Abstrict For the regeneration of a liquid desiccant, a stripping agent is
used which is liquid at ambient temperature and pressure, and forms
a heteroazeotrope with water, along with the following steps: (a)
distillation of the water-laden liquid desiccant to form vapor and
partially regenerated liquid desiccant; (b) reboil partially regenerated
liquid desiccant; (c) stripping of partially regenerated liquid
desiccant during (a) and (b), using vaporized stripping agent; (d)
a condensing of vapor the exiting the distillation, the condensation
producing two liquid phases, one mainly water and the other mainly
stripping agent; (e) heating the stripping agent-rich liquid phase
exiting step (d) to generate a vapor phase which is richer in water
than said liquid phase and a water-depleted liquid phase; and (f)
returning the vaporized liquid phase exiting step (e) to step (c).
Claims We claim:
1. A liquid desiccant regeneration process using a stripping agent,
wherein the stripping agent is liquid at ambient temperature and
pressure, and forms a heteroazeotrope with water; and the process
comprises:
(a) distilling a water laden liquid desiccant in a distillation
zone comprising at least one rectification stage to produce an overhead
vapor and a partially regenerated liquid desiccant;
(b) reboiling in a reboil zone said partially regenerated liquid
desiccant to provide a vapor phase and residual partially regenerated
liquid desiccant;
(c) stripping in a stripping zone the residual partially regenerated
liquid desiccant from step (b), using vaporized stripping agent,
to provide regenerated liquid desiccant;
(d) condensing the overhead vapor exiting distillation step (a),
the condensation producing two liquid phases, a water-rich liquid
phase and a stripping agent-rich liquid phase;
(e) heating the stripping agent-rich liquid phase from step (d)
to generate a vapor phase richer in water than said liquid phase
and a water-depleted liquid stripping agent phase; and
(f) vaporizing at least a portion of resultant water-depleted liquid
stripping agent phase from step (e) said portion being substantially
sufficient to maintain a constant flow rate of vaporized stripping
agent in step (c);
(g) utilizing resultant vaporized water-depleted stripping agent
from step (f) in step (c); and
(h) collecting the regenerated liquid desiccant from step (c) in
a reservoir.
2. A process according to claim 1 wherein the vapor phase generated
during step (e) is returned to a position upstream of step (d).
3. A process according to claim 1 wherein a portion of the stripping
agent-rich liquid phase exiting step (d) is returned to step (a)
and placed in contact with the distillation vapor.
4. A process according to claim 3 wherein the temperature in the
reboiling step (b) is between 50.degree. and 250.degree. C.
5. A process according to claim 3 wherein the absolute pressure
in the distillation zone, the reboil zone, the stripping zone and
the reservoir is between 0.5 and 2 bar.
6. A process according to claim 3 wherein a fixed portion of water-depleted
liquid stripping agent phase from step (e) is vaporized in step
(f) and evacuating any excess water-depleted liquid stripping agent
from the process.
7. A process according to claim 1 wherein the water depleted liquid
stripping agent exiting step (e) is vaporized before being transported
to stripping step (c).
8. A process according to claim 1 wherein the water depleted liquid
stripping agent phase exiting step (e) is transported in liquid
form towards stripping step (c) and vaporized during the course
thereof, and the resultant vaporized form is employed as the stripping
agent.
9. A process according to claim 1 wherein steps (a) and (c) are
carried out in separate apparatus.
10. A process according to claim 1 wherein steps (a) and (c) are
carried out simultaneously in the same apparatus, the water, depleted
liquid stripping agent phase from the heating step (e) being transported
towards the reboil zone of step (b).
11. A process according to claim 10 wherein the water-depleted
stripping agent phase from the heating step (e) is introduced into
the reboil zone in liquid form and is vaporized therein.
12. A process according to claim 10 wherein the water-depleted
stripping agent phase is vaporized before introduction into the
reboil zone.
13. A process according to claim 1 wherein the liquid desiccant
is a glycol.
14. A process according to claim 13 wherein the glycol is triethylene
glycol.
15. A process according to claim 1 wherein the stripping agent
is a mixture of hydrocarbons.
16. A process according to claim 15 wherein the stripping agent
comprises a major amount of benzene.
17. A process according to claim 1 wherein the temperature in
the reboiling step (b) is between 150.degree. and 250.degree. C.
18. A process according to claim 1 wherein the absolute pressure
in the distillation zone, the reboil zone, the stripping zone and
the reservoir is between 0.5 and 2 bar.
19. A process according to claim 1 wherein a fixed portion of
water-depleted liquid stripping agent phase from step (e) is vaporized
in step (f) and evacuating any excess water-depleted liquid stripping
agent from the process.
Description BACKGROUND OF THE INVENTION
Gaseous streams, for example natural or refined gas, are usually
dehydrated to control, inter alia, the water dew point of the gaseous
stream and avoid hydrate or ice formation.
