METHOD OF PREPARING IONIC FLUIDS

Abstract

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 solution of ethyl bromide; and (e) removing N-methylpyrrolidine and ethyl bromide from the first aqueous solution of MEP.

Claims

1-23. (canceled)

24. A method of preparing MEP comprising 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 varies; (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 solution of ethyl bromide; and (e) removing N-methylpyrrolidine and ethyl bromide from the first aqueous solution of MEP.

25. The method of preparing MEP of claim 24, wherein during step a the reaction temperature is maintained lower than 50? C.;

26. The method of preparing MEP of claim 24, wherein step b occurs when the excess of ethyl bromide to the N-methylpyrrolidine falls within a range of 3:1 to 1.85:1.

27. The method of preparing MEP of claim 24, wherein step b occurs when the excess of ethyl bromide to the N-methylpyrrolidine falls within a range of 2:1 to 1.85:1.

28. The method of preparing MEP of claim 24, wherein during step b the excess of ethyl bromide to the N-methylpyrrolidine within a range of 3:1 to 2:1.

29. The method of preparing MEP of claim 24, wherein and a slurry of MEP is formed in the excess of ethyl bromide in step b, and the slurry of MEP and excess ethyl bromide is allowed to cool to 25? C. between steps b and c.

30. The method of preparing MEP of claim 24, wherein in step c the water is purified water selected from the group consisting of de-ionized water, reverse osmosis water, and distilled water.

31. The method of preparing MEP of claim 24, wherein step d is performed using a phase cut.

32. The method of preparing MEP of claim 24, wherein step e sparging with a noble gas is used for removal of N-methylpyrrolidine and ethyl bromide.

33. The method of preparing MEP of claim 24, wherein step e sparging with a gas is used for removal of N-methylpyrrolidine and ethyl bromide, wherein said gas is non-reactive relative to MEP, N-methylpyrrolidine, and ethyl bromide.

34. The method of preparing MEP of claim 33, wherein the sparging is performed at a temperature of between 30? C. and 50? C.

35. The method of preparing MEP of claim 33, wherein at the end of step e the pH is between 6 and 9.

36. The method of preparing MEP of claim 33, wherein at the end of step e the pH is between 6 and 9 due to ethyl bromide.

37. The method of preparing MEP of claim 24, wherein in step a, the reactor is selected from the group consisting of a container, a tank, a vessel, a pressure vessel, a pipe, a conduit, and a flask.

38. The method of preparing MEP of claim 24, wherein in step a, the reactor is insulated.

39. The method of preparing MEP of claim 24, wherein in step a, the reactor is a jacketed vessel.

40. The method of preparing MEP of claim 24, wherein in step e, N-methylpyrrolidine is removed until its concentration in the first aqueous solution of MEP is less than 2000 parts per million.

41. The method of preparing MEP of claim 42, wherein in step e, N-methylpyrrolidine is removed until its concentration in the first aqueous solution of MEP is not detectable.

42. The method of preparing MEP of claim 24, wherein in step e, ethyl bromide is removed until only trace amounts of ethyl bromide remain in the first aqueous solution of MEP

43. The method of preparing MEP of claim 44, wherein in step e, ethyl bromide is removed until its concentration in the first aqueous solution of MEP is not detectable.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] 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.

[0029] FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

[0030] FIG. 2 is a C13 Nuclear magnetic resonance (NMR) spectroscopy of the collected aqueous solution of MEP in CD3CN.

DETAILED DESCRIPTION

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] The following is an example of a preferred method of making MEP in one embodiment.

[0038] 1. Obtain the following starting materials: [0039] (a) ethyl bromide, [0040] (b) N-methylpyrrolidine, and [0041] (c) water (preferably distilled, de-ionized, or reverse osmosis)

[0042] 2. Start with ethyl bromide in a reactor which can be a container, tank, vessel, pressure vessel, pipe, conduit or flask.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 6. Add purified water to the reactor causing the MEP to enter the aqueous phase and creating a 2-phase system: [0047] (i) a top layer having the MEP dissolved in the added water (with traces of unreacted ethyl bromide and N-methylpyrrolidine), and [0048] (ii) a bottom layer having ethyl bromide and traces of water.
Purified water can be of several types including without limitation de-ionized water, reverse osmosis water, and distilled water. In one embodiment the water is purified to minimize or eliminate contamination in the two phase system.

