Patent Application
20240158346
Not applicable
Not applicable
Various embodiments relate to a low cost process to make quaternary ammonium compounds (ionic liquids or liquids to be used as electrolytes) for flow batteries for use in battery electrolytes as a bromine complexing agent. N-methyl-N-ethylpyrrolidinium (“MEP”) is a quaternary ammonium complex.
While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
Quaternary ammonium cations, also known as quats, are positively charged polyatomic ions of the structure NR4+R being an alkyl group or an aryl group. Unlike the ammonium ion (NH4+) and the primary, secondary, or tertiary ammonium cations, the quaternary ammonium cations are permanently charged, independent of the pH of their solution. Quaternary ammonium salts or quaternary ammonium compounds (called quaternary amines in oilfield parlance) are salts of quaternary ammonium cations.
An ionic liquid is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below some arbitrary temperature, such as 100° C. (212° F.). A salt, in chemistry, substance produced by the reaction of an acid with a base. A salt consists of the positive ion (cation) of a base and the negative ion (anion) of an acid. The reaction between an acid and a base is called a neutralization reaction. When in solution or the molten state, most salts are completely dissociated into negatively and positively charged ions and are good electrolytes (conductors of electricity).
Ionic liquids are usually prepared by a reaction of an alkyl halide (typically a bromide, such as ethyl bromide, which is a compound of bromine with another element or group, especially a salt containing the anion Br− or an organic compound with bromine bonded to an alkyl radical) with a tertiary amine (e.g., N-methylpyrrolidine) in a solvent (e.g. acetonitrile) and then crystallizing the product and filtering to isolate the solid. The previously isolated solid is then dissolved in water to make an electrolyte solution that can be used in a flow battery. Water does not work well as a solvent in the reaction because it causes hydrolysis of ethyl bromide lowering the pH to less than 2 (see e.g., Example 4).
In organic chemistry, amines are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkyl or aryl group (these may respectively be called alkylamines and arylamines; amines in which both types of substituents are attached to one nitrogen atom may be called alkylarylamines). Various amines include amino acids, biogenic amines, trimethylamine, and aniline.
Alkyl halides are compounds in which one or more hydrogen atoms in an alkane have been replaced by halogen atoms (fluorine, chlorine, bromine or iodine). Alkyl halides can be classified as primary, secondary, or tertiary. Alkanes are organic compounds that consist entirely of single-bonded carbon and hydrogen atoms and lack any other functional groups. Alkanes have the general formula CnH2n+2 and can be subdivided into the following three groups: the linear straight-chain alkanes, branched alkanes, and cycloalkanes.
Bromine complexing agent are chemical species capable of binding with metal ions or other chemical entities in a system through its single or multiple sites. These sites have lone pairs of electrons which can be donated to the d orbitals of a metal ion, forming coordination bonds. This results in a coordination compound.
Most processes in the literature of preparing quaternary ammonium compounds utilize a solvent which is required to be removed after creation of the compounds.
While certain novel features of this invention shown and described below are pointed out in the annexed claims, the invention is not intended to be limited to the details specified, since a person of ordinary skill in the relevant art will understand that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation may be made without departing in any way from the spirit of the present invention. No feature of the invention is critical or essential unless it is expressly stated as being “critical” or “essential.”
In one embodiment a process is provided to make quaternary ammonium compounds (ionic liquids) in water.
In one embodiment is provided a method of making ionic liquids in water for flow batteries to be used in battery electrolytes as a bromine complexing agent.
In one embodiment is provided a method of making ionic liquids, without the need for solvents, in water for flow batteries to be used in battery electrolytes as a bromine complexing agent.
In one embodiment is provided a method of preparing MEP including the steps of: (a) adding N-methylpyrrolidine to an excess amount of ethyl bromide located in a reactor, wherein the N-methylpyrrolidine will react with the ethyl bromide forming MEP, wherein the reaction will have a reaction temperature that can varies over time; (b) stopping addition of N-methylpyrrolidine when the excess of ethyl bromide to the N-methylpyrrolidine falls within a range of 3:1 to 1.5:1; (c) adding water to the reactor creating a two phase system to develop which includes: (i) a top layer containing aqueous MEP and (ii) a bottom layer containing ethyl bromide; (d) separating the top layer from the bottom layer yielding a first aqueous solution of MEP and a second layer of ethyl bromide; and (e) removing trace amounts of unreacted N-methylpyrrolidine and ethyl bromide from the first aqueous solution of MEP.