To dehydrate it, the gas is usually placed in contact with a hydrophilic
liquid desiccant, among the most popular being chemicals of the
glycol family. Triethylene glycol (TEG) is the most widely used,
but monoethylene glycol (MEG), diethylene glycol (DEG) or tetraethylene
glycol (T4EG) may also be used. The water-laden desiccant is then
transported to a thermal regeneration apparatus in which most of
the water absorbed by the desiccant is vaporized and eliminated.
However, it is well known that it is not possible to separate the
water completely from the desiccant using a thermal technique at
atmospheric pressure, since the desiccant degrades at a temperature
below the normal boiling point. TEG, for example, boils at 285.degree.
C., but the regeneration temperature is normally limited to 204.degree.
C. The purity of regenerated TEG is then about 99% by weight.
For greater purity, one conventional method consists in following
the thermal reconcentration step with a stripping step using a dry
or low water content gas, for example a portion of the gaseous stream
dehydrated by the desiccant. This type of process, described in
detail in United States patent U.S. Pat. No. 3105748 produces
a purity of about 99.9% by weight of the regenerated desiccant.
However, apart from generally resulting in a dry loss, one problem
in using gas as a stripping agent is that it prevents condensation
of hydrocarbons and other heavy substances absorbed by the desiccant
during the dehydration step and vaporized at the same time as the
water during reboiling and stripping. In particular, aromatics thus
liberated cannot be recondensed and are flared or evacuated unchanged
into the atmosphere.
To overcome these drawbacks, the stripping gas may be replaced
by a circuit containing a condensable agent, normally a hydrocarbon
or mixture of hydrocarbons. In this type of process, described in
detail in United States patent U.S. Pat. No. 3471370 the stripping
agent is recovered after condensation at the head of the thermal
concentration stage and separation of the water condensed therewith.
When very high purity of regenerated desiccant is required, for
example greater than 99.99% by weight for TEG, a stripping agent
which is itself very dry must be employed. If, for example, the
stripping agent forms part of the dehydrated gaseous stream, it
has been suggested that the water content of this gas can be further
reduced by contacting it with a portion of the high purity regenerated
desiccant, said portion then being returned to the stripping stage.
This type of process is described in detail in United States patent
U.S. Pat. No. 3867112. If a condensable stripping agent is used,
dehydration under pressure of this agent by various means has been
proposed.
SUMMARY OF THE INVENTION
The discovery that it is possible to regenerate the dessicating
agent to a very high level of purity and limit emission of heavy
hydrocarbons in economic fashion by employing a condensable stripping
agent and dehydrating it in novel fashion forms the object of the
present invention.
Generally, a liquid desiccant regeneration process using a stripping
agent in accordance with the invention is characterized in that:
i)- the stripping agent is liquid at ambient temperature and pressure,
and forms a heteroazeotrope with water;
ii)- the process comprises the following steps:
(a) a distillation step comprising at least one rectification step
for the water-laden liquid desiccant to form vapor and partially
regenerated liquid;
(b) a reboil step for the partially regenerated liquid desiccant,
(c) a stripping step carried out on the partially regenerated liquid
desiccant during steps (a) and (b), using the vaporized stripping
agent;
(d) a condensation step for the vapor exiting distillation step
(a), the condensation producing two liquid phases, one mainly water
and the other mainly stripping agent;
(e) heating the stripping agent-rich liquid phase exiting step
(d) to generate a vapor phase which is richer in water than said
liquid phase and a water-depleted liquid phase; and
(f) returning the liquid phase exiting step (e) to step (c).
One of the principal objects of the present invention is constituted
by the discovery that heating the water-saturated liquid stripping
agent exiting condensation step (d) substantially reduces the residual
quantity of water in the stripping agent at low energy cost, even
when the boiling point of the stripping agent is lower than that
of water. This is achieved by exploiting the heteroazeotrope between
water and the stripping agent.
The inventive process is thus particularly suitable when it is
necessary to regenerate the desiccant to a very high purity, requiring
the use of a stripping agent which is itself almost anhydrous, and
also when it is undesirable to lose noncondensable stripping agent
either for economic reasons or to limit emission into the atmosphere
of higher hydrocarbons or other substances of comparable volatility.
Steps (a) and (c) of the inventive process may be carried out successively
in separate apparatus or simultaneously in the same apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
Various other objects, features and attendant advantages of the
present invention will be more fully appreciated as the same becomes
better understood when considered in conjunction with the accompanying
drawings, in which like reference characters designate the same
or similar parts throughout the several views, and wherein:
FIGS. 1 2 and 4 are schematic flow sheets of preferred comprehensive
embodiments of the invention, wherein the distillation and stripping
steps are conducted in series.
