1. A method for producing 2,7-octadien-1-ol comprising:
subjecting butadiene and water to a telomerization in the presence of a palladium catalyst, a tertiary amine and carbon dioxide, the palladium catalyst comprising a water-soluble triarylphosphine and a palladium compound, the water-soluble triarylphosphine comprising two or more sulfonate groups;
mixing a telomerization solution obtained by the telomerization with an organic solvent having a dielectric constant of 2 to 18 at 25\xb0 C. to form a liquid having an aqueous phase and an organic phase; and
carrying out phase separation of the liquid in the presence of carbon dioxide by recovering the 2,7-octadien-1-ol from the organic phase while retaining the palladium catalyst in the aqueous phase.
2. The method according to claim 1, wherein the water-soluble triarylphosphine is represented by the following general formula (I):
wherein:
R1, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms;
R7, R8, and R9 each independently represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms;
p, q, and r each independently represent an integer of 0 to 2;
M’s may be the same as or different from each other, and each M represents a cation of a metal atom belonging to Group 1 or an ammonium cation derived from a tertiary amine where the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 3 to 27;
n represents 0 or 1; and
sulfonate groups (\u2014SO3M) are each at a meta-binding position or a para-binding position to the phosphorous atom of the water-soluble triarylphosphine.
3. The method according to claim 2, wherein:
R1, R3, R5, R7, R8, and R9 each independently represent a hydrogen atom, a methyl group, or a methoxy group;
R2, R4, and R6 are a hydrogen atom;
M’s each independently represent a cation of an alkali metal atom or the ammonium cation derived from a tertiary amine; and
the sulfonate groups (\u2014SO3M) are each at the meta-binding position to the phosphorous atom of the water-soluble triarylphosphine.
4. The method according to claim 2, wherein:
R1, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom, a methyl group, or a methoxy group;
p, q, and r are each 0;
M’s each independently represent a cation of a lithium atom, a cation of a sodium atom, a cation of a potassium atom, or the ammonium cation derived from a tertiary amine; and
the sulfonate groups (\u2014SO3M) are each at a diagonal binding position of R1, R3, or R5 on the benzene ring.
5. The method according to claim 4, wherein:
R1, R3, and R5 are all the same as each other and each represent a hydrogen atom or a methyl group;
p, q, and r are each 0, and
M’s are the same as each other and each represent a cation of a lithium atom, a cation of a sodium atom, a cation of a potassium atom, or the ammonium cation derived from a tertiary amine.
6. The method according to claim 2, wherein:
at least two of R1, R3, and R5 are each an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
7. The method according to claim 6, wherein at least two of R1, R3, and R5 are each a methyl group.
8. The method according to claim 2, wherein M is an ammonium cation derived from a tertiary amine where the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 5 to 24.
9. The method according to claim 8, wherein M is an ammonium cation derived from a tertiary amine wherein the total number of carbon atoms of a group bonded to the nitrogen atom of the tertiary amine is 5 to 7.
10. The method according to claim 1, wherein the phase separation is carried out at a temperature of 130\xb0 C. or lower and a total pressure, after introduction of carbon dioxide, of 0.1 MPa (gauge pressure) or more.
11. The method according to claim 10, wherein the phase separation is carried out at a temperature of 5\xb0 C. to 90\xb0 C., and a total pressure, after introduction of carbon dioxide, of 0.5 MPa to 3 MPa (gauge pressure).
12. The method according to claim 1, wherein the telomerization is carried out at a temperature of 130\xb0 C. or lower and a total pressure, after introduction of carbon dioxide, of 0.5 MPa (gauge pressure) or more.
13. The method according to claim 1, wherein at least a part of the palladium catalyst in the aqueous phase is reused in the telomerization.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. An apparatus for heating a reductant delivery line using coolant from an internal combustion engine, the reductant delivery line receiving reductant from a reductant tank containing reductant and a portion of a coolant line being positioned within the reductant tank, comprising:
a coolant temperature module configured to determine a reductant tank outlet coolant temperature target; and
a coolant flow rate module configured to generate a coolant valve flow rate command and transmit the coolant valve flow rate command to a coolant valve controllable to regulate a flow rate of coolant through the coolant line, the coolant valve flow rate command being based on the reductant tank outlet coolant temperature target, a reductant tank inlet coolant temperature, and a reductant tank reductant temperature.
2. The apparatus of claim 1, wherein the coolant valve flow rate command comprises a pulse-width modulation signal.
3. The apparatus of claim 1, wherein the coolant flow rate module generates the coolant valve flow rate command independent of an ambient temperature.
4. The apparatus of claim 1, wherein the coolant flow rate module generates the coolant flow rate command based on a feedforward model.
5. The apparatus of claim 1, wherein the coolant valve flow rate command is further based on a rate of change of the reductant tank reductant temperature over time.
