US2206284A - Concentrated aqueous solutions of the ammonium salts of disubstituted dithiophosphoric acids - Google Patents
Concentrated aqueous solutions of the ammonium salts of disubstituted dithiophosphoric acids Download PDFInfo
- Publication number
- US2206284A US2206284A US300582A US30058239A US2206284A US 2206284 A US2206284 A US 2206284A US 300582 A US300582 A US 300582A US 30058239 A US30058239 A US 30058239A US 2206284 A US2206284 A US 2206284A
- Authority
- US
- United States
- Prior art keywords
- ammonium salts
- dithiophosphoric acids
- aqueous solutions
- acids
- concentrated aqueous
- 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
- 239000002253 acid Substances 0.000 title description 26
- 150000007513 acids Chemical class 0.000 title description 18
- 150000003863 ammonium salts Chemical class 0.000 title description 13
- 239000007864 aqueous solution Substances 0.000 title description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 239000000908 ammonium hydroxide Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005188 flotation Methods 0.000 description 6
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 3
- ZMTWSJBCWBBWLJ-UHFFFAOYSA-N di(pentan-2-yloxy)-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCC(C)OP(S)(=S)OC(C)CCC ZMTWSJBCWBBWLJ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- -1 di-substituted dithiophosphoric acids Chemical class 0.000 description 1
- 238000009291 froth flotation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Definitions
- the present invention relates to promoters for use in the froth flotation and mineral separation of sulflde ores and the like. More particularly it relates to concentrated aqueous solutions of the 5 ammonium salts ofdisubstituted dithiophosphoric acids and methods of preparation.
- dialkyl and/or dlaryl -dithiophosphoric acids have been used on a large scale for the flotation of various sulflde and precious metal ores for which they have been found to be very eflfective promoters. While these dlthiophosphoric acid derivatives are excellent promoters there are, however, certain undesirable factors.
- ammonium salts of these di-substituted dithiophosphoric acids are diflicult to prepare in the anhydrous form and usually occur in the form of either solids, pastes, or rather stiii jellies which are relatively unstable.
- ammonium salts in the form of solids or pastes are not only diflicult to prepare, but are diflicult to handle and to dissolve, disperse or dilute with water when it is desired to feed themn'nto a flotation.
- dithlophosphoric acids to render them less em as is practical (i. e., 28-30% m) in order that the product will contain a maximum and relaphoric acids can be prepared in a concentrated aqueous solution of uniform strength suitable for use, as a flotation reagent,and that the stability of such solutions is insured by maintaining an excess of ammonia.
- the excess ammonia while 5 it prevents the presence of any free disubstituted dithiophosphoric acids which would be hydrolyzed in the presence of water, does not interfere with the use of such solutions as flotationreagents.
- disubstituteddithiophosphoric acids such as diaryl dithiophosphoric acids or dialkyl dithiophosphoric acids are added to aqua ammonia (i. e., ammonium hydroxide containing 28-30% Nl-l'a) in quantities that will leave an excess of ammonium hydroxide after neutralizing 15 the acid, to give a stable concentrated aqueous solution of the ammonium salt.
- aqua ammonia i. e., ammonium hydroxide containing 28-30% Nl-l'a
- the concentrated aqueous solution so produced may be dissolved in water to give more dilute solutions which can be readily fed to an ore flotation circuit when such products are used as ore flotation tively uniform quantity of active ingredient.
- ammonium hydroxide solution employed preferably contains 28 to 30% NH: weaker 35 solutions may be used' and solutions containing only about 25% NH: have been found to produce satisfactory results.
- disubs'tituted dithiophosphoric acids used need not be amolutely pure but may be used in the crude form having im- 40 in connection with other promoters or collectors, to
- Example 1 100 grams of 26 B. aqua ammonia were placed in a 3 neck flask surrounded by acooling bath and fitted with a mechanical agitator, thdrmometer and dropping funnel. 500 grams of a crude mixture of approximately 80% diaryl dithiophosphoric acids (cresyl, xylenyl, etc.) and of free cresylic acid" were placed in the dropping funnel. The crude acid was added to Example 2 are limited to and include only such radicals when they are hydrocarbons.