FIG. 3 is a partial flow sheet wherein the distillation and stripping
steps are conducted simultaneously.
DETAILED DESCRIPTION OF THE FIGURES
One specific embodiment of the inventive process will now be described
in further detail with reference to FIG. 1. In this embodiment,
the vapor phase generated during step (e) may be returned upstream
of step (d) and the water-depleted liquid phase exiting step (e)
is vaporized before being returned to step (b) or step (c).
The charge to be treated arrives via conduit 1 at exchanger E1
positioned at the head of distillation apparatus D1; from here it
is carried by conduit 2 to exchanger E2 where it is heated by regenerated
liquid desiccant entering from conduit 4. The charge exits exchanger
E2 via conduit 3 and enters distillation apparatus D1 which is mounted
over, in descending order, a reboil zone R1 a stripping zone S1
and a reservoir B1.
The temperature in reboil zone R1 is normally between 150.degree.
C. and 250.degree. C.
The absolute pressure in the assembly constituted by distillation
apparatus D1 reboiler R1 stripping zone S1 and reservoir B1 is
normally between 0.5 and 2 bar.
The majority of the water and substances lighter than the dessicating
agent absorbed thereby are vaporized in reboiler R1. The water-depleted
liquid desiccant falls under gravity from reboiler R1 into stripping
zone S1 where it is brought into contact with a counter-current
of dehydrated stripping agent entering reservoir B1 via conduit
16.
The regenerated liquid desiccant exits reservoir B1 by conduit
4 traverses exchanger E2 where it is cooled by the charge entering
by conduit 2 and leaves the process via conduit 5.
Water, stripping agent and other substances vaporized in reboiler
R1 leave distillation apparatus D1 through exchanger E1 by conduit
6 and are mixed, if necessary, with vapor arriving from phase separator
B3 via conduit 12 then cooled in condenser C1 exiting via conduit
7 to enter decenter B2.
From here, the lightest compounds are evacuated from the process
in gaseous form via conduit 8; water is evacuated from the process
via conduit 9 along with other hydrophilic substances; stripping
agent and other hydrophobic substances, which are saturated with
water, are carried via conduit 10 through pump P1 to exchanger E3
where they are partially vaporized and carried via conduit 11 to
phase separator B3.
In general, the vapor phase generated in exchanger E3 which is
more water-rich than the liquid arriving via conduit 10 can be
evacuated from the process. However, it is more advantageous to
return it via conduit 12 to a point upstream of condenser C1 with
the vapor exiting distillation apparatus D1 by conduit 6.
The liquid phase exiting phase separator B3 via conduit 13 which
is depleted in water compared with the liquid entering via conduit
10 is split so as to maintain a constant flowrate of stripping
agent in the circuit loop: a fixed portion is carried to evaporator
E4 via conduit 15; any excess, due to absorption by the dessicating
agent of part of the gaseous stream treated during the dehydration
step (not shown in the figure), is evacuated from the process via
conduit 14.
The vapor phase exiting evaporator E4 via conduit 16 is carried
to reservoir B1.
A second embodiment of the inventive process will now be described
with reference to FIG. 2.
In this embodiment, a portion of the stripping agent rich separated
after step (d) is brought into contact with a counter-current of
vapor in step (a).
The charge to be treated enters exchanger E201 via conduit 201
where it is reheated by the regenerated liquid desiccant entering
via conduit 203. The heated charge exits exchanger E201 via conduit
202 and enters distillation apparatus D201 which is mounted over,
in descending order, reboil zone R201 stripping zone S201 and reservoir
B201.
Vapor rising from reboil zone R201 is brought into contact in distillation
apparatus D201 with a counter-current of a liquid phase mainly composed
of stripping agent arriving via conduit 210.
The temperature in reboil zone R201 is normally between 150.degree.
C. and 250.degree. C.
The absolute pressure in the assembly constituted by distillation
apparatus D201 reboiler R201 stripping zone S201 and reservoir
B201 is normally between 0.5 and 2 bar.
In reboiler R201 the majority of the water and substances lighter
than the dessicating agent and absorbed thereby are vaporized. The
water-depleted liquid desiccant falls under gravity from reboiler
R201 into stripping zone S201 where it comes into contact with a
counter-current of dehydrated stripping agent entering reservoir
B201 via conduit 216.
Regenerated liquid desiccant exits reservoir B201 via conduit 203
travels through exchanger E201 where it is cooled by the charge
arriving via conduit 201 and is evacuated from the process via
conduit 204.
Water, stripping agent and other substances vaporized in reboiler
R201 leave distillation apparatus D201 via conduit 205 and are mixed
if necessary with vapor arriving from phase separator B203 via conduit
212 then cooled in condenser C201 from which they are carried via
conduit 206 to decanter B202.
