WO2011075422A1 - Methods for production of high concentration of arginine bicarbonate solution at high pressue - Google Patents
Methods for production of high concentration of arginine bicarbonate solution at high pressue Download PDFInfo
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- WO2011075422A1 WO2011075422A1 PCT/US2010/059992 US2010059992W WO2011075422A1 WO 2011075422 A1 WO2011075422 A1 WO 2011075422A1 US 2010059992 W US2010059992 W US 2010059992W WO 2011075422 A1 WO2011075422 A1 WO 2011075422A1
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- WIPO (PCT)
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- arginine
- slurry
- bicarbonate
- carbon dioxide
- temperature
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
Definitions
- Arginine bicarbonate has use in various industrial applications, including use in personal care compositions, such as oral care compositions.
- personal care compositions such as oral care compositions.
- U.S. Patent No. 6,524,558 describes the use of arginine bicarbonate and calcium carbonate for preventing or treating dental hypersensitivity.
- Arginine bicarbonate may be produced by bubbling carbon dioxide gas through a saturated arginine aqueous solution at room temperature and pressure.
- 6,217,851 describes preparing arginine bicarbonate from arginine hydroxide by bubbling carbon dioxide or by adding dry ice in excess into a solution of arginine free base.
- the existing process is slow, requiring 24 to 48 hours to complete the reaction.
- Carbon dioxide has very limited solubility in water, and releasing the gas into the solution produces a maximum concentration of 1.2x10 "5 M at room temperature and its natural partial pressure (3.5xl0 ⁇ 4 atmosphere).
- the solubility of arginine in water is only 15% weight/weight at room temperature.
- Producing a concentrated arginine bicarbonate solution (e.g. ,40%) requires the continual addition of arginine to the solution, thereby increasing production time and requiring constant monitoring of the reaction.
- there is a need to improve methods to manufacture arginine bicarbonate.
- a method of producing arginine bicarbonate including contacting carbon dioxide having a pressure of least 34474 Pa (5 psi) with a starting slurry containing arginine at a temperature of at least 30°C; adding arginine to the contacted slurry to increase the arginine content to greater than 65% by weight; contacting the increased arginine slurry with carbon dioxide until the slurry has a pH below 9; and recovering arginine bicarbonate from the slurry.
- a process for producing arginine bicarbonate includes contacting an arginine water slurry with carbon dioxide having a pressure greater than 551580 Pa (80 psi); heating the arginine water slurry to a temperature within the range of from 60°C to 80°C; adding arginine to the slurry until arginine comprises 65%> by weight; contacting carbon dioxide with the increased arginine slurry until the slurry has a pH below 9;cooling the slurry to a temperature of 25°C.
- a method of producing arginine bicarbonate including subjecting an arginine water slurry to elevated pressure and temperature; contacting the slurry with carbon dioxide to form a slurry comprising arginine and bicarbonate in excess of 65% by weight of arginine; and recovering arginine bicarbonate from the slurry.
- Figure 1 illustrates reaction products from various conditions in clear plastic bottles, wherein arginine was added to a Parr reactor in: right (sample #l)-single step; middle (sample #2)-two steps; and left (sample #3)-three steps.
- compositions and the methods may comprise, consist essentially of, or consist of the elements described therein.
- the method involves a surprisingly simple reaction to produce a high concentration of arginine bicarbonate salt by reacting a source of gaseous carbon dioxide and an arginine slurry under elevated temperature and low pressure to form an arginine and bicarbonate anion solution, wherein the salt is then recovered from solution.
- the initial reaction is faster than existing methods, 90 minutes vs. over 24 hours, and yields a more concentrated solution of arginine and bicarbonate anion (above 50%, and in certain
- the method is directed to a surprisingly simple reaction to produce a high concentration of arginine bicarbonate salt solution by reacting a source of gaseous carbon dioxide and an arginine slurry under elevated temperature and pressure to form an arginine and bicarbonate anion solution, wherein the salt is then recovered from solution.
- the initial reaction is faster than existing methods, from 10 to 20 minutes vs. over 24 hours, and yields a more concentrated solution of arginine and bicarbonate anion (in certain embodiments in excess of 75% vs. 40%).