In one embodiment the reactor can be a container, a tank, a vessel, a pressure vessel, a pipe, a conduit, or a flask. In one embodiment the reactor can be insulated such as by jacketing.
In one embodiment, during step “a” the reaction temperature is maintained lower than 50° C.
In one embodiment during step “b” the excess of ethyl bromide to the N-methylpyrrolidine remains reduces to be within a range of 3:1 to 1.85:1. In one embodiment the excess of ethyl bromide to the N-methylpyrrolidine reduces to be within a range of 2:1 to 1.85:1. In one embodiment the excess of ethyl bromide to the N-methylpyrrolidine reduces to be within a range of 3:1 to 2:1.
In one embodiment during step “b” a slurry of MEP is formed in the excess of ethyl bromide and this slurry of MEP and excess ethyl bromide is allowed to cool to 25° C. between steps “b” and “c”.
In one embodiment during step “c” the water is purified water. Preferably, the purified water can be de-ionized water, reverse osmosis water, and/or distilled water.
In one embodiment step “d” is performed using a phase cut.
In one embodiment step “e” is performed by sparging with a noble gas to remove trace amounts of unreacted N-methylpyrrolidine and ethyl bromide from the first aqueous solution of MEP, which can be N2. In one embodiment step “e” is performed by sparging with a gas is used for removal of trace amounts of unreacted N-methylpyrrolidine and ethyl bromide, wherein said gas is non-reactive relative to MEP, N-methylpyrrolidine, and ethyl bromide. In one embodiment the sparging is performed when the first aqueous solution of MEP is between 30° C. and 50° C. In one embodiment at the end of step “e” the pH is between 6 and 9. In one embodiment during step “e” removal of trace amounts of unreacted N-methylpyrrolidine in the first aqueous solution of MEP causes the pH to reduce to between 6 and 9.
In one embodiment during step “e”, N-methylpyrrolidine is removed until its concentration in the first aqueous solution of MEP is less than 2,000 parts per million. In one embodiment during step “e”, N-methylpyrrolidine is removed until its concentration in the first aqueous solution of MEP is less than 1,000 parts per million. In one embodiment during step “e”, N-methylpyrrolidine is removed until its concentration in the first aqueous solution of MEP is less than 500 parts per million. In one embodiment removal is continued the concentration of N-methylpyrrolidine in the first aqueous solution of MEP is not detectable.
In one embodiment ethyl bromide is removed until its concentration in the first aqueous solution of MEP is not detectable. Removal of the ethyl bromide is preferred to minimize hydrolysis and pH drift of the first aqueous solution of MEP to be less than 6.
The drawings constitute a part of this specification and include exemplary embodiments to the invention, which may be embodied in various forms.
For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements.
Detailed descriptions of one or more preferred embodiments are provided herein. It is to be understood, however, that the present invention may be embodied in various forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching one skilled in the art to employ the present invention in any appropriate system, structure or manner.
Water was used as a solvent in early experiments in making MEP from ethyl bromide and N-methylpyrrolidine. However, hydrolysis occurred between the ethyl bromide and water generating HBr that reacted with the amine forming amine salts and lowering the pH.
Surprisingly, it was discovered that the reaction could be run with an excess of the alkyl halide (e.g., ethyl bromide) to act as both: (i) a solvent and (ii) a reactant. After the reaction is complete and the temperature is lowered to prevent or minimize hydrolysis, deionized water can be added to the reactants causing the formation of two liquid phases. The first aqueous phase has the ionic liquid (e.g., aqueous MEP) and the second organic phase has the remaining excess alkyl halide (e.g., ethyl bromide). The organic phase (e.g., ethyl bromide) can be recycled to the next cycle for forming MEP (e.g., forming an excess of ethyl bromide compared to added N-methylpyrrolidine) and the aqueous phase with ionic liquid can be used as is without requiring removal of a solvent or further purification.
In various embodiments MEP can be made by adding N-methylpyrrolidine to an excess of ethyl bromide as the solvent thereby causing MEP to form as a solid or slurry, and subsequently adding water to dissolve the MEP in the water.
