U.S. patent number 3,675,436 [Application Number 05/014,047] was granted by the patent office on 1972-07-11 for desalination process.
This patent grant is currently assigned to Struthers Scientific and International Corporation. Invention is credited to Neophytos Ganiaris.
United States Patent |
3,675,436 |
Ganiaris |
July 11, 1972 |
DESALINATION PROCESS
Abstract
The freeze desalination of sea water is accomplished using the
refrigeration potential released during the regassification of
liquified natural gas. Sea water feed is cooled in an ice melter
and feed cooler to near freezing, the feed is mixed with cold
brine, and the feed is passed to a crystallizer wherein ice
crystals are formed by direct contact with a refrigerant which has
been cooled by the evaporation of the liquid natural gas. Ice
crystals are separated from a slurry led from the crystallizer and
the ice crystals are fed into the ice melter and feed cooler in
which a refrigerant in a closed cycle condenses to melt ice and
evaporates to cool feed. Fresh water is separated from condensed
refrigerant in the ice melter and feed cooler. Refrigerant is
stripped from the fresh water and brine passing from the system. In
the crystallizer, gaseous refrigerant emerging from the feed is
condensed by liquid refrigerant spraying into a tray suspended
above the feed.
Inventors: |
Ganiaris; Neophytos (Riverdale,
NY) |
Assignee: |
Struthers Scientific and
International Corporation (N/A)
|
Family
ID: |
21763259 |
Appl.
No.: |
05/014,047 |
Filed: |
February 25, 1970 |
Current U.S.
Class: |
62/535; 62/50.2;
62/544; 62/532 |
Current CPC
Class: |
F17C
9/04 (20130101); C02F 1/22 (20130101); C02F
2103/08 (20130101); F17C 2223/0153 (20130101); Y02A
20/124 (20180101); Y02A 20/132 (20180101); Y02A
20/128 (20180101); F17C 2227/0351 (20130101); F17C
2221/033 (20130101); F17C 2223/0161 (20130101); F17C
2221/035 (20130101); F17C 2260/032 (20130101); F17C
2227/0393 (20130101); F17C 2265/05 (20130101) |
Current International
Class: |
C02F
1/22 (20060101); F17C 9/00 (20060101); F17C
9/04 (20060101); B01d 009/04 () |
Field of
Search: |
;62/58,52 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Yudkoff; Norman
Assistant Examiner: Foster; R. T.
Claims
What is claimed is:
1. In the process of desalination using the refrigeration potential
of liquified natural gas during regassification, the steps of:
a. passing the liquified natural gas through a heat exchanger to
receive heat and become regassified thereby;
b. circulating a liquid refrigerant through the heat exchanger to
give up heat therein and become cooled;
c. introducing a saline feed into a crystallizer providing a liquid
crystallization zone and a vapor span thereabove;
d. introducing cooled refrigerant into the liquid crystallization
zone to rise and vaporize therein and form an ice-brine slurry;
e. spraying and catching cooled liquid refrigerant in the vapor
span of the crystallizer above the crystallization zone to condense
vaporized refrigerant emerging from the slurry, control of the
spraying of refrigerant maintaining temperature and pressure
conditions in the vapor span of the crystallizer;
f. recirculating at least some condensed and sprayed refrigerant
for cooling in step (b);
g. withdrawing the ice brine slurry from the crystallizer;
h. separating the slurry into ice and brine; and
i. melting the ice as a product.
2. The process according to claim 1 wherein in step (d) the feed is
mechanically agitated for mixing with the slurry in the
crystallization zone.
3. The process according to claim 1 with the additional step of
storing liquid refrigerant, refrigerant from storage being
recirculated through the heat exchanger in step (b) and refrigerant
from storage being sprayed into the crystallizer in step (e),
sprayed and condensed refrigerant withdrawn from the crystallizer
being partly introduced into the crystallization zone and being
partly recirculated for further cooling in step (f).
4. The process according to claim 3 wherein, in step (i) ice is
melted to cool incoming feed used in step (c).
5. The process according to claim 4 wherein step (i) comprises the
steps of (j) introducing the ice onto first plates in a closed
container of a melter-cooler having a liquid refrigerant therein,
(k) introducing feed onto second plates in the container, the
liquid refrigerant vaporizing on contact with the feed on the
second plates and condensing to melt ice on the first plates, and
(l) decanting melted ice from liquid refrigerant and withdrawing
the melted ice from the container, liquid refrigerant flowing in
the container onto the second plates to contact and cool feed on
vaporizing.
6. The combination according to claim 5 wherein in step (h) part of
the brine is recycled by being mixed with feed in step (c), and the
remainder of the brine is passed from the system.
7. The combination according to claim 6 wherein the melted ice in
step (l) is stripped of refrigerant and the brine in step (h) is
stripped of refrigerant.
8. The process according to claim 7 wherein the refrigerant of
steps (b), (d), (e) and (f) is n-butane, the n-butane being sprayed
into the vapor span of the crystallizer at a temperature below
20.degree.F. in step (e), the temperature of the n-butane
introduced into the crystallization zone being within 5.degree.F.
of the temperature of the feed.