- a composition of matter comprising a stable, concentrated, aqueous solution of the ammonium salts of at least one of the compounds included in the group consisting of dialkyl and diaryl dithiophosphoric acids, said solution containing an amount of ammonium hydroxide in excess of the amount required to neutralize the acid.
- a stable, concentrated, aqueous solution of the ammonium salt of a dialkyl dithiophosphoric acid said solution containing an amount of ammonium hydroxide in excess of the amount rethereby leaving a slight excess of ammonium hydroxide.
- alkyl and aryl* used in the claims 5. A method of preparing stable, concentrated, aqueous solutions or the ammonium salts of diaryl dithiophosphoric acids which comprise adding diaryl dithiophosphoric acids to ammonium hydroxide containing about 28% NH: in quantities insuflicient to neutralize the ammonia, thereby leaving a slight excess of ammonium hydroxide.
- a stable, concentrated, aqueous solution of the ammonium salt of dicresyl dithiophosphoric acid said solution containing an amount of am: monium hydroxide in excess of the amount required to neutralize the acid.
- a stable, concentrated, aqueous solution of the ammonium salt of di-secondary amyl dithiophosphoric acid said solution containing an amount ofammonium hydroxide in excess of the amount required to neutralize the acid.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Jul z, 1940 PATENT OFFICE CONCENTBATED AQUEOUS SOLUTIONS OF THE AMLIONIUM SALTS F DISUBSTI- TUTED DITHIOPHOSPHORIC ACIDS David W. Jayne, Jr., Old Greenwich, Conn, as-
signor to American Cyanamid Company, New
York, N. Y., a corporation of Maine Application October #1, 1939, Serial No. 309,582
No Drawing.
1 Claims. (01. zszs) The present invention relates to promoters for use in the froth flotation and mineral separation of sulflde ores and the like. More particularly it relates to concentrated aqueous solutions of the 5 ammonium salts ofdisubstituted dithiophosphoric acids and methods of preparation.
The dialkyl and/or dlaryl -dithiophosphoric acids have been used on a large scale for the flotation of various sulflde and precious metal ores for which they have been found to be very eflfective promoters. While these dlthiophosphoric acid derivatives are excellent promoters there are, however, certain undesirable factors.
, which accompany their use. For example, they are only slightly soluble in water and certain-of the dialkyl dlthiophosphoric acids are very corrosive and therefore require special containers and precaution in transportation, storage, handling, etc. Also water has a endency to cause rather rapid decomposition of the disubstituted cient as promoters and hence somewhat limits their use, particularly where it is desired to feed the reagent in the form of aqueous solutions, which presents important advantages.
To overcome the objectionable features of the disubstituted dithiophosphoric acids it has been proposed to use various salts of these acids, among which are the ammonium salts. There are, however, some undesirable properties possessed by certain of the ammonium salts which have not been satisfactorily solved heretofore. The ammonium salts of these di-substituted dithiophosphoric acids are diflicult to prepare in the anhydrous form and usually occur in the form of either solids, pastes, or rather stiii jellies which are relatively unstable. These ammonium salts in the form of solids or pastes are not only diflicult to prepare, but are diflicult to handle and to dissolve, disperse or dilute with water when it is desired to feed themn'nto a flotation.
dithlophosphoric acids to render them less em as is practical (i. e., 28-30% m) in order that the product will contain a maximum and relaphoric acids can be prepared in a concentrated aqueous solution of uniform strength suitable for use, as a flotation reagent,and that the stability of such solutions is insured by maintaining an excess of ammonia. The excess ammonia, while 5 it prevents the presence of any free disubstituted dithiophosphoric acids which would be hydrolyzed in the presence of water, does not interfere with the use of such solutions as flotationreagents.
In the preferred method of carrying out this 10 invention disubstituteddithiophosphoric acids, such as diaryl dithiophosphoric acids or dialkyl dithiophosphoric acids are added to aqua ammonia (i. e., ammonium hydroxide containing 28-30% Nl-l'a) in quantities that will leave an excess of ammonium hydroxide after neutralizing 15 the acid, to give a stable concentrated aqueous solution of the ammonium salt. The concentrated aqueous solution so produced may be dissolved in water to give more dilute solutions which can be readily fed to an ore flotation circuit when such products are used as ore flotation tively uniform quantity of active ingredient. While the ammonium hydroxide solution employed preferably contains 28 to 30% NH: weaker 35 solutions may be used' and solutions containing only about 25% NH: have been found to produce satisfactory results. 'The disubs'tituted dithiophosphoric acids used need not be amolutely pure but may be used in the crude form having im- 40 in connection with other promoters or collectors, to
trothers or the like, for example, the addition of a small amount of thiocarbanilid in many instances produces improved flotation results. The invention will'be further illustrated by the following examples which are included for purposes 01 illustration and the invention is not limited thereto.