- a method of producing arginine bicarbonate including contacting carbon dioxide having a pressure of least 34474 Pa (5 psi) with a starting slurry containing arginine at a temperature of at least 30°C; adding arginine to the contacted slurry to increase the arginine content to greater than 65% by weight; contacting the increased arginine slurry with carbon dioxide until the slurry has a pH below 9; and recovering arginine bicarbonate from the slurry.
- a process for producing arginine bicarbonate includes contacting an arginine water slurry with carbon dioxide having a pressure greater than 551580 Pa (80 psi); heating the arginine water slurry to a temperature within the range of from 60°C to 80°C; adding arginine to the slurry until arginine comprises 65% by weight; contacting carbon dioxide with the increased arginine slurry until the slurry has a pH below 9;cooling the slurry to a temperature of 25°C.
- a method of producing arginine bicarbonate including subjecting an arginine water slurry to elevated pressure and temperature; contacting the slurry with carbon dioxide to form a slurry comprising arginine and bicarbonate in excess of 65% by weight of arginine; and recovering arginine bicarbonate from the slurry.
- the arginine slurry includes arginine and a solvent, in certain embodiments water, wherein the subsequent portions of arginine are added stepwise or continuously in the form of a free base or salt.
- the arginine water slurry is in a ratio of 50:50 by weight with respect to the first portion of arginine. Subsequent portions of arginine may be added until the ratio of arginine to water is in excess of 1.8: 1, in certain embodiments in excess of 1.9: 1, in certain embodiments in excess of 2.0: 1, and in certain embodiments in excess of 2.5 : 1.
- the arginine used in the methods in certain embodiments is selected from L-arginine, D-arginine, or a mixture thereof.
- the arginine also can be provided by arginine hydroxide, arginine hydrochloride, or a mixture thereof.
- the carbon dioxide can be provided to the reaction as a gas under pressure from 34474 Pa (5 psi) to 1723689 Pa (250 psi), in certain embodiments from in excess of 275790 Pa (40 psi) to in excess of 551580 Pa (80 psi), and in certain embodiments at 551580 Pa (80 psi).
- the bicarbonate ion can be generated by providing sodium bicarbonate to the slurry.
- the arginine slurry and carbon dioxide can be maintained under elevated temperature and pressure for 10 minutes to 20 minutes.
- the arginine slurry and carbon dioxide therefore can be maintained under elevated temperature and pressure for 10 minutes to 5 hours, in certain embodiments from 10 minutes to 4 hours, and in certain embodiments from 10 minutes to 2-4 hours, for commercial scale production.
- the arginine slurry can first be heated to a temperature within the range of from 30°C to 80°C, in certain embodiments from 50°C to 80°C for the duration of the reaction, then cooled to a temperature within the range of from 0°C to 40°C after completion of the reaction, in certain embodiments from 0°C to 25°C.
- the arginine slurry in certain embodiments has a pH of 10 to 14.
- the arginine bicarbonate solution has a pH of from 7 to 10, in certain embodiments a pH of 7.5 to 8.5 ( or 7.0 to 9.0). That is, the reaction is believed to be substantially completed when the pH of the resulting solution containing the arginine bicarbonate is below 9.0.
- the present method in certain embodiments begins with the formation of an arginine slurry comprising arginine and a solvent, in certain embodiments water.
- arginine free base is only slightly soluble at water at room temperature, the addition of arginine to water forms a slurry, wherein a majority of the arginine is insoluble.
- Any form of arginine may be utilized to form the slurry, e.g., arginine free base (in D or L form, usually L-form), or an arginine salt.
- arginine salts e.g., hydrochloride, and pharmaceutically acceptable salts
- salts may be used or mixtures of free base and salts may be used in combination to form the slurry.
- the slurry in certain embodiments is produced by the addition of 10% to 90%> weight of arginine to the solvent, e.g., 20% to 80%, 30% to 70%, 40% to 60%.
- the slurry may then be agitated to create a homogenous mixture.
- the initial pH of the slurry is generally 12 for arginine free base, e.g., 10 to 13.
- the arginine water slurry is in a ratio of 50:50 w/w.
