-1) (AMPS) =N:1 Metal Reserve Ratio.
Example 1 1428 pounds of sodium sulfonate of about 3.5%
sodium content are blended with 1428 pounds of a lubricating oil stock such as l00@100 neutral in a kettle of suitable size equipped with means of heating and stirring. The mixture is then heated.
When the temperautre of the agitated mass has reached 180-190 F., 333 pounds of anhydrous CaCl dissolved in 1,000 pounds of water, and 212 pounds of anhydrous Na CO dissolved in 1,000 pounds of water are added simultaneously and at the same rate, taking care that the solutions do not come in contact before entering the oil sulfonate mixture, and that they enter the oil as near the middle of the vortex of the agitation as possible. As soon as both solutions are in the mix, CO is introduced near the bottom of the kettle and allowed to bubble slowly through the mix throughout the operation. About pounds is sufficient for a batch of this size, and serves tovmainta'in the balance of CO in the carbonate during processing. Although the use of CO is .preferre.d, lit.is not absolutely necessary.
Stirring and heating are continued until thetemperature has reached 380 F., at which .point the water is substantially removed. The product is then filtered.
The theoretical Ca content of Ca(SO R)2CaCO in a l to l dilution with mineral oil is 3.93%. Repeated batches made by the method described above have shown a Ca content of around 4% It will be obvious to 'those skilled in the art that the carbonate-calcium chain can be lengthened to give yet greater calcium content, and that many anions other than the carbonate may be employed. These anions, however, to be of practical benefit, must be polybasic and weak enough that their presence in the oil in the free state will not destroy the basicity of the calcium cation.
A good example of the latter class is the alkali metal borate such as borax.
Example 2 1428 pounds of sodium sulfonate (Na content approximately 3.5%) and 1428 pounds of the above neutral lubricating stock are blended with heating and stirring in a blending kettle. At ISO- F. an aqueous solution of 763 pounds borax in sufiicient water to effect complete solution and an aqueous solution of 333 pounds anhydrous CaCl in 1,000 pounds of water are added simultaneously and separately in the same manner as in Example 1 with the exception that no CO is employed. Heating and stirring are continued to expel water exactly as in Example 1 and the resultant product is filtered.
This product has the formula Ca(SO R) 2CaB O- and is a bright viscous dark-colored oil-soluble compound.
On analysis this compound showed 3.79% Ca, 2.65% B, and had a sulfated ash of 21.35%.
Theoretical: 3.70 Ca 2.65 B.
The structural formula is believed to be as follows:
' Cat-O- In the foregoing, it is readily seen that an important feature of the invention is the conversion of sodium to calcium sulfonate and the creation of alkaline reserve in the same operation without the aid of alkaline earth oxides or hydroxides.
The oxidation inhibitor thathas heretofore been added as a separate ingredient maybe introduced .byincorporating a dithiophosphate in the sulfonate molecule itself.
Example 3 V 1428 pounds of sodium sulfonate (-Na content about 3.5% and 1428 pounds neutralllubricatin'g stock were blended as in the other examples. 55S pounds anhydrous CaCl were dissolved in 1,000 pounds water. 222.3 pounds'P S were added slowly to a Solution off159 pounds anhydrous Na CO in 75 0pounds water at boiling temperature. A.vigo;rous reaction ensued, with a'result ant dark brownish green solution. 265 pounds anhydrous Na CO were dissolved in 7 50 pound's water.
At 1:80190 F., the CaCl and NagCO solutions were added simultaneously to 'the agitating oil vsulfonate mass, and immediately after, the P S Na5CO3 solution was added as quickly as possible, the speed being gov= erned by the foaming of the mass, which makes it necessary to add the solution in small portions.
As before, the mass is heated with constant agitation to 380 400 F. to remove the water, then filtered.