In various embodiments is provided a method of preparing MEP including the steps of: (a) adding N-methylpyrrolidine to an excess amount of ethyl bromide located in a reactor, wherein the N-methylpyrrolidine will react with the ethyl bromide forming MEP, wherein the reaction will have a reaction temperature that can vary over time; (b) stopping addition of N-methylpyrrolidine when the excess of ethyl bromide to the N-methylpyrrolidine falls within a range of 3:1 to 1.5:1; (c) adding water to the reactor creating a two phase system to develop which includes: (i) a top layer containing aqueous MEP and (ii) a bottom layer containing ethyl bromide; (d) separating the top layer from the bottom layer yielding a first aqueous solution of MEP and a layer ethyl bromide; and (e) removing trace amounts of unreacted N-methylpyrrolidine and ethyl bromide from the first aqueous solution of MEP.
In various embodiments, distillation can be used to remove the alkyl halide (e.g., ethyl bromide) from the reaction mass after the water has been added (e.g., removal of ethyl bromide from the two phases of (i) aqueous MEP and (ii) ethyl bromide) but the temperature should remain as low enough to prevent hydrolysis.
The following is an example of a preferred method of making MEP in one embodiment.
1. Obtain the following starting materials:
2. Start with ethyl bromide in a reactor which can be a container, tank, vessel, pressure vessel, pipe, conduit or flask.
3. Add N-methylpyrrolidine to the reactor causing an exothermic reaction with the ethyl bromide tending to increase the temperature. Preferably, the rate of N-methylpyrrolidine added to the reaction is limited to prevent the temperature from exceeding 50° C. Also preferably, during the reaction an excess of ethyl bromide to N-methylpyrrolidine should be maintained in a ratio of least 1.85:1.
4. Discontinue adding N-methylpyrrolidine to the reactor when the excess ratio of ethyl bromide to N-methylpyrrolidine is between 3:1 and 1.5:1. Preferably, addition of N-methylpyrrolidine is stopped when the excess ratio of ethyl bromide to N-methylpyrrolidine is between 2:1 and 1.85:1.
5. Allow the reaction to cool to 25° C. At this point a white slurry of MEP in excess ethyl bromide can be seen in the reactor.
6. Add purified water to the reactor causing the MEP to enter the aqueous phase and creating a 2-phase system:
7. Separate the upper and bottom layers. Separation can be done by various methods such as using a phase cut of the bottom layer of ethyl bromide (e.g., draw off the bottom layer or draw off the top layer). The recovered bottom layer of ethyl bromide can optionally be reused in the process of forming MEP from adding N-methylpyrrolidine to an excess of ethyl bromide. It is preferred that the recycled ethyl bromide is dried to remove trace water (e.g., drying agent such as magnesium sulfate or distillation).
8. Removal of residual or trace amounts of unreacted ethyl bromide and N-methylpyrrolidine from the aqueous solution of MEP. Removal can be done by various methods such as sparging with a non-reactive gas (such as an inert gas, e.g., N2) and a small amount of heating of the aqueous solution of MEP phase after separation from the ethyl bromide phase. The non-reactive gas is preferably non-reactive relative to MEP, N-methylpyrrolidine, and/or ethyl bromide. For example, the non-reactive gas can be an inert gas such as a noble gas (e.g., N2). Preferably, the sparging is performed at a temperature between 30° C. to 50° C., alternatively between 20° C. to 50° C.; 30° C. to 45° C., or 45° C. to 50° C. The sparging preferably removes trace amounts of unreacted ethyl bromide and N-methylpyrrolidine from the aqueous solution of MEP. The removal of the trace amounts of unreacted N-methylpyrrolidine (which is basic) will reduce the pH of the aqueous solution of MEP. During this removal step, the trace amounts of unreacted N-methylpyrrolidine are removed causing the pH preferably to reduce (e.g., from a starting pH of 11.5 and preferably lowering to a more neutral state such as between 6 and 9). During this removal step, removal of the trace amounts of ethyl bromide will stop hydrolysis of this remaining ethyl bromide which otherwise would cause the pH to drift over time.
Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.
Initial Charges
Testing of the MEP provided the following results:
Theoretical composition of Br− for 65% MEP in water=26.8% (weight percent), and measured was 26.44%
Good quality aqueous solution of MEP product was produced. Literature values for solubility of water in ethyl bromide is listed as 0.896 g/100 mls and solubility of ethyl bromide in water 0.9% at 25° C. Recovered 97% of excess ethyl bromide used, which means only lost 3%. Possible improvement by drying ethyl bromide layer before recycling to next reaction. Can use a nitrogen sparge for removing residual last traces of ethyl bromide from the aqueous phase of MEP.
Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.