- the slurry may be heated to 30°C to 80°C, e.g., to 40°C, to 50°C, to 55°C, to 60°C, to 65°C, or to 70°C to increase the solubility of the arginine.
- the arginine water slurry is first heated from 60°C to 80°C.
- the solubility of carbon dioxide into the slurry may be increased by decreasing the temperature of the solution; however, this decreases the solubility of the arginine. Thus, it is desired that a careful balance be maintained between solubility of both components.
- the pressurized vessel may be temperature controlled.
- One method of increasing the solubility of the carbon dioxide into the slurry is to provide the carbon dioxide at a lower temperature than that of a slurry, for example, by introducing carbon dioxide as dry ice, or a cooled gas. In certain embodiments, carbon dioxide gas is used in the present reaction. Additionally, direct cooling of the slurry may be significant.
- the solubility of carbon dioxide into the slurry may be increased by increasing the partial pressure of the carbon dioxide in the reaction vessel.
- the reaction between the carbon dioxide and the arginine slurry may occur at 34474 Pa (5 psi) to 1034214 Pa (150 psi), e.g., to 344738 Pa (50 psi), to 413685 Pa (60 psi), to 482633 Pa (70 psi), to 551580 Pa (80 psi), to 620528 Pa (90 psi), to 689476 Pa (100 psi), to 758423 Pa (1 10 psi), to 827371 Pa (120 psi), or to 965266 Pa (140 psi).
- the pressure typically is maintained within a range of from 137895 Pa (20 psi) to 551580 Pa (80 psi) in order to take advantage of the higher solubility of C0 2 gas in water at higher partial C0 2 pressure.
- a high pressure reaction vessel such as a Parr instrument model 425HC T316 can be used.
- arginine powder is added to a reactor containing water in a 50:50 arginine water ratio and reacted with carbon dioxide gas compressed at pressure in excess of 134474 Pa (5 psi) and a temperature greater than 50° C to 75° C until an almost clear solution is formed. Subsequent portions of powder arginine are added to the resulting clear solution until the ratio of arginine to water is 1.9: 1. Depending on the completion of the reaction, in certain embodiments when no solid arginine remains, the arginine bicarbonate solution is clear and colorless, and the pH is less than 9.0, then additional carbon dioxide may be added to the reaction vessel.
- an arginine bicarbonate solution having a final concentration in excess of 50%, in certain embodiments in excess of 60%>, in certain embodiments, in excess of 65%o, in certain embodiments in excess of 70%>, and in certain embodiments in excess of 75% (even as high as 76%) arginine bicarbonate can be obtained.
- the reaction between the arginine slurry and carbon dioxide may be allowed to proceed for 10 to 20 minutes.
- the reaction time required to obtain an arginine bicarbonate solution having a final concentration in excess of 50% arginine bicarbonate is also from 10 minutes to 20 minutes.
- the completion of the reaction may be gauged by monitoring the presence of undissolved arginine in the slurry, as arginine in the presence of bicarbonate anions are highly soluble compared to the arginine itself.
- Another method to monitor the reaction is to measure the pH of the solution in the reaction vessel directly, or sample the solution and measure its pH in an open container at room temperature. In certain embodiments, the pH can be measured as a means of assessing whether the reaction has completed, and, in certain embodiments, the pH be below 9.0 before completion of the reaction.
- the arginine bicarbonate salt may be recovered by any means known by those of skill in the art.
- the present methods may be utilized to produce arginine bicarbonate in single batches, or may be used in a continuous process, such as in continuous stirred tank reactors, fluidized bed reactors, and plug flow reactors. Those skilled in the art will be capable of carrying out the methods described herein in single batch or continuous processes, using the guidelines provided herein.
- ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range.
- all references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls. It is understood that when formulations are described, they may be described in terms of their ingredients, as is common in the art, notwithstanding that these ingredients may react with one another in the actual formulation as it is made, stored and used, and such products are intended to be covered by the formulations described.
- a slurry of pH 12 containing 50% L-arginine by weight and 50% water by weight is prepared by mixing 85 g of L-arginine with 85 g of water at room temperature. The slurry is heated to 55°C under gentle agitation. Approximately 50% of the L-arginine is determined to be dissolved by visual observation.