Example 1 100 grams of 26 B. aqua ammonia were placed in a 3 neck flask surrounded by acooling bath and fitted with a mechanical agitator, thdrmometer and dropping funnel. 500 grams of a crude mixture of approximately 80% diaryl dithiophosphoric acids (cresyl, xylenyl, etc.) and of free cresylic acid" were placed in the dropping funnel. The crude acid was added to Example 2 are limited to and include only such radicals when they are hydrocarbons.
quired to neutralize the acid.
What I claim is: V
1. A composition of matter comprising a stable, concentrated, aqueous solution of the ammonium salts of at least one of the compounds included in the group consisting of dialkyl and diaryl dithiophosphoric acids, said solution containing an amount of ammonium hydroxide in excess of the amount required to neutralize the acid.
2. A stable, concentrated, aqueous solution of the ammonium salt of a dialkyl dithiophosphoric acid, said solution containing an amount of ammonium hydroxide in excess of the amount rethereby leaving a slight excess of ammonium hydroxide.
50 g. of 26 36. aqua ammonia were placed in a 3 neck flask fitted with a mechanical agitator, thermometer and dropping funnel and surrounded by a cooling bath. 200 g. of crude di-secondary amyl dithiophosphoric acid were placed in the dropping funnel and the acid added to the aqua ammonia, with agitation, at such a rate that the temperature of the batch was maintained between and 30 C. The product (aqueous ammonium salt of di-secondary amyl dithiophosphoric acid) was a clear dark yellowgreen, homogeneous liquid, containing about 18% water. The product readily dissolved in water to give a somewhat cloudy, dilute, alkaline soluq tion.
The term alkyl and aryl* used in the claims 5. -A method of preparing stable, concentrated, aqueous solutions or the ammonium salts of diaryl dithiophosphoric acids which comprise adding diaryl dithiophosphoric acids to ammonium hydroxide containing about 28% NH: in quantities insuflicient to neutralize the ammonia, thereby leaving a slight excess of ammonium hydroxide.
6. A stable, concentrated, aqueous solution of the ammonium salt of dicresyl dithiophosphoric acid, said solution containing an amount of am: monium hydroxide in excess of the amount required to neutralize the acid.
7. A stable, concentrated, aqueous solution of the ammonium salt of di-secondary amyl dithiophosphoric acid, said solution containing an amount ofammonium hydroxide in excess of the amount required to neutralize the acid.
' DAVID W. JAYNE, JR.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US300582A US2206284A (en) | 1939-10-21 | 1939-10-21 | Concentrated aqueous solutions of the ammonium salts of disubstituted dithiophosphoric acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US300582A US2206284A (en) | 1939-10-21 | 1939-10-21 | Concentrated aqueous solutions of the ammonium salts of disubstituted dithiophosphoric acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2206284A true US2206284A (en) | 1940-07-02 |
Family
ID=23159714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US300582A Expired - Lifetime US2206284A (en) | 1939-10-21 | 1939-10-21 | Concentrated aqueous solutions of the ammonium salts of disubstituted dithiophosphoric acids |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2206284A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476037A (en) * | 1945-04-05 | 1949-07-12 | Socony Vacuum Oil Co Inc | Wax-substituted diaryl dithiophosphoric acids and salts thereof |
| US2819232A (en) * | 1954-03-01 | 1958-01-07 | American Cyanamid Co | Dithiophosphate coating composition and process for preparing cellular resin therefrom |
| US3086653A (en) * | 1960-12-12 | 1963-04-23 | American Cyanamid Co | Concentrated aqueous solutions of alkali and alkaline earth metal salts of phospho-organic compounds |