Testing of the MEP provided the following results:
Good quality MEP made with exceptionally low APHA (13) color looking water white. For the comparison of pH versus sparging time it can be seen that the pH is being lowered over time which is believed due to the sparging removal of trace amounts of unreacted N-methylpyrrolidine.
Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.
Testing of the MEP provided the following results:
Crude is as the MEP came out of the reactor. GAC is after treatment with granulated activated carbon.
During the reaction a non aqueous solvent appears to prevent any hydrolysis products as using water as the solvent to start with causes a small amount of hydrolysis to occur to make HBr and ethanol. The HBr will also make an amine salt which is also undesirable. Completing the reaction in an excess of ethyl bromide and then doing a solvent swap with reverse osmosis water prevents prior hydrolysis.
After distillation about 92% of the excess ethyl bromide was recovered. It is expected that this excess ethyl bromide can be recycled and used in a second process to make MEP.
If released to water, bromoethane will be removed through hydrolysis and volatilization. Aqueous hydrolysis half-lives range from 5 days (at 35° C.) to 21-30 days (at 25° C.). The volatilization half-lives from a model river and pond have been estimated to be 3.2 hours and 38.2 hours, respectively.
If released to soil, bromoethane will be susceptible to hydrolysis under wet soil conditions. Its detection in landfill leachate demonstrates that environmental leaching can occur. Evaporation from moist and dry soils may occur based on its Henry's law constant and a high vapor pressure. Biodegradation of bromoethane is expected to be an important fate process in both water and soil.
It is desired to optimize the purification system for maximizing MEP yield. For example, different amounts of GAC can be used, and washing GAC prior to use plus other absorbents such as alumina can be used. There was an increase in K and a little Zn and Ba increase after GAC treatment.
When compared to experiments using water as solvent-atmospheric pressure to make MEP, the water-solvent prepared aqueous solution of MEP had much lower pH and more color.
Better than doing reaction water as a solvent but still not optimized. Although GAC improves the color of the MEP (from 228 to 117 APHA) the color is still not preferred. Additionally, the pH has improved (2.86 to 5.6), but still not within the preferred range of 6 to 9.
Experimental Section
Glass reactor (500 ml 3 neck) setup with magnetic stirrer, thermocouple, and reflux condenser.
Before treatment with of granulated activated carbon (“GAC”) the pH is 1.77 and the color is orange. 200 g of the crude MEP was treated with 20 g of GAC for 3 hours and then filtered leaving 179 g of a white liquid with a pH of 5.59.
Testing of the MEP after treatment with GAC provided the following results:
This is 194.11 g MEP in total 444.11 g solution giving 43.7% solution in water
Metals are low due to running reaction in glassware, and preferably would specify a glass lined reactor for making this product. pH is also higher than experiments where the MEP was made with water as the solvent in a 316 SS pressure reactor. APHA color is high and requires GAC treatment. Use of GAC increases amounts of trace metals such as Ca, K, Mg, Na, and Zn which is not preferable. Removal of ethyl bromide by distillation results in an exceptionally low pH aqueous solution of MEP.
Added ethyl bromide to the reactor, quickly added N-methylpyrrolidine to reactor and buttoned up. Passed N2 subsurface for 5 minutes to flush out all the air then released all pressure and closed all valves. Started stirrer but no heat applied, noted exotherm starting and pressure slowly increasing with temperature.
Setup distillation unit, pot temp to 82° C., distilled of 18 g of ethyl bromide 320 g fluid left in pot:
Treated fluid (290 g) with 50 g of GAC for 24 hour then filtered to give a 260 g of a very light colored fluid.
Testing of the MEP provided the following results:
There was Fe and Cr pickup from 316SS reactor. Need to do reaction in glass lined steel or other suitable materials to avoid metal pickup. APHA color is high and requires GAC treatment possibly because of the high reaction temperature of 80° C. Use of GAC increases amounts of trace metals. Removal of ethyl bromide by distillation results in an exceptionally low pH aqueous solution of MEP. This is not a preferred method of making MEP.
All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise.
It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of methods differing from the type described above. Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention set forth in the appended claims. The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims.
This is a continuation of U.S. full utility patent application Ser. No. 17/983,873 filed on Nov. 9, 2022 (issuing as U.S. Pat. No. 11,827,599 on Nov. 28, 2023), the entirety of which is incorporated herein by reference and priority to/of which is hereby claimed.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17983873 | Nov 2022 | US |
| Child | 18519337 | US |