The resultant product was a bright, dark-colored oilsoluble product which gave the following analysis:
Ca 5.7% P 2.315%
The detailed combination of the Ca is:
1.5% is thiophosphate 1.28% is neutral sulfonate 2.92% is alkaline reserve Due to the fact that the principal reactions of converting the sodium mahogany sulfonate to the alkaline earth metal sulfonate and loading it with alkaline reserve takes place in a simple reaction, it appears evident that the method of this invention lends itself readily to the continuous production of the alkaline loaded sulfonates.
The additives of this invention may be added to any of the ordinary petroleum lubricating oils by primarily heating and stirring the mixture of oil and additive until the additive is dissolved. In general, the amount of additive employed may be any amount up to about 20% by weight of the oil. A satisfactory amount has been found to be about 5%. All percentages expressed herein are by weight.
Having described my invention as related to the embodiments set out herein, it is my intention that the invention be not limited by any of the details of description unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the accompanying claims.
I claim:
1. A novel method of making an additive for a lubricating oil which comprises: (a) concurrently introducing into a quantity of an alkali metal petroleum sulfonate two separate salt solutions, the first of said salt solutions consisting of an aqueous solution of an alkaline earth metal halide and the second of said salt solutions consisting of an aqueous solution of an alkali metal salt selected from the group consisting of an alkali metal carbonate and an alkali metal borate, (b) admixing said salt solutions with said sulfonate, (c) the molar ratio of the said alkaline earth metal halide to the member selected from the group consisting of alkali metal carbonate and alkali metal borate being (N-l-l): N, where N is the number of mols of the alkali metal salt, (d) heating said admixture of materials sufliciently to maintain a temperature above about 200 F. and for a period of time sufliciently long to drive ofi? all the water, and (e) recovering the resulting product.
2. The method according to claim 1, wherein the temperature of the alkali metal sulfonate is maintained between about 180 and 200 F. while said two solutions are being added.
3. The method according to claim 1 wherein the alkali metal carbonate is sodium carbonate.
4. The method according to claim 1 wherein the alkali metal borate is sodium borate.
5. The method according to claim 1 wherein said admixture is heated to a temperature between 200 F. and 400 F.
6. The method according to claim 1 wherein the alkali metal sulfonate is diluted with a neutral oil prior to admixing with said solutions.
7. The oil additive prepared by the method of claim 1.
References Cited in the file of this patent UNITED STATES PATENTS 2,767,209 Assetf et al. Oct. 16, 1956 2,794,829 Waarden et al. June 4, 1957 FOREIGN PATENTS 721,886 Great Britain Jan. 12, 1955 202,606 Australia Apr. 28, 1955
Claims (1)
1. A NOVEL METHOD OF MAKING AN ADDITIVE FOR A LUBRICATING OIL WHICH COMPRISES: (A) CONCURRENTLY INTRODUCING INTO A QUANTITY OF AN ALKALI METAL PETROLEUM SULFONATE TWO SEPARATE SALT SOLUTIONS, THE FIRST OF SAID SALT SOLUTION CONSISTING OF AN AQUEOUS SOLUTION OF AN ALKALINE EARTH METAL HALIDE AND THE SECOND OF SAID SALT SOLUTIONS CONSISTING OF AN AQUEOUS SOLUTION OF AN ALKALI METAL SALT SELECTED FROM THE GROUP CONSISTING OF AN ALKALI METAL CARBONATE AND AN ALKALI METAL BORATE, (B) ADMIXING SAID SALT SOLUTIONS WITH SAID SULFONATE, (C) THE MOLAR RATIO OF THE SAID ALKALINE EARTH METAL HALIDE TO THE MEMBER SELECTED FROM THE GROUP CONSISTING OF ALKAKLI METAL CARBONATE AND ALKALI METAL BORATE BEING (N+1): N, WHERE N IS THE NUMBER OF MOLS OF THE ALKALI METAL SALT, (D) HEATING SAID ADMIXTURE OF MATERIALS SUFFICIENTLY TO MAINTAIN A TEMPERATURE ABOVE ABOUT 200* F. AND FOR A PERIOD OF TIME SUFFICIENTLY LONG TO DRIVE OFF ALLTHE WATER, AND (E) RECOVERING THE RESULTING PRODUCT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US610396A US2902511A (en) | 1956-09-17 | 1956-09-17 | Oil additive and process for its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US610396A US2902511A (en) | 1956-09-17 | 1956-09-17 | Oil additive and process for its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2902511A true US2902511A (en) | 1959-09-01 |