[0049] 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).

[0050] 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., N.sub.2) 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., N.sub.2). 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.

EXAMPLES

Example 1 Reaction to Make MEP in Excess Ethyl Bromide as Solvent then Solvent Swap with Water-Pot Temperature Kept at 40? C. or Less

Questions to Answer

[0051] 1. Can the reaction be run in glassware at atmospheric pressure under reflux solely with an excess ethyl bromide? [0052] 2. Can a solvent swap be performed after reaction to replace ethyl bromide with purified (e.g., reverse osmosis) water? [0053] 3. Effects of pH on keeping pot temperature<40? C. during solvent swap. [0054] 4. What is the yield recovery for ethyl bromide?
FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

Experimental Section

Reactants:

[0055]

TABLE-US-00001 N-methyl-N- ethylpyrrolidinium bromide: ethyl bromide: N-methylpyrrolidine CAS #69227-51-6 MW = 108.97 MW = 85.15 Pyrrolidinium, 1-ethyl-1- methyl-,bromide Bpt = 38? C. Bpt = 76-80? C. 1-methyl-1-ethyl pyrrolidinium-bromide Density = 1.47 Density = 0.82 MW 194.11

[0056] Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.

[0057] Initial Charges

TABLE-US-00002 N-methylpyrrolidine: 85.15 g 1 mole (added via dropping funnel) ethyl bromide: 218 g (2 moles)

Solvent Swap

[0058] RO Water: 110 g

TABLE-US-00003 TABLE 1 Addition of N-methylpyrrolidine Over Time N-methyl- Time Temp pyrrolidine (am) (? C.) (MP) (mls) Comments 7:45 18.7 0 start of reaction 7:47 20.2 20 7:56 27.4 35 8:00 33.2 45 8:04 43.5 70 ethyl bromide is refluxing 8:08 44.2 85 8:13 44.9 90 8:17 45 95 all MP has been added and reaction is starting to cool 8:20 45 8:32 43.3 9:08 38.8 9:30 25 Added 110 g of RO water and stirred to dissolve all the MEP. MEP is very soluble in water. Phase separated bottom layer to give 106.2 g of ethyl bromide. Top layer set up in distillation mode with an N.sub.2 sparge to help remove unreacted trace amounts of ethyl bromide and MP. 10:30 36.4 10:34 47.7 10:37 49.1 10:40 49.2 10:52 45.3 A very small amount of distillate was collected and some hung up in condenser.

[0059] Testing of the MEP provided the following results:

TABLE-US-00004 N-methylpyrrolidine 240 ppm pH 9.02 Color APHA 69 % Water 48.1% Density: 1.194 kg/m.sup.3 at 22? C.

TABLE-US-00005 TABLE 2 Tested Anions and Cations Amount Anion/Cation Detected (ppm) F <1 Cl 9 Br 264,438 NO.sub.3 <1 PO.sub.4 <1 SO.sub.4 27 NH.sub.4 N/A

TABLE-US-00006 TABLE 3 AN-3532-HPZB-171 Test Results for Reaction to Make MEP Amount Detected Element Crude (ppm) Ag <1 Al <1 As <1 B <1 Ba 7 Be <1 Ca <1 Cd <1 Co <1 Cr <1 Cu <1 Fe <1 K <1 Li <1 Mg 4 Mn <1 Mo <1 Na 16 Ni <1 P <1 Pb <1 Sb <1 Se <1 Si <1 Sn <2 Sr <1 Ti <1 V <1 Zn <3
Theoretical composition of Br.sup.? for 65% MEP in water=26.8% (weight percent), and measured was 26.44%

Conclusions

[0060] 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.

Example 2: Reaction to Make MEP in 2? Excess Ethyl Bromide Evaluating pH Versus Sparge Time

Questions to Answer

[0061] 1. Can the reaction be run in glassware at atmospheric pressure under reflux solely with an excess ethyl bromide? [0062] 2. Can a solvent swap be performed after reaction to replace ethyl bromide with purified (e.g., reverse osmosis) water? [0063] 3. Effects of pH on keeping pot temperature<40? C. during solvent swap. [0064] 4. What is the yield recovery for ethyl bromide? [0065] 5. Use of N.sub.2 Sparge to remove residual ethyl bromide measure pH versus sparge time at 40? C.
FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

Experimental Section

Reactants: Same as in Example 1.