From here, the lightest compounds are evacuated from the process
in gaseous form via conduit 207; the water is evacuated from the
process via conduit 208 along with other hydrophilic substances;
stripping agent and other hydrophobic substances, saturated with
water, are carried via conduit 209 through pump P201 in part via
conduit 211 to exchanger E202 and in part via conduit 210 to distillation
zone D201 where it comes into contact with a counter-current of
vapor rising from reboil zone R201 through distillation zone D201.
The first portion is partially vaporized in exchanger E202 and carried
via conduit 217 to phase separator B203.
In general, the vapor phase generated in exchanger E202 which
is more water-rich than the liquid arriving via conduit 211 can
be evacuated from the process. However, it is more advantageous
to return it via conduit 212 to a position upstream of condenser
C201 with the vapor leaving distillation apparatus D201 via conduit
205.
The liquid phase leaving phase separator B203 via conduit 213
which is depleted in water compared with the liquid arriving via
conduit 211 is split so as to maintain a constant flowrate of stripping
agent in the circuit: a fixed portion is returned to evaporator
E203 via conduit 215; any excess, resulting from absorption by the
dessicating agent of part of the gaseous stream treated during the
dehydration step (not shown in the figure), is evacuated from the
process via conduit 214.
The vapor phase exiting evaporator E203 is carried to reservoir
B201 via conduit 216.
Other configurations may be employed for the process according
to the invention; evaporator E4 in FIG. 1 (E203 in FIG. 2) may for
example be dispensed with and stripping agent introduced in liquid
form into reservoir B1 in FIG. 1 (B201 in FIG. 2), where it would
be evaporated by direct contact with the liquid desiccant at high
temperature.
A further modification of the inventive process consists in carrying
out the distillation and stripping steps simultaneously as shown
in FIG. 3: the charge arrives via conduit 301 and the stripping
agent, which may or may not have been previously vaporized, is introduced
directly into reboiler R301 via conduit 302. Distillation apparatus
D301 and stripping zone S301 are thus combined. Regenerated desiccant
exits the reboiler via conduit 304 while the vapor exits distillation
apparatus D301 via conduit 303.
A further variation of the inventive process consists in carrying
out the distillation, reboiling, stripping and condensation steps
as indicated in FIG. 4: after passing through exchangers E401 and
E402 the charge is introduced into distillation apparatus D401
via conduit 401 and falls by gravity into reboiler R401. The vapor
phase generated in reboiler R401 rises into the distillation apparatus
D401 and leaves this apparatus via conduit 402. The partially regenerated
desiccant is pumped from reboiler R401 through pump P401 and via
conduits 403 and 404 to stripping zone S401 which is mounted over
reservoir B401. Regenerated desiccant leaves reservoir B401 via
conduit 405 heats the charge in exchanger E402 and is evacuated
from the process via conduit 415. Stripping agent and stripped water
leave stripping zone S401 via conduit 406 and are mixed if necessary
with vapor carried via conduit 411 from phase separator B403 then
cooled in condenser C401 and separated in decanter B402 from which
light compounds exit in vapor form via conduit 407 water and other
hydrophilic substances which may be present are evacuated via conduit
408 and stripping agent and other hydrophobic substances which
may be present are carried via conduit 409 through pump P402 to
exchanger E403 where a water-rich vapor phase V1 and a water-depleted
liquid phase L1 are generated. Phases V1 and L1 are carried via
conduit 410 to phase separator B403; vapor phase V1 leaves via conduit
411 and is mixed with the vapor leaving stripping zone S401 via
conduit 406; liquid phase L1 leaves phase separator B403 via conduit
416 and is divided into a surplus portion evacuated from the process
via conduit 413 and a fixed portion carried by conduit 412 to evaporator
E404 where it is vaporized and introduced into balloon reservoir
B401 via conduit 414. A still further solution consists in reinjecting
the stripping agent and stripped water leaving S401 via 406 into
reboiler R401 and condensing and separating them downstream of
distillation apparatus D401 as shown in the preceding schemes (FIGS.
1 to 3).
The inventive process may, for example, be applied to regeneration
of a desiccant from the glycol family such as monoethylene glycol
(MEG), diethylene glycol (DEG), triethylene glycol (TEG) or tetraethylene
glycol (T4EG); said desiccant may, for example, be used to dehydrate
a natural or refined gas.
The stripping agent may, for example, be a hydrocarbon or mixture
of hydrocarbons, and may in this case contain a significant proportion
of aromatic compounds, in particular benzene.
A particularly appropriate application is where the desiccant absorbs
natural substances which are compatible with the stripping agent
as defined in the present invention from the effluent to be dehydrated.
The process then has a surplus of stripping agent which not only
removes the need for any additions but may also be a profit source.
These applications are not limiting and the inventive process may
be applied to regeneration of any liquid desiccant, regardless of
the nature of the dehydrated effluent. |