Family
ID=24444848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US610396A Expired - Lifetime US2902511A (en) | 1956-09-17 | 1956-09-17 | Oil additive and process for its preparation |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2902511A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3055829A (en) * | 1958-07-07 | 1962-09-25 | Texaco Inc | Method of incorporating metal complexes in a base oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB721886A (en) * | 1950-12-29 | 1955-01-12 | Bataafsche Petroleum | Processes for the preparation of basic alkaline earth metal petroleum sulphonates |
| US2767209A (en) * | 1952-11-03 | 1956-10-16 | Lubrizol Corp | Complexes of dissimilar metals and methods of making same |
| US2794829A (en) * | 1953-02-17 | 1957-06-04 | Shell Dev | Preparation of basic polyvalent metal salts of organic sulfonic acids |
-
1956
- 1956-09-17 US US610396A patent/US2902511A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB721886A (en) * | 1950-12-29 | 1955-01-12 | Bataafsche Petroleum | Processes for the preparation of basic alkaline earth metal petroleum sulphonates |
| US2767209A (en) * | 1952-11-03 | 1956-10-16 | Lubrizol Corp | Complexes of dissimilar metals and methods of making same |
| US2794829A (en) * | 1953-02-17 | 1957-06-04 | Shell Dev | Preparation of basic polyvalent metal salts of organic sulfonic acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3055829A (en) * | 1958-07-07 | 1962-09-25 | Texaco Inc | Method of incorporating metal complexes in a base oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3560389A (en) | Liquid detergent bleach composition | |
| US2535101A (en) | Sulfonate base lubricating grease | |
| KR940011358A (en) | Process for preparing potassium tetrafluoroaluminate or potassium hexafluoroaluminate | |
| US2902511A (en) | Oil additive and process for its preparation | |
| US3132068A (en) | Solid alkali iodide compositions and process for producing the same | |
| US4021460A (en) | Method for manufacturing α-sulfo fatty acid ester salt | |
| US2145015A (en) | Dry disinfecting composition and method of making the same | |
| US3047509A (en) | Process for preparing a mixture of soap and fatty-acyl-aminomethane sulfonate | |
| US3925230A (en) | Non-caking laundry sour | |
| US2845340A (en) | Method of making complex fertilizer | |
| JPS57111396A (en) | Lithium-containing grease composition | |
| US2791562A (en) | Method of producing dry detergent | |
| US3325413A (en) | Process of producing detergent compositions containing alkali metal silicates | |
| DK152377B (en) | WATER-FREE HANDWASH WASTE | |
| US2802847A (en) | Basic zirconyl soaps and method for preparing the same | |
| DE2136672A1 (en) | Washing and cleaning compsns - contg as builders water-soluble salts of polymeric alpha-hydroxy or alpha-amino-acrylic acids | |
| US2556959A (en) | Dentifrice and method of preparing same | |
| SU418263A1 (en) | EXOTHERLIC SLAG FORMULATING STEEL MIXTURE | |
| CA1051617A (en) | Non-caking laundry sour | |
| EP0071021B1 (en) | Use of sodium triphosphate for preparing washing compositions | |
| US2116884A (en) | Manufacture of lead-manganese | |
| US431044A (en) | Oscae | |
| US1625483A (en) | Casein glue | |
| US2454736A (en) | Alkaline earth metal petroleum sulfonate compositions | |
| US1555796A (en) | Manufacture of sodium formate from carbon monoxide |