9. The combination according to claim 8 wherein the refrigerant in
the melter-cooler is n-butane, the melter-cooler at an equilibrium
pressure and temperature of about 16 psia at 34.degree.F.
Description
BACKGROUND OF THE INVENTION
It is known to obtain water of high purity from sea water or
similar salines by the freezing of the water in the solutions by
direct contact with a volatile refrigerant and then separating and
melting the ice crystals so formed. The refrigerant vapors leaving
the crystallization zone are conventionally condensed by being
compressed and brought back into a heat exchange relationship with
the cold ice crystal product. Additional cooling for condensation
of the refrigerant is usually provided by cooling water or seat
water at ambient temperatures. After condensation, the liquid
refrigerant is returned to the crystallization zone and the
operation is repeated.
SUMMARY OF THE INVENTION
The main purpose of this invention is to provide a process for the
freeze desalination of sea water or the like using the
refrigeration potential of liquified natural gas when it is
revaporized for distribution. In the practice of this invention,
liquified natural gas is passed through a heat exchanger to receive
heat from a refrigerant such as n-butane which is stored in a
reservoir and circulated through the heat exchanger. This
revaporizes the liquified natural gas for use.
In a novel crystallizer, the cold refrigerant is sprayed into a
tray in the top of the crystallizer to condense refrigerant vapors
in the tray. Some of the refrigerant drawn from the tray is
returned to the refrigerant reservoir and some of the liquid
refrigerant is introduced into a feed solution in the bottom of the
crystallizer to vaporize therein and grow ice crystals. The feed
introduced into the crystallizer is sea water which is cooled to
about 36.degree.F. in a combined melter-cooler unit. Cold brine is
added to the feed which is then passed into the crystallizer.
A slurry of brine and ice crystals is drawn from the crystallizer
and introduced into a wash column in which the ice crystals are
separated from the brine. Some of the brine is passed through a
debutanizer and out of the system and some of the brine is mixed
with feed and introduced into the crystallizer as described. Ice
from the wash column passes into the melter-cooler unit.
The melter-cooler unit is a closed unit having an upper and a lower
portion. Ice is deposited on trays in the upper portion and melted
by the condensation of n-butane rising from the lower portion.
Melted ice and liquid n-butane are collected in the center of the
unit and the water is drawn from below the liquid n-butane and
passed from the system through a debutanizer. Liquid n-butane flows
from the center of the unit onto trays in the lower half of the
unit. Feed water is introduced into the trays in the bottom half of
the unit to flow downward on the trays and become cooled to
36.degree.F. as it vaporizes the n-butane which rises upward to
become condensed in the upper half as described. Cold feed drawn
from the bottom of the unit is passed to the crystallizer as
described. Refrigerant need only be added to the melter-cooler unit
to make up for any losses therefrom.
The particular freeze desalination process of this invention takes
full advantage of the refrigeration potential of liquified natural
gas so that it may produce fresh water at about $0.50 per 1,000
gallons. Since the cost of building and operating a regassification
facility are substantial, this invention offers the possibility of
producing a useful product as well as regassifying the liquified
natural gas. This will have a great economic advantage.
The particular process of this invention provides a desalination
facility which requires no moving parts other than pumps.
Maintenance will be reduced to a minimum and all the refrigeration
potential will be used.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE of the drawing is a schematic diagram of the apparatus
required to carry out the process of this invention with some of
the elements of the apparatus shown in vertical section.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawing in detail, liquified natural gas is stored
in a tank 10 or other suitable reservoir at substantially
atmospheric pressure. The reservoir 10 would be of sufficient
capacity to hold the discharge of one or more supertankers. The
liquified natural gas would then be regassified continuously or as
required. The liquified natural gas is pumped by pump 11 through
line 12 to a heat exchanger 13.
A tank 14 is provided to store a refrigerant such as n-butane. A
pump 15 circulates the n-butane through lines 16 and 17 between the
heat exchanger 13 and tank 14. Thus, the liquified natural gas is
regassified from a liquid at -260.degree.F. to a gas approaching
20.degree.F. in heat exchanger 13. The gas can be produced at any
conventional desired pressure and may be allowed to further absorb
heat to reach ambient temperatures if desired. The regassification
is continuous as heat is constantly added in the heat exchanger 13
by the refrigerant. Heat exchanger 13 may be of any suitable type.
The chilled refrigerant in tank 14 is used for the desalination of
sea water in the following manner.
Crystallizer 18 has sea water feed mixed with brine at a
temperature near the ice point introduced into it through pipe 19.
The feed is mechanically agitated by agitator blades 20 as it is
cooled below its freezing point (about 23.degree.F.) by the direct
contact evaporation of liquid n-butane introduced therein through
pipe 21 and a perforated spreader 22. A tray 23 is disposed in the
upper portion of crystallizer 18 above the feed level. Pump 24
passes cold refrigerant