[0066] Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.

Initial Charges

[0067]

TABLE-US-00007 N-methylpyrrolidine: 85.15 g 1 mole (added via dropping funnel) ethyl bromide: 218 g (ChemUniverse) 2 moles

Solvent Swap

[0068] RO Water: 110 g

TABLE-US-00008 TABLE 4 Reaction HPZB-193: Addition of N-methylpyrrolidine Over Time N-methyl- Time Temp pyrrolidine (am) (? C.) (MP) (mls) Comments 9:00 18.3 0 9:06 22.1 30 9:26 41.7 50 9:31 45.2 100 9:33 45.2 all 9:40 46.0 9:45 45.2 10:10 41.4 40:48 35.6 11.15 30 Added 110 g of RO water and turned up stirrer speed to dissolve all the MEP. Temp went to 26? C. Performed a phase cut removing the bottom layer. Top layer was 305.76 g and setup for N.sub.2 sparge versus time and temperature.

TABLE-US-00009 TABLE 5 N.sub.2 Sparging Over Time Time Temp (24 hr) (? C.) pH Comments 11:28 23.8 11.47 Turned on heat. 11.33 27.8 11.27 11.36 32 11.15 11.37 33.5 11.11 11.38 34.2 11.08 11.39 34.6 11.03 11.53 34.5 10.6 Heat turned up. 12.38 49.4 9.04 Heat off. 12.41 48.7 8.98 13.01 34.8 8.93 13:41 24.3 8.9 14:55 20.9 8.81 N.sub.2 Sparge stopped. 292 g of clear MEP = 96.05% Yield (probably lost some water lost by sparging as well)

[0069] Testing of the MEP provided the following results:

TABLE-US-00010 N-methylpyrrolidine 208 ppm pH 8.65 (day 1) and 8.17 (day 5) Color APHA 13 % Water 33.0% Density: 1.1965 kg/m.sup.3 at 21? C.

TABLE-US-00011 TABLE 6 Tested Anions and Cations Anion/Cation Amount Detected (ppm) F <7 Cl <13 Br 272,303 NO.sub.3 <26 PO.sub.4 <39 SO.sub.4 <26 NH.sub.4 <48

TABLE-US-00012 TABLE 7 AN-3532-HPZB-171 Test Results for Reaction to Make MEP Amount Detected Element Crude (ppm) Ag <1 Al <1 As <1 B 2 Ba <1 Be <1 Ca <1 Cd <1 Co <1 Cr <1 Cu <1 Fe <1 K 5 Li <1 Mg 2 Mn <1 Mo <1 Na <1 Ni <1 P <1 Pb <1 Sb <1 Se <1 Si 5 Sn <1 Sr <1 Ti <1 V <1 Zn <1

Conclusions

[0070] 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.

Example 3 To Make MEP in Excess Ethyl Bromide as Solvent then Solvent Swap with Water

Questions to Answer

[0071] 1. Can the reaction be run in glassware at atmospheric pressure under reflux solely with an excess ethyl bromide? [0072] 2. Can a solvent swap be performed after reaction to replace ethyl bromide with purified (e.g., reverse osmosis) water? [0073] 3. What is the yield recovery for ethyl bromide?
FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

Experimental Section

Reactants: Same as in Example 1.

[0074] Glass reactor (500 ml 4 neck) setup with overhead stirrer, thermocouple, reflux condenser and pressure equalized dropping funnel.

Initial Charges

[0075]

TABLE-US-00013 N-methylpyrrolidine: 85.15 g 1 mole (added via dropping funnel) Ethyl Bromide: 218 g (VWR) 2 moles

