USRE25394E - Corrosion-inhibited liquid fertilizer - Google Patents
Corrosion-inhibited liquid fertilizer Download PDFInfo
- Publication number
- USRE25394E USRE25394E US25394DE USRE25394E US RE25394 E USRE25394 E US RE25394E US 25394D E US25394D E US 25394DE US RE25394 E USRE25394 E US RE25394E
- Authority
- US
- United States
- Prior art keywords
- liquid fertilizer
- corrosion
- phosphate
- fluosilicate
- fertilizer compositions
- 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
Links
- 239000003337 fertilizer Substances 0.000 title description 32
- 239000007788 liquid Substances 0.000 title description 29
- 238000005260 corrosion Methods 0.000 title description 13
- 239000000203 mixture Substances 0.000 description 38
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- TWGUZEUZLCYTCG-UHFFFAOYSA-N Sodium fluorosilicate Chemical compound [Na+].[Na+].F[Si-2](F)(F)(F)(F)F TWGUZEUZLCYTCG-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 230000001264 neutralization Effects 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N Ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 239000005696 Diammonium phosphate Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 4
- 235000019838 diammonium phosphate Nutrition 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 orthophosphate ion Chemical class 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ITHIMUMYFVCXSL-UHFFFAOYSA-P Ammonium fluorosilicate Chemical compound [NH4+].[NH4+].F[Si-2](F)(F)(F)(F)F ITHIMUMYFVCXSL-UHFFFAOYSA-P 0.000 description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L Dipotassium phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M Monopotassium phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 231100000078 corrosive Toxicity 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- UUHPPUWEDCVPCO-UHFFFAOYSA-N dipotassium;hexafluorosilicon(2-) Chemical compound [K+].[K+].F[Si-2](F)(F)(F)(F)F UUHPPUWEDCVPCO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000885 phytotoxic Effects 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 210000003692 Ilium Anatomy 0.000 description 1
- 241000209082 Lolium Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- XLWGXJXTOLOMNF-UHFFFAOYSA-J P(=O)([O-])([O-])[O-].[Cl-].[N+](=O)([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Cl-].[N+](=O)([O-])[O-] XLWGXJXTOLOMNF-UHFFFAOYSA-J 0.000 description 1
- 240000007742 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 210000002700 Urine Anatomy 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000002939 deleterious Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
Definitions
- This invention relates to improved liquid fertilizer compositions which are characterized by a material reduction in the corrosion of storage containers and application equipment. More specifically this invention relates to corrosion-inhibited liquid fertilizer compositions which are suitably used in aluminum equipment.
- the substantially neutral liquid fertilizer compositions are generally formulated by various mixtures of monoammonium phosphate, diammonium phosphate, ammonium nitrate, ammonium sulfate, urea, potassium chloride, potassium nitrate, monopotassium phosphate, dipotassium phosphate and the like or by the use of anhydrous ammonia, aqua ammonia, phosphoric acid, potassium hydroxide and the like to directly produce a substantially neutral salt solution.
- the neutral liquid fertilizer solutions can be a solution of ammonium phosphate or ammonium phosphate to which has been added ammonium nitrate, urea, potassium chloride and the like to form a variety of N-P or NPK liquid fertilizers.
- the pH of the liquid fertilizer composition preferably ranges from about 6 to about 8.
- fertilizer compositions are conventionally labeled in terms of the principal nutrient com.- ponents therein, i.e. nitrogen, phosphorus and potassium, wherein phosphorus and potassium are given in terms of P 0 and K 0, respectively, and the N-PK designation hereinabove and hereinafter employed will be understood in these terms.
- the pH of the above formulations as a l to 10 dilution with water will vary between about 6 to about 8 and most will vary between about 6.5 to about 7.5.
- the subject liquid fertilizer compositions can also contain minor amounts of surfactants to facilitate the assimilation of the nutrient composition by the plant, minor amounts of essential trace elements in available form and the like.
