WO2016168112A1 - Reduced freezing temperature phosphoric acid compositions and methods - Google Patents
Reduced freezing temperature phosphoric acid compositions and methods Download PDFInfo
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- WO2016168112A1 WO2016168112A1 PCT/US2016/026904 US2016026904W WO2016168112A1 WO 2016168112 A1 WO2016168112 A1 WO 2016168112A1 US 2016026904 W US2016026904 W US 2016026904W WO 2016168112 A1 WO2016168112 A1 WO 2016168112A1
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- WIPO (PCT)
- Prior art keywords
- phosphoric acid
- phosphates
- phosphate
- alkalin
- additive
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
Definitions
- the present disclosure relates to compositions and methods for phosphoric acid compositions having a reduced freezing temperature compared to neat phosphoric acid.
- the freezing of the phosphoric acid is reduced by combining the phosphoric acid with an additive that reduces the freezing of the phosphoric acid composition.
- Phosphoric Acid has a typical concentration of 75, 80 and 85%.
- One of the drawbacks of phosphoric acid is that, as its concentration increases, its freezing temperature also increases. As a result, the main strength of acid used for various applications remains 75%wt which freezes at -18C; as it is easier to handle and store during cold season. A considerable amount of phosphoric acid is being transported and stored every year in large quantities, mainly at 75% or sometimes but more rarely, at 85%, requiring heating equipment to prevent solidification.
- Typical phosphoric acid at 85% concentration freezes below 21.1 °C or 70°F which limit its usage during cooler season or requires permanent heating system to avoid crystal formation; when crystal formation occurs, it causes delays in manufacturing processes where it is used and ultimately has a significant cost impact.
- the present disclosure is directed to phosphoric acid compositions having a reduced freezing temperature compared to neat phosphoric acid.
- the reduction in freezing temperature is obtained by combining the phosphoric acid with an additive that reduces the freezing temperature of the phosphoric acid composition.
- the increase in the freezing temperature of the phosphoric acid, at a designated concentration, is caused by a reduction of phosphoric acid solubility.
- Any additive that can cause solvation and/or partial neutralization of the phosphoric acid without the addition of water may be used, therefore increasing solubility of the crystals at a lower temperature.
- the additive could be formed in situ by adding the related alcohol of the phosphoric acid ester.
- the invention is directed to a low freezing temperature phosphoric acid composition including phosphoric acid having an acid
- the additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid,
- alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
- the invention is directed to a method to prepare low freezing temperature phosphoric acid composition including the steps of
- a phosphoric acid having an acid concentration of between 50% and 95% by weight expressed as H 3 PO 4 content and from about 0.01% by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid.
- FIG. 1 illustrates a comparison of the freezing temperatures of typical 75% acid, typical 85% and the phosphoric acid composition of the present invention.
- the present invention is directed to compositions and methods of a
- phosphoric acid composition which provides reduced freezing compared to neat phosphoric acid, and in addition, provides improved storage, handling and reduces freight cost.
- the phosphoric acid composition of the present invention will not freeze during extreme cold temperature, allowing manufacturing operations to continue in contrast to competitive composition in the art. In addition, this will also provide decreased freight cost over time as heat is not required in transport or use.
- the invention is directed to a low freezing temperature phosphoric acid composition including phosphoric acid having an acid
- the additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tributylphosphate, dibutyl butyl phosphonate , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals
- the phosphoric acid composition (referred to as LT-85%) is an 85% phosphoric acid with a freezing temperature below - 19°C (4°F).
- the phosphoric acid may be produced by a variety of methods, and may have the purity required for a typical application.
- the reduced freezing phosphoric acid of the present invention may be used for any purpose for which neat phosphoric acid may be used.
- the reduced freezing phosphoric acid can be added to asphalt to produce improved asphalt for road pavements.
- the invention is directed to a method to prepare low freezing temperature phosphoric acid composition including the steps of combining a phosphoric acid having an acid concentration of between 50% and 95% by weight expressed as H 3 PO 4 content and from about 0.01 % by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid.
- the method achieves the same effect by creating the additive in situ by adding for instance the alcohol related to the phosphoric acid ester to be used as the additive.
- the ester is made typically by reacting phosphoric acid and the related alcohol; which would be ethanol in this situation. Therefore, adding the ethanol directly into the phosphoric acid, the ester is formed in situ; triethylphosphoric acid ester.