Solvent Swap

[0076] RO Water: 110 g

TABLE-US-00014 TABLE 8 Addition of N-methylpyrrolidine Over Time N-methyl- Time Temp pyrrolidine (am) (? C.) (MP) (mls) Comments 8:05 19.3 0 218 g of ethyl bromide placed in the reactor. 8:07 20.3 10 Started to add N-methylpyrrolidine dropwise. 8:14 23.4 15 8:22 27 20 8:29 33.3 30 8:31 37 35 8:35 40.9 35 Hard reflux of ethyl bromide started so stopped addition of MP to lower reflux. 8:36 40.8 35 8:57 38.9 35 Restarted adding MP. 9:04 38.9 45 9:15 40.4 60 9:20 42.8 80 9:31 43.7 all in 10:20 37.7 Solid MEP has crashed out of excess ethyl bromide. A white slurry of MEP can be seen. 10:25 28.2 110 g of reverse osmosis water was added to dissolve the MEP (perform the solvent swap). In the reactor there is now a top layer of aqueous MEP and a bottom layer of ethyl bromide. 36.9 Setup reactor for distillation and heat applied using an isomantle. Reflux of ethyl bromide started at 36.9? C. 40.5 Hard reflux of ethyl bromide started with lots of distillate being collected by distillation. 60.1 100 g of ethyl bromide collected (92% recovery based on excess charge)

[0077] FIG. 2 graphically illustrates various C13 Nuclear magnetic resonance (NMR) spectroscopy testing results on the collected aqueous solution of MEP. The following is a Peak List: 10 peaks: [0078] 1: 137 Hz (9.04 ppm) [0079] 2: 325 Hz (21.44 ppm) [0080] 3: 723 Hz (47.60 ppm) [0081] 4: 727 Hz (47.85 ppm) [0082] 5: 731 Hz (48.10 ppm) [0083] 6: 902 Hz (59.36 ppm) [0084] 7: 905 Hz (59.53 ppm) [0085] 8: 966 Hz (63.57 ppm) [0086] 9: 969 Hz (63.76 ppm) [0087] 10: 972 Hz (63.95 ppm)
It is noted that for the collected aqueous solution of MEP there was no sign of N-methylpyrrolidine (it was not detectable in the C13 NMR).

[0088] Testing of the MEP provided the following results:

TABLE-US-00015 Crude GAC Treated N-methylpyrrolidine none detected 76 ppm pH 6.2 (going to 5.6 2.86 on standing) Color APHA 228 117 % Water N/A N/A
Crude is as the MEP came out of the reactor. GAC is after treatment with granulated activated carbon.

TABLE-US-00016 TABLE 9 AN-3529-HPZB-167 Test Results for Reaction to Make MEP Amount Detected GAC Element Crude (ppm) Treated (ppm) Ag <1 <1 Al <1 <1 As <1 <1 B <1 3 Ba <1 <1 Be <1 <1 Ca <1 <1 Cd <1 <1 Co <1 <1 Cr <1 <1 Cu <1 <1 Fe <1 <1 K <1 70 Li <1 <1 Mg <1 <1 Mn <1 <1 Mo <1 <1 Na 45 30 Ni <1 <1 P <1 <1 Pb <1 <1 Sb <1 <1 Se <1 <1 Si <1 <1 Sn <1 <1 Sr <1 <1 Ti <1 <1 V <1 <1 Zn <6 9 [0089] Yield: 298 g of pale yellow liquid with pH 6.20 [0090] Theory yield=304.11 g (194.11 g MEP plus 110 g water) [0091] Crude Yield=98% [0092] Took 195 g yellow liquid plus 5 g of granulated activated carbon (GAC) and stirred for 2 hrs then filtered to leave 185 g of a water white liquid. pH 8.34. [0093] 5% loss [0094] Purified yield=93%

Conclusions

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

Example 4 Make MEP in Glass Reactor with Water as Solvent

Questions to Answer

[0102] 1. Can the reaction be run in glassware at atmospheric pressure under reflux using water as the solvent?
FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

[0103] Experimental Section

Reactants: Same as in Example 1.

[0104] Glass reactor (500 ml 3 neck) setup with magnetic stirrer, thermocouple, and reflux condenser.

Initial Charges

[0105]

TABLE-US-00017 N-methylpyrrolidine: 85.15 g 1 mole Water 250 g Ethyl Bromide: 180 g 1.65 moles (Lot # 1902141030724 from Chem Universe 99.6%)

TABLE-US-00018 TABLE 10 Addition of N-methylpyrrolidine to Water Over Time (slight exotherm from 28 to 31? C.), heat of solution N-methyl- Time Temp pyrrolidine (am) (? C.) (MP) (mls) Comments 8:40 31 0 8:43 31 35 8:44 31 75 8:45 31 105 9:07 49 105 Reflux of ethyl bromide seen so stopped addition of MP to lower reflux. 9:30 42 135 9:40 38.8 165 10:00 35 180 Little to no reflux of ethyl bromide. Color is pale yellow. 10:30 38 Setup reactor for distillation, temperature set at 100? C. 10:30 102 Small amount of distillate came over, mixture now orange 443 g crude MEP in water Theory 444.15 g Crude yield = 99.7%

[0106] 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.