| US3355017A (en) * | 1963-12-06 | 1967-11-28 | American Cyanamid Co | Method for effecting ore flotation |
| US3925218A (en) * | 1974-08-01 | 1975-12-09 | American Cyanamid Co | Concentration of ore by flotation with solutions of aqueous dithiophosphates and thionocarbamate as collector |
| US3971836A (en) * | 1974-08-16 | 1976-07-27 | Minerec Corporation | Amine-stabilized dialkyl dithiophosphates |
| US4036746A (en) * | 1974-08-16 | 1977-07-19 | Minerec Corporation | Flotation with amine-stabilized dialkyl dithiophosphates |
| US4261846A (en) * | 1979-07-23 | 1981-04-14 | United States Borax & Chemical Corporation | Composition for froth flotation of zinc sulfide |
| US4530758A (en) * | 1982-05-17 | 1985-07-23 | Thiotech, Inc. | Ore flotation method |
| US4879022A (en) * | 1987-07-14 | 1989-11-07 | The Lubrizol Corporation | Ore flotation process and use of mixed hydrocarbyl dithiophosphoric acids and salts thereof |
| US5082554A (en) * | 1990-06-15 | 1992-01-21 | The Lubrizol Corporation | Flotation process using metal salts of phosphorus acids |
| US5094746A (en) * | 1990-06-15 | 1992-03-10 | The Lubrizol Corporation | Flotation process using a mixture of collectors |
| US5147572A (en) * | 1990-06-15 | 1992-09-15 | The Lubrizol Corporation | Flotation composition using a mixture of collectors |
| US5189195A (en) * | 1991-07-30 | 1993-02-23 | Miles Inc. | Process for producing stable, low odor S,S,S-tributylphosphorotrithioate |
| WO1993017029A1 (en) * | 1992-02-28 | 1993-09-02 | The Lubrizol Corporation | Concentrated aqueous metal dithiophosphates and methods of using the same |
-
1939
- 1939-10-21 US US300582A patent/US2206284A/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2476037A (en) * | 1945-04-05 | 1949-07-12 | Socony Vacuum Oil Co Inc | Wax-substituted diaryl dithiophosphoric acids and salts thereof |
| US2819232A (en) * | 1954-03-01 | 1958-01-07 | American Cyanamid Co | Dithiophosphate coating composition and process for preparing cellular resin therefrom |
| US3086653A (en) * | 1960-12-12 | 1963-04-23 | American Cyanamid Co | Concentrated aqueous solutions of alkali and alkaline earth metal salts of phospho-organic compounds |
| US3355017A (en) * | 1963-12-06 | 1967-11-28 | American Cyanamid Co | Method for effecting ore flotation |
| US3925218A (en) * | 1974-08-01 | 1975-12-09 | American Cyanamid Co | Concentration of ore by flotation with solutions of aqueous dithiophosphates and thionocarbamate as collector |
| US3971836A (en) * | 1974-08-16 | 1976-07-27 | Minerec Corporation | Amine-stabilized dialkyl dithiophosphates |
| US4036746A (en) * | 1974-08-16 | 1977-07-19 | Minerec Corporation | Flotation with amine-stabilized dialkyl dithiophosphates |
| US4261846A (en) * | 1979-07-23 | 1981-04-14 | United States Borax & Chemical Corporation | Composition for froth flotation of zinc sulfide |
| US4530758A (en) * | 1982-05-17 | 1985-07-23 | Thiotech, Inc. | Ore flotation method |
| US4879022A (en) * | 1987-07-14 | 1989-11-07 | The Lubrizol Corporation | Ore flotation process and use of mixed hydrocarbyl dithiophosphoric acids and salts thereof |
| US5082554A (en) * | 1990-06-15 | 1992-01-21 | The Lubrizol Corporation | Flotation process using metal salts of phosphorus acids |
| US5094746A (en) * | 1990-06-15 | 1992-03-10 | The Lubrizol Corporation | Flotation process using a mixture of collectors |
| US5147572A (en) * | 1990-06-15 | 1992-09-15 | The Lubrizol Corporation | Flotation composition using a mixture of collectors |
| US5189195A (en) * | 1991-07-30 | 1993-02-23 | Miles Inc. | Process for producing stable, low odor S,S,S-tributylphosphorotrithioate |
| WO1993017029A1 (en) * | 1992-02-28 | 1993-09-02 | The Lubrizol Corporation | Concentrated aqueous metal dithiophosphates and methods of using the same |
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