Apparatus and methods to preserve catalyst activity in an epoxidation process
View Patent ↗Apparatus and methods are provided for forming and processing multiphasic systems. In one embodiment, the invention provides a process for the manufacture of an epoxide, including reacting an olefinically unsaturated compound with an oxidant in the presence of a buffer component and a water-soluble manganese complex disposed in an aqueous phase having a first pH level in a first multiphasic system, adjusting the pH of the aqueous phase to a second pH level less than the first pH level, isolating at least a portion of the aqueous phase from the first multiphasic system, adjusting the pH of the at least a portion of the aqueous phase to a third pH level greater than the second pH level, and introducing the at least a portion of the aqueous phase into a second multiphasic system.
1. A process for processing a multiphasic system comprising:
reacting an olefinically unsaturated compound with an oxidant in the presence of a buffer component and a water-soluble manganese complex disposed in an aqueous phase having a first pH level in a first multiphasic system;
adjusting the pH of the aqueous phase to a second pH level less than the first pH level;
isolating at least a portion of the aqueous phase from the first multiphasic system and retaining the water-soluble manganese complex in the aqueous phase;
adjusting the pH of the at least a portion of the aqueous phase to a third pH level greater than the second pH level; and
introducing the at least a portion of the aqueous phase into a second multiphasic system, wherein adjusting the pH of the aqueous phase to the second pH level comprises inactivating the water-soluble manganese complex and wherein adjusting the pH of the at least a portion of the aqueous phase to the third pH level comprises reactivating the water-soluble manganese complex.
2. The process according to claim 1 , wherein reacting the olefinically unsaturated compound with the oxidant in the first multiphasic system comprises:
adding the oxidant and the water-soluble manganese complex as aqueous components to the first multiphasic system; and
dispersing the olefinically unsaturated compound into the aqueous phase.
3. The process according to claim 1 , wherein the first pH level is from greater than 2.5 to 6.
4. The process according to claim 1 , wherein the second pH level is 2.5 or less.
5. The process according to claim 1 , wherein the adjusting the pH of the aqueous phase to the second pH level comprises adding an acid selected from the group oxalic acid, acetic acid, formic acid, nitric acid, hydrochloric acid, sulphuric acid, and combinations thereof.
6. The process according to claim 1 , wherein the third pH level is from greater than 2.5 to 6.
7. The process according to claim 1 , wherein adjusting the pH of the aqueous phase to the third pH level comprises adding a base selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide, potassium carbonate, sodium carbonate, potassium oxalate, sodium oxalate, and combinations thereof.
8. The process of claim 1 , wherein the first pH level and the third pH level are the same pH level.
9. The process of claim 1 , further comprising:
reacting a second olefinically unsaturated compound with a second oxidant in the presence of a second buffer component and the water-soluble manganese complex in an aqueous phase having the third pH level in the second multiphasic system.
10. The process of claim 1 , wherein the water-soluble manganese complex has a first Turn Over Number rate from 2000 TON/hr to about 20,000 TON/hr at the first pH level, a second Turn Over Number rate from about 0 TON/hr to less than 2000 TON/hr at the second pH level, and a third Turn Over Number rate from 2000 TON/hr at the third pH level.
11. The process of claim 1 , wherein a time period between adjusting the pH of the aqueous phase to a second pH level and adjusting the pH of the aqueous phase to a third pH level is from about 1 minute to about 120 minutes.
12. The process of claim 1 , wherein the manganese complex comprises:
a mononuclear species of the formula (I):
[LMnX m ]Y (I),
a binuclear species of the formula (II):
[LMn(μ-X) m MnL]Y n (II), or
a polynuclear species of the formula (III):
[L n Mn n (μ-X) m ]Y n (III), and
wherein Mn is manganese; L or each L is independently a polydentate ligand, each X is independently a coordinating species and each μ-X is independently a bridging coordinating species, wherein Y is a non-coordinating counter ion and m is from 1 to 4 and n is from 1 to 2.
13. The process of claim 12 , wherein each coordinating species and each bridging coordinating species is selected from the group consisting of RO − , Cl − , Br − , I − , F − , NCS − , N 3 − , I 3 − , NH 3 , NR 3 , RCOO − , RSO 3 − , RSO 4 − , OH − , O 2− , O 2 2− , HOO − , H 2 O, SH − , CN − , OCN − , C 2 O 4 2− , and SO 4 2− and combinations thereof, wherein R is a C 1 -C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combinations thereof, and Y is a non-coordinating counter ion.
14. The process of claim 1 , further comprising adding a second manganese complex to the second multi-phasic system.
15. The process of claim 13 , wherein Y is an anion selected from the group consisting of RO − , Cl − , Br − , I − , F − , SO 4 2− , RCOO − , PF 6 − , tosylate, triflate (CF 3 SO 3 − ) and a combination thereof with R once again being a C 1 to C 20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl and combination thereof.