6. The apparatus of claim 1, wherein the reductant tank outlet coolant temperature target is defined by a predetermined upper temperature threshold and a predetermined lower temperature threshold.
7. The apparatus of claim 1, wherein the reductant tank outlet coolant temperature target comprises a coolant temperature value sufficient to thaw reductant in the reductant tank during operation of the internal combustion engine, prevent refreezing of the reductant in the reductant tank during operation of the internal combustion engine, and maintain a temperature of reductant in the reductant tank and reductant delivery line below a maximum tolerable temperature during operation of the internal combustion engine.
8. The apparatus of claim 1, further comprising a heat exchange power module configured to determine a heat exchange power factor, the heat exchange power module determining the heat exchange power factor according to a first mode when the reductant tank reductant temperature is above a freezing temperature of the reductant and according to a second mode when the reductant tank reductant temperature is below the freezing temperature of the reductant, wherein the coolant valve flow rate command is based on the determined heat exchange power factor.
9. The apparatus of claim 8, wherein in the first mode, the heat exchange power factor is determined by multiplying together a level of reductant in the reductant tank, a rate of change of the reductant tank reductant temperature, and a specific heat of the reductant in the reductant tank.
10. The apparatus of claim 8, wherein in the second mode, the heat exchange power factor comprises a predetermined constant.
11. The apparatus of claim 8, further comprising a coolant temperature difference module configured to determine a difference between the reductant tank outlet coolant temperature target and the reductant tank inlet coolant temperature, wherein the coolant valve flow rate command is based on the difference between the reductant tank outlet coolant temperature target and the reductant tank inlet coolant temperature.
12. The apparatus of claim 11, further comprising a comparison module configured to compare the heat exchange power factor and the difference between the reductant tank outlet coolant temperature target and the reductant tank inlet coolant temperature against a predetermined look-up table to determine a coolant valve modulation signal value, wherein the coolant valve flow rate command corresponds with the determined coolant valve modulation signal value.
13. A reductant heating system, comprising:
a coolant line comprising a first portion positionable in heat exchanging communication with reductant in a reductant tank and a second portion positionable in heat exchanging communication with reductant in a reductant line, the reductant line configured to receive reductant from the reductant tank, wherein the second portion receives coolant exiting the reductant tank from the first portion;
a flow regulation device coupled to the coolant line and configured to regulate the flow rate of coolant entering the first portion of the coolant line; and
a controller communicable in signal transmitting communication with the flow regulation device to vary the flow rate of coolant through the first portion of the coolant line to achieve a desired temperature of coolant exiting the reductant tank in the second portion of the coolant line based on a temperature of coolant entering the reductant tank via the first portion and a temperature of reductant in the reductant tank.
14. The reductant heating system of claim 13, further comprising a temperature sensor coupled to the coolant line and configured to sense the temperature of coolant entering the reductant tank via the first portion of the coolant line.
15. The reductant heating system of claim 14, wherein the controller is further configured to vary the flow rate of coolant entering the first portion of the coolant line based on a rate of change of the temperature of reductant in the reductant tank.
16. The reductant heating system of claim 15, wherein the controller is further configured to vary the flow rate of coolant entering the first portion of the coolant line based on a specific heat of the reductant in the reductant tank.
17. The reductant heating system of claim 16, wherein the controller is further configured to vary the flow rate of coolant entering the first portion of the coolant line based on a level of reductant in the reductant tank.
18. The reductant heating system of claim 17, wherein the controller is further configured to vary the flow rate of coolant entering the first portion of the coolant line based on a difference between the temperature of the coolant sensed by the temperature sensor and the desired temperature of coolant in the second portion of the coolant line.
19. The reductant heating system of claim 18, wherein the controller is further configured to vary the flow rate of coolant entering the first portion of the coolant line based on a shape of the reductant tank and a specific heat of the coolant.
20. The reductant heating system of claim 13, wherein the second portion of the coolant line winds about the reductant line.
21. A method for heating reductant in a reductant line coupled to a reductant tank, comprising:
sensing a temperature of coolant entering a coolant line positioned in heat transfer communication with reductant in the reductant line and reductant tank;
determining upper and lower temperature thresholds of reductant in the reductant line; and
regulating a single flow regulating valve to adjust a flow rate of coolant through the coolant line based on the sensed temperature of coolant entering the coolant line, a desired temperature of coolant exiting the reductant tank, and a temperature of reductant in the reductant tank to maintain the temperature of reductant in the reductant line below the upper temperature threshold and above the lower temperature threshold.
22. The method of claim 21, wherein regulating the single flow regulating valve comprises adjusting the flow rate of coolant through the coolant line to maintain a temperature of reductant in the reductant tank above a threshold.