- the desired liquid fertilizer composition can be formulated batchwise or by a continuous process as will be readily understood by those skilled in the art.
- EXAMPLE 1 Since the high phosphate content liquid fertilizer composition was found to cause the most severe corrosion rate of the various formulations, the 8-24-0 composition was selected such that the following evaluation results would generally exemplify the most drastic corrosive effects which might be met in the field.
- a liquid fertilizer composition (8-24-0) was prepared by dissolving 1.07 parts by weight of monoarnmonium phosphate and 328.1 parts by weight of diammonium phosphate in 564.9 parts by Weight of water. Similar" compositions were prepared which contained varying amounts of fluorine, as sodium fluosilicate, as a corrosion inhibitor in the said liquid fertilizer composition. The corrosion rates of the liquid fertilizer compositions on 350 aluminum at 140 F. are shown in the following table:
- a 3-9-9 formulation was prepared by dissolving 4 pounds of monoammonium phosphate, 12.3 pounds of diammonium phosphate and 14.5 of potassium chloride in 69.2 pounds of water per 100 pounds of liquid fertilizer composition and a 10-5-5 formulation was prepared by dissolving 2.2 pounds of monoammonium phosphate, 6.8 pounds of diammonium phosphate, 24 pounds of ammonium nitrate and 8.1 pounds of potassium chloride in 58.9 pounds of water per 100 pounds of liquid fertilizer composition.
- the aforesaid liquid fertilizer compositions were inhibited by the addition thereto of about 250 p.p.m. of fluorine as sodium fluosilicate and the rate of corrosion evaluated in the presence of 380 aluminum at about 140 F., it was found that the corrosion rate of each of said fertilizer compositions was reduced to substantially zero.
Description
United States Patent 25,394 CORROSION-INHIBITED LIQUID FERTILIZER COMPOSITIONS Carl Robert Martinson, Belleville, Ill., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporatlou of Delaware No Drawing. Original No. 3,024,099, dated Mar. 6, 1962, Ser. No. 660,038, May 20, 1957. Application for reissue Sept. 26, 1962, Ser. No. 228,214
This invention relates to improved liquid fertilizer compositions which are characterized by a material reduction in the corrosion of storage containers and application equipment. More specifically this invention relates to corrosion-inhibited liquid fertilizer compositions which are suitably used in aluminum equipment.
An early source of nitrogen in agricultural application was the use of ammonium nitrate solutions. The ammonium nitrate solutions were generally held in aluminum storage tanks and dispensed in the field with aluminum equipment. Accordingly, the industry has a considerable present investment in aluminum storage vessels and application equipment. In recent years there has been a Re. 25,394 Reissuecl June 11, 1963 "ice preferred suitable fiuosilicates are sodium fluosilicate, ammonium fluosilicate and potassium fiuosilicate.
The substantially neutral liquid fertilizer compositions are generally formulated by various mixtures of monoammonium phosphate, diammonium phosphate, ammonium nitrate, ammonium sulfate, urea, potassium chloride, potassium nitrate, monopotassium phosphate, dipotassium phosphate and the like or by the use of anhydrous ammonia, aqua ammonia, phosphoric acid, potassium hydroxide and the like to directly produce a substantially neutral salt solution. Thus the neutral liquid fertilizer solutions can be a solution of ammonium phosphate or ammonium phosphate to which has been added ammonium nitrate, urea, potassium chloride and the like to form a variety of N-P or NPK liquid fertilizers. The pH of the liquid fertilizer composition preferably ranges from about 6 to about 8.
As is well known, fertilizer compositions are conventionally labeled in terms of the principal nutrient com.- ponents therein, i.e. nitrogen, phosphorus and potassium, wherein phosphorus and potassium are given in terms of P 0 and K 0, respectively, and the N-PK designation hereinabove and hereinafter employed will be understood in these terms.