[0107] Testing of the MEP after treatment with GAC provided the following results:

TABLE-US-00019 N-methylpyrrolidine 135 ppm pH 4.48 Color APHA 126

TABLE-US-00020 TABLE 11 Tested Anions and Cations Amount Anion/Cation Detected (ppm) F <1 Cl 46.3 Br 168,486 NO.sub.3 <1 PO.sub.3 103 SO.sub.4 20.5 NH.sub.4 N/A

TABLE-US-00021 TABLE 12 AN-3520-HPZB-160 Test Results for Reaction to Make MEP in H2O At Atm Amount Detected Element Crude (ppm) Ag <1 Al <1 As <1 B <1 Ba <1 Be <1 Ca 13 Cd <1 Co <1 Cr <1 Cu <1 Cu <1 Fe <1 K 692 Li <1 Mg 49 Mn <1 Mo <1 Na 51 Ni <1 P <1 Pb <1 Sb <1 Se <1 Si <1 Sn <1 Sr <1 Ti <1 V <1 Zn <3
This is 194.11 g MEP in total 444.11 g solution giving 43.7% solution in water [0108] Theory wt % Br.sup.?=18%. [0109] Found wt % Br.sup.?=16.84%

Conclusions

[0110] 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.

Example 5 Make MEP in Glass Reactor with Water as Solvent

Questions to Answer

[0111] 1. Reaction N-methylpyrrolidine with ethyl bromide to make N-methyl-N-ethylpyrrolidinium bromide [0112] 2. Use Ethyl bromide in excess (50%) [0113] 3. Use water as the solvent [0114] 4. Temperature 80? C. for Hours [0115] 5. Best isolation procedure (heat solution to flash of excess ethyl bromide) [0116] 6. Puritydesire free N-methylpyrrolidine<2000 ppm
FIG. 1 shows the chemical reaction of N-methylpyrrolidine with ethyl bromide to form MEP.

Experimental Section

Reactants: Same as in Example 1.

[0117] Added ethyl bromide to the reactor, quickly added N-methylpyrrolidine to reactor and buttoned up. Passed N.sub.2 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.

Initial Charges

[0118]

TABLE-US-00022 Initial Charges N-methylpyrrolidine: 85.15 g 1 mole Water 110 g Ethyl Bromide: 164 g 1.5 moles

TABLE-US-00023 TABLE 13 Forming MEP Time Reaction Temp (am) Time (? C.) psi Comments 8:00 30 4 Flushed with N.sub.2 8:17 63 14 8:30 68 24 9:30 75 34 Max exotherm turned on heat set to 80? C. 9:50 80 40 12:30 80 41 Heat off and applied cooling 12:36 about 4 15 10 Released pressure and emptied liquid from hours at reactor (350 g). 80? C.

Results and Discussion

[0119] 350 g amber liquid (359 g was charged to reactor)

[0120] Setup distillation unit, pot temp to 82? C., distilled of 18 g of ethyl bromide 320 g fluid left in pot:

[0121] 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. [0122] pH 0.14

[0123] Testing of the MEP provided the following results:

TABLE-US-00024 pH 0.14 Color APHA 149

TABLE-US-00025 TABLE 14 Tested Anions and Cations Anion/Cation Amount Detected (ppm) F 4.7 Cl 53.4 Br 289,179 NO.sub.3 <1 PO.sub.3 135 SO.sub.4 39.2 NH.sub.4 N/A

TABLE-US-00026 TABLE 15 AN-3519-HPZB-156 Test Results for Reaction to Make MEP in H2O Amount Detected Element Crude (ppm) Ag 46 Al <1 As <1 B <1 Ba <1 Be <1 Ca 102 Cd <1 Co <1 Cr 104 Cu <1 Fe 73 K 1590 Li <1 Mg 172 Mn 7 Mo 2 Na 118 Ni 52 P 60 Pb <1 Sb <1 Se <1 Si 16 Sn <1 Sr 2 Ti <1 V <1 Zn <7

Conclusions

[0124] 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.

[0125] All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise.

[0126] 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.