- the additive used to reduce the freezing of the phosphoric acid is present in a concentration sufficient to reduce the freezing of the phosphoric acid to the desired value.
- additives that may be used to reduce the freezing of phosphoric acid include polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonate, phosphinate, thiodiester phosphate, thiotriester phosphate, phosphonate, phosphinate, organic solvents , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates or combinations thereof. Further, additional potential additives are provided in Table I.
- surfactants used in asphalt emulsions such as Evotherm® and CecabaseTM, may be used to produce the reduced freezing phosphoric acid.
- the additive is present in concentrations between 0.01% by weight to 10% by weight. In other embodiments, the additive is present in concentrations between 0.02% by weight to 5% by weight. The additive may be added to achieve a concentration of 0.1 % by weight in the phosphoric acid.
- triethylphosphate was added phosphoric acid having a concentration of 85% wt. expressed as H 3 PO 4 content to achieve a concentration of 0.3% by weight of (85%LT).
- the freezing of neat phosphoric acid i.e. phosphoric acid 85% wt. was monitored at temperatures ranging from -19C, fridge
Abstract
The present disclosure is related to a low freezing temperature phosphoric acid composition. Phosphoric Acid (PA) has a typical concentration of 75, 80 and 85%. One of the drawbacks of phosphoric acid is that, as its concentration increases, its freezing temperature also increases. As a result, the main strength of acid used for various applications remains 75%wt which freezes at -18C; as it is easier to handle and store during cold season. A considerable amount of phosphoric acid is being transported and stored every year in large quantities, mainly at 75% or sometimes but more rarely, at 85%, requiring heating equipment to prevent solidification.
Description
REDUCED FREEZING TEMPERATURE PHOSPHORIC ACID
COMPOSITIONS AND METHODS
Cross-Reference To Related Applications
[001] This application claims priority under 35USC 1 19(e) to United States Provisional Application No. 62/146,473 filed April 13, 2015, incorporated herein in its entirety.
Field of the Invention
[002] The present disclosure relates to compositions and methods for phosphoric acid compositions having a reduced freezing temperature compared to neat phosphoric acid. The freezing of the phosphoric acid is reduced by combining the phosphoric acid with an additive that reduces the freezing of the phosphoric acid composition.
Background of the Invention
[003] Phosphoric Acid (PA) has a typical concentration of 75, 80 and 85%. One of the drawbacks of phosphoric acid is that, as its concentration increases, its freezing temperature also increases. As a result, the main strength of acid used for various applications remains 75%wt which freezes at -18C; as it is easier to handle and store during cold season. A considerable amount of phosphoric acid is being transported and stored every year in large quantities, mainly at 75% or sometimes but more rarely, at 85%, requiring heating equipment to prevent solidification.
[004] In some heating processes, however, increased phosphoric acid temperature might not be desirable. This is expensive and "pumping" may be difficult, particularly when the phosphoric acid is provided in a plastic storage container
which is not able to withstand the required higher temperature to allow the phosphoric acid to be pumped.
[005] Typical phosphoric acid at 85% concentration freezes below 21.1 °C or 70°F which limit its usage during cooler season or requires permanent heating system to avoid crystal formation; when crystal formation occurs, it causes delays in manufacturing processes where it is used and ultimately has a significant cost impact.
[006] As a standard procedure in the industry, when heating is not preferred and when the process allows it, the recognized alternative is to use a lower strength of phosphoric acid: i.e. 75% acid with a freezing point of -17°C, which still could freeze during harsh winter condition and ultimately increase freight cost for users as unnecessary water is being transported.
[007] Accordingly, it would be desirable to have a phosphoric acid composition that provides the desired phosphoric acid concentration while having a lower freezing that allows easy handling at lower temperatures than required by current phosphoric acid products.
Summary of the Invention
[008] The present disclosure is directed to phosphoric acid compositions having a reduced freezing temperature compared to neat phosphoric acid. The reduction in freezing temperature is obtained by combining the phosphoric acid with an additive that reduces the freezing temperature of the phosphoric acid composition. The increase in the freezing temperature of the phosphoric acid, at a designated concentration, is caused by a reduction of phosphoric acid solubility. Any additive that can cause solvation and/or partial neutralization of the phosphoric acid without the addition of water may be used, therefore increasing solubility of the crystals at
a lower temperature. The additive could be formed in situ by adding the related alcohol of the phosphoric acid ester.
[009] In a first embodiment, the invention is directed to a low freezing temperature phosphoric acid composition including phosphoric acid having an acid
concentration of between 50% and 95% wt. expressed as H3PO4 content and from about 0.01 % by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid. The additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid,
tributylphosphate, dibutyl butyl phosphonate and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
[0010] In another embodiment, the invention is directed to a method to prepare low freezing temperature phosphoric acid composition including the steps of
combining a phosphoric acid having an acid concentration of between 50% and 95% by weight expressed as H3PO4 content and from about 0.01% by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid.
Brief Description of the Drawings
[0011] FIG. 1 illustrates a comparison of the freezing temperatures of typical 75% acid, typical 85% and the phosphoric acid composition of the present invention.
Detailed Description of the Invention
[0012] The present invention is directed to compositions and methods of a
phosphoric acid composition which provides reduced freezing compared to neat
phosphoric acid, and in addition, provides improved storage, handling and reduces freight cost.
[0013] The phosphoric acid composition of the present invention will not freeze during extreme cold temperature, allowing manufacturing operations to continue in contrast to competitive composition in the art. In addition, this will also provide decreased freight cost over time as heat is not required in transport or use.
Moreover, the absence of heat required and the reduced freight has a positive impact in terms of carbon footprint and related environmental issues.
The increase in the freezing temperature of the phosphoric acid, at its
concentration, is caused by a reduction of phosphoric acid solubility versus temperature. Any additive that can cause solvation and/or partial neutralization of the phosphoric acid without the addition of water may be used therefore increasing solubility of the crystals at a lower temperature.
[0014] In a first embodiment, the invention is directed to a low freezing temperature phosphoric acid composition including phosphoric acid having an acid
concentration of between 50% and 95% by weight expressed as H3P04 content and from about 0.01% by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid, wherein the additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tributylphosphate, dibutyl butyl phosphonate , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium
phosphates for instance as well as metal phopshates such as transition metals phosphates .
[0015] In a particular example of the present invention, the phosphoric acid composition (referred to as LT-85%) is an 85% phosphoric acid with a freezing temperature below - 19°C (4°F).
[0016] Additional components such as surfactants or salts can also be included without departing from the spirit of the invention. The phosphoric acid may be produced by a variety of methods, and may have the purity required for a typical application.
[0017] The reduced freezing phosphoric acid of the present invention may be used for any purpose for which neat phosphoric acid may be used. In addition the reduced freezing phosphoric acid can be added to asphalt to produce improved asphalt for road pavements.
[0018] Appreciating the concept of the present invention, one skilled in the art would recognize multiple applications where the phosphoric acid compositions of the present invention could be used in addition to asphalt, including but not limited to water treatment, food application, fertilizer, detergency and metal finishing.
[0019] In another embodiment, the invention is directed to a method to prepare low freezing temperature phosphoric acid composition including the steps of combining a phosphoric acid having an acid concentration of between 50% and 95% by weight expressed as H3PO4 content and from about 0.01 % by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid.
[0020] In a particular embodiment, the method achieves the same effect by creating the additive in situ by adding for instance the alcohol related to the phosphoric acid ester to be used as the additive. As a non-limiting example of this concept using triethylphosphoric acid ester as an additive, the ester is made typically by reacting phosphoric acid and the related alcohol; which would be ethanol in this situation. Therefore, adding the ethanol directly into the phosphoric acid, the ester is formed in situ; triethylphosphoric acid ester.
100211 The additive used to reduce the freezing of the phosphoric acid is present in a concentration sufficient to reduce the freezing of the phosphoric acid to the desired value. Examples of additives that may be used to reduce the freezing of phosphoric acid include polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonate, phosphinate, thiodiester phosphate, thiotriester phosphate, phosphonate, phosphinate, organic solvents , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates or combinations thereof. Further, additional potential additives are provided in Table I.
[0022] Table I
[0024] The following example of an embodiment of the invention demonstrates that the types of additives described above can reduce the freezing of phosphoric acid at temperatures as low as 30 degree Celsius to levels where the phosphoric acid can be easily handled and pumped without heating. These examples are not intended to limit the full scope of the invention in any manner.