- EXAMPLE 2 The solution of EXAMPLE 2 is stirred with a spatula to make a suspension. 10 grams of dry ice is added to the vessel, and the vessel is sealed. The pressure is allowed to increase to, and maintained at 620528 Pa (90 psi). The vessel is opened after 3 minutes, and a thick clear colorless solution was observed without precipitation. The solution is dropped to 12°C producing an arginine bicarbonate solution of 60% concentration, having a final pH of 8.8. Arginine bicarbonate salt is recovered by freeze drying.
- Arginine water slurry and compressed C0 2 gas are reacted in a series of reactions performed in a 300ml high pressure reactor from Parr Instruments (425HC 300 ml cylinder, commercially available from Parr Instruments, Moline, Illinois) with a C0 2 injection port and fittings.
- the reactor included a port with an L-shaped stainless steel tube wherein the tube went to the bottom of the reactor. This port served as the C0 2 inlet port, which allowed C0 2 gas to be blown directly into the reactants, so that it also served as the mixer/agitator.
- the reactor also included a T-connector that connected the reactor to a purge valve and emergency relief valve at the top for safety.
- the reactor body sat inside a thermo-bath, so that the reaction temperature could be precisely controlled.
- thermo-bath is allowed to reach its preset temperature. Powder L-arginine is mixed with deionized water in the high pressure reactor by a spatula. The reactor is capped, its purge valve is kept open, and then the reactor is placed into the thermo-bath so that the reactants could reach the desired temperature. After thermo-equilibrium is reached in the thermo-bath, the compressed C0 2 gas is introduced into the reactor. The purge valve is kept partially open so that there is constant flow of C0 2 gas through the reactor to provide agitation. The gas pressure is regulated using a dual stage regulator on the C0 2 tank, and the pressure reading is taken from the gauge on the regulator.
- the purge valve Since the purge valve is always open, the pressure inside the reactor is slightly lower than the value shown on the regulator gauge. Each reaction is allowed to progress for a constant time period, then the C0 2 gas supply is turned off. The reactor is opened immediately, and the contents in the reactor are transferred into a plastic container. The plastic container is capped tightly and submerged into a tap water bath at room temperature to cool it down. The pH of the final solution at room temperature is measured with a standard glass electrode pH meter.
- arginine bicarbonate samples are prepared, in which the arginine is added all at once in sample 1 and stepwise in samples 2 and 3. In all three samples, the reaction temperature is 75°C and the pressure is maintained at 551580 Pa (80 psi) for a total time of 12 minutes.
- arginine bicarbonate is prepared by adding to the reactor vessel an arginine water slurry in a ratio in excess of 1.8: 1 of arginine to water in one step. It was found that the slurry was more like "damp powder" in solid form.
- the reactor is opened immediately and the rest of arginine powder, less than 20% of total arginine, is added, and mixed with the clear solution inside the reactor by a spatula.
- the reactor is closed and compressed C0 2 gas is introduced into the reactor again.
- the reaction is allowed to run for another 7 minutes for a total of 12 minutes reaction time.
- An almost clear solution with barely any visible amount of solid arginine was obtained, as shown in the clear plastic bottle in the middle of Figure 1.