Various illustrative neutral liquid fertilizer compositions are shown in the following table wherein the various components are indicated in parts by weight.
Phos- M ono- Diam- Ammo- Ammophorlc ammomonlum Potas- Potas- No. lN-P-k Ammonia mum Ilium Urea acid niurn phossium sium lTVuter nitrate sulfate (75%) phosphate chloride nitrate phate growing demand for liquid fertilizers generally, i.e. fertilizer compositions which also contain P 0 with or without K 0 to provide a complete liquid formulation. However it was found that the presence of liquid fertilizer compositions containing P 0 caused excessive corrosion to the aluminum equipment which was then in wide use.
It is the principal object of this invention to provide a substantially neutral liquid fertilizer composition con taining P 0 which can be stored and dispensed with aluminum equipment. Another object of this invention is to provide a substantially neutral liquid fertilizer composition containing P 0 which is characterized by a low rate of corrosion when employed with aluminum equipment. Other objects will be apparent from the following disclosure.
It has now been found that from about 200 up to about 500 ppm. of fluoride as a soluble fiuosilicate when present in substantially neutral liquid fertilizer compositions containing the phosphate nutrient, i.e. the orthophosphate ion, provides a liquid fertilizer composition which can be employed in aluminum equipment. The
The pH of the above formulations as a l to 10 dilution with water will vary between about 6 to about 8 and most will vary between about 6.5 to about 7.5.
The subject liquid fertilizer compositions can also contain minor amounts of surfactants to facilitate the assimilation of the nutrient composition by the plant, minor amounts of essential trace elements in available form and the like. The desired liquid fertilizer composition can be formulated batchwise or by a continuous process as will be readily understood by those skilled in the art.
The following examples are illustrative of the instant invention.
EXAMPLE 1 Since the high phosphate content liquid fertilizer composition was found to cause the most severe corrosion rate of the various formulations, the 8-24-0 composition was selected such that the following evaluation results would generally exemplify the most drastic corrosive effects which might be met in the field.
A liquid fertilizer composition (8-24-0) was prepared by dissolving 1.07 parts by weight of monoarnmonium phosphate and 328.1 parts by weight of diammonium phosphate in 564.9 parts by Weight of water. Similar" compositions were prepared which contained varying amounts of fluorine, as sodium fluosilicate, as a corrosion inhibitor in the said liquid fertilizer composition. The corrosion rates of the liquid fertilizer compositions on 350 aluminum at 140 F. are shown in the following table:
I.p.rn, fln- Rate oi eor- N0. urine as rosiun (mils/ N mSiFn year) It was also found that the presence of minor amounts of the sodium fluosilicate was beneficial even in the less corrosive liquid fertilizer compositions. Thus a 3-9-9 formulation was prepared by dissolving 4 pounds of monoammonium phosphate, 12.3 pounds of diammonium phosphate and 14.5 of potassium chloride in 69.2 pounds of water per 100 pounds of liquid fertilizer composition and a 10-5-5 formulation was prepared by dissolving 2.2 pounds of monoammonium phosphate, 6.8 pounds of diammonium phosphate, 24 pounds of ammonium nitrate and 8.1 pounds of potassium chloride in 58.9 pounds of water per 100 pounds of liquid fertilizer composition. When the aforesaid liquid fertilizer compositions were inhibited by the addition thereto of about 250 p.p.m. of fluorine as sodium fluosilicate and the rate of corrosion evaluated in the presence of 380 aluminum at about 140 F., it was found that the corrosion rate of each of said fertilizer compositions was reduced to substantially zero.
Qualitative and quantitative evaluation of the liquid fertilizer compositions containing up to 500 p.p.m. of fluorine as sodium fiuosilicate conclusively demonstrated that the inhibited fertilizer compositions produced no phytotoxic effect on the germination or growth of radish, cucumber, tomato and rye grass seeds.
The aforesaid a plants do not have particularly hardy seedlings, accordingly, it can be reasonably concluded that since the inhibited formulation exhibits no deleterious effects to these seedlings, it can be safely used with any seedlings and/or plants. However, it is recommended that concentrations greater than 500 p.p.m. of fluorine should be avoided as such solutions may be phytotoxic to some plants.
What is claimed is:
I. A process for inhibiting the corrosion of aluminum by aqueous liquid fertilizer compositions having a pH between about 6 and about 8 and containing an inorganic orthophosphate salt selected from the group consisting of monoammom'um orthophosphate, diammonium orthophosphate, monopotassium orthophosphate and dipotassium orthophosphate, said process comprising the incorporation therein of an eflective corrosion inhibiting amount of a soluble fluosilicate compound selected from the group consisting of sodium fluosilicate, potassium fluosilicate and ammonium fluosilicate.
2. A process as in claim 1, wherein said fluosilicate compound is sodium fluosilicate.
3 [1]. A method of inhibiting the corrosion of aluminum equipment by aqueous, liquid fertilizer compositions having a pH between about 6 and about 8 and containing an inorganic orthophosphate salt selected from the group consisting of monoammonium orthophosphate, diamrnonium orthophosphate, monopotassium orthophosphate, and dipotassium orthophosphate, said method comprising the incorporation therein of from about 200 to about 500 p.p.m. of fluorine as a soluble fluosilicate compound selected from the group consisting of sodium fluosilicate, potassium fluosilicate, and ammonium fluosilicate.
4 [2]. The method of claim 3 [1], wherein about 500 p.p.m. fluorine as sodium fluosilicate is employed.
References Cited in the file of this patent or the origmal patent UNITED STATES PATENTS 2,028,343 Michel Jan. 21, 1936 2,238,651 Keenan Apr. 15, 1941 2,586,709 Phillips Feb. 19, 1952 2,719,781 Hesch Oct. 4, 1955 2,732,290 Vana et a1 Jan. 24, 1956 2,739,886 Facer Mar. 27, 1956 2,778,712 Caldwell Jan. 22, 1957 FOREIGN PATENTS 736,215 Great Britain Sept. 7, 1955
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE25394E true USRE25394E (en) | 1963-06-11 |
Family
ID=2094227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US25394D Expired USRE25394E (en) | Corrosion-inhibited liquid fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE25394E (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223649A (en) * | 1962-11-06 | 1965-12-14 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
| US3275566A (en) * | 1965-09-16 | 1966-09-27 | Monsanto Co | Corrosion-inhibited phosphate solutions |
| US3293189A (en) * | 1962-11-06 | 1966-12-20 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
| US3338829A (en) * | 1964-05-06 | 1967-08-29 | Monsanto Co | Corrosion-inhibited ammonium orthophosphate solutions and compositions useful for manufacturing them |
| US3342749A (en) * | 1964-06-02 | 1967-09-19 | Monsanto Co | Corrosion inhibited phosphate solutions |
| US3364149A (en) * | 1964-05-13 | 1968-01-16 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
-
0
- US US25394D patent/USRE25394E/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3223649A (en) * | 1962-11-06 | 1965-12-14 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
| US3293189A (en) * | 1962-11-06 | 1966-12-20 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
| US3338829A (en) * | 1964-05-06 | 1967-08-29 | Monsanto Co | Corrosion-inhibited ammonium orthophosphate solutions and compositions useful for manufacturing them |
| US3364149A (en) * | 1964-05-13 | 1968-01-16 | Monsanto Co | Corrosion-inhibited phosphate solutions and compositions useful for manufacturing them |
| US3342749A (en) * | 1964-06-02 | 1967-09-19 | Monsanto Co | Corrosion inhibited phosphate solutions |
| US3275566A (en) * | 1965-09-16 | 1966-09-27 | Monsanto Co | Corrosion-inhibited phosphate solutions |
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