[0025] Example 1
[0026] In this example, triethylphosphate was added phosphoric acid having a concentration of 85% wt. expressed as H3PO4 content to achieve a concentration of 0.3% by weight of (85%LT). The freezing of neat phosphoric acid (i.e. phosphoric acid 85% wt.) was monitored at temperatures ranging from -19C, fridge
compartment set at ~2C. and compared over a period of 6 month to the freezing of the Typical 75% acid and Typical 85% acid. Whereas the 85%LT and 75% acid remained liquid, the 85% neat acid started exhibiting crystals. The results are shown in FIG. I.
Claims
1. A low freezing temperature phosphoric acid composition comprising phosphoric acid having an acid concentration of between 50% and 95% wt expressed as H3PO4 content and from about 0.01 % by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid, wherein the additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tributylphosphate, dibutyl butyl phosphonate, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
2. A low freezing temperature phosphoric acid composition comprising phosphoric acid having an acid concentration of between 50% and 95% wt expressed as H3PO4 content and from 0.02% by weight to 0.2% by weight of an additive that reduces the freezing temperature of the phosphoric acid, wherein the additive is selected from the group consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tributylphosphate, dibutyl butyl phosphonate, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates
such as transition metals phosphates and combinations thereof and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
3. A method to prepare low freezing temperature phosphoric acid composition comprising the steps of :
(i) combining a phosphoric acid having an acid concentration of between 50% and 95% wt expressed as H3PO4 content and from about 0.01 % by weight to about 10% by weight of an additive that reduces the freezing temperature of the phosphoric acid.
4. The method of claim 3, wherein the additive is selected from the group
consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tributylphosphate, dibutyl butyl phosphonate , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
5. A method to increase the freezing temperature of a solution containing
phosphoric acid at a defined concentration consisting of the steps of:
(i) combining phosphoric acid crystals at a defined concentration with an additive the will increase solubility of the crystals at a lower temperature.
6. The method of claim 6, wherein the additive causes solvation of the
phosphoric acid crystals.
7. The method of claim 6 or 7, wherein the additive causes partial
neutralization of the phosphoric acid crystals.
8. The method of claim 6 wherein the additive is selected from the group
consisting of polyamines, amines, amidazoline, amidoamine, diester phosphate, triester phosphate, phosphonates, phosphinates, thiodiester phosphate, thiotriester phosphate, organic solvents, 2-ethyl hexyl phosphoric acid, tri butyl phosphate, dibutyl butyl phosphonate , alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates and combinations thereof, alkalin, alkalin earth phosphates salts such as sodium, potassium, magnesium phosphates for instance as well as metal phopshates such as transition metals phosphates.
9. The method of claim 3 or 5, wherein the additive is formed in situ by adding the related alcohol of the phosphoric acid ester .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201562146473P | 2015-04-13 | 2015-04-13 | |
| US62/146,473 | 2015-04-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016168112A1 true WO2016168112A1 (en) | 2016-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2016/026904 WO2016168112A1 (en) | 2015-04-13 | 2016-04-11 | Reduced freezing temperature phosphoric acid compositions and methods |
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| WO (1) | WO2016168112A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106882775A (en) * | 2017-03-10 | 2017-06-23 | 苏州博洋化学股份有限公司 | A kind of low condensation point phosphoric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2273781A (en) * | 1938-01-08 | 1942-02-17 | Monsanto Chemicals | Means for transmitting heat and power |
| US5219675A (en) * | 1989-06-30 | 1993-06-15 | Yamaha Hatsudoki Kabushiki Kaisha | Electrolyte for fuel cell |
-
2016
- 2016-04-11 WO PCT/US2016/026904 patent/WO2016168112A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2273781A (en) * | 1938-01-08 | 1942-02-17 | Monsanto Chemicals | Means for transmitting heat and power |
| US5219675A (en) * | 1989-06-30 | 1993-06-15 | Yamaha Hatsudoki Kabushiki Kaisha | Electrolyte for fuel cell |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106882775A (en) * | 2017-03-10 | 2017-06-23 | 苏州博洋化学股份有限公司 | A kind of low condensation point phosphoric acid |
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