Abstract
Description
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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CA2780491A CA2780491C (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressure |
MX2012005972A MX2012005972A (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressue. |
US13/515,829 US9035093B2 (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressure |
EP10803308.5A EP2513048B1 (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressure |
RU2012130360/04A RU2518901C2 (en) | 2009-12-18 | 2010-12-13 | Methods for high-pressure preparation of high-concentrated solution of arginine bicarbonate |
BR112012014739A BR112012014739A2 (en) | 2009-12-18 | 2010-12-13 | Methods for producing high concentration high pressure arginine bicarbonate solution |
JP2012544665A JP2013514357A (en) | 2009-12-18 | 2010-12-13 | Method for producing high concentration arginine bicarbonate solution at high pressure |
AU2010332017A AU2010332017B2 (en) | 2009-12-18 | 2010-12-13 | Method for production of high concentration of arginine bicarbonate solution at high pressure |
CN201080057648.2A CN102666481B (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressure |
ZA2012/03667A ZA201203667B (en) | 2009-12-18 | 2012-05-18 | Methods for production of high concentration of arginine bicarbonate solution at high pressure |
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US28784609P | 2009-12-18 | 2009-12-18 | |
US61/287,846 | 2009-12-18 |
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WO2011075422A1 true WO2011075422A1 (en) | 2011-06-23 |
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PCT/US2010/059992 WO2011075422A1 (en) | 2009-12-18 | 2010-12-13 | Methods for production of high concentration of arginine bicarbonate solution at high pressue |
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US (1) | US9035093B2 (en) |
EP (1) | EP2513048B1 (en) |
JP (1) | JP2013514357A (en) |
CN (1) | CN102666481B (en) |
AR (1) | AR079651A1 (en) |
AU (1) | AU2010332017B2 (en) |
BR (1) | BR112012014739A2 (en) |
CA (1) | CA2780491C (en) |
CO (1) | CO6460720A2 (en) |
MX (1) | MX2012005972A (en) |
MY (1) | MY157789A (en) |
RU (1) | RU2518901C2 (en) |
SA (1) | SA110320038B1 (en) |
TW (1) | TWI510458B (en) |
WO (1) | WO2011075422A1 (en) |
ZA (1) | ZA201203667B (en) |
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CN108929248A (en) * | 2018-07-02 | 2018-12-04 | 无锡晶海氨基酸股份有限公司 | A kind of preparation method of L-arginine hydrochloride |
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US10203434B2 (en) | 2013-03-15 | 2019-02-12 | Blue Planet, Ltd. | Highly reflective microcrystalline/amorphous materials, and methods for making and using the same |
JP2019062742A (en) | 2016-02-24 | 2019-04-25 | 味の素株式会社 | Methods for producing l-amino acids |
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CN113416480A (en) * | 2021-07-06 | 2021-09-21 | 安徽江锐新材料有限公司 | Anti-corrosion water-based acrylic polyurethane finish paint and preparation process thereof |
CN114570295A (en) * | 2022-03-25 | 2022-06-03 | 上海吉量医药工程有限公司 | Method for rapidly preparing triethylamine carbonate buffer solution |
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2010
- 2010-12-13 CA CA2780491A patent/CA2780491C/en not_active Expired - Fee Related
- 2010-12-13 RU RU2012130360/04A patent/RU2518901C2/en not_active IP Right Cessation
- 2010-12-13 EP EP10803308.5A patent/EP2513048B1/en active Active
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WO2000078270A1 (en) * | 1999-06-23 | 2000-12-28 | The Research Foundation Of State University Of New York | Dental anti-hypersensitivity composition and method |
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CN108929248A (en) * | 2018-07-02 | 2018-12-04 | 无锡晶海氨基酸股份有限公司 | A kind of preparation method of L-arginine hydrochloride |
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AU2010332017A1 (en) | 2012-06-21 |
AR079651A1 (en) | 2012-02-08 |
MY157789A (en) | 2016-07-29 |
JP2013514357A (en) | 2013-04-25 |
TW201139346A (en) | 2011-11-16 |
US9035093B2 (en) | 2015-05-19 |
BR112012014739A2 (en) | 2016-04-05 |
AU2010332017B2 (en) | 2013-08-15 |
EP2513048B1 (en) | 2016-11-16 |
TWI510458B (en) | 2015-12-01 |
EP2513048A1 (en) | 2012-10-24 |
CO6460720A2 (en) | 2012-06-15 |
CN102666481A (en) | 2012-09-12 |
CA2780491C (en) | 2014-09-30 |
SA110320038B1 (en) | 2015-01-01 |
CN102666481B (en) | 2015-03-11 |
RU2012130360A (en) | 2014-01-27 |
ZA201203667B (en) | 2015-08-26 |
RU2518901C2 (en) | 2014-06-10 |
US20120296117A1 (en) | 2012-11-22 |
MX2012005972A (en) | 2012-06-19 |
CA2780491A1 (en) | 2011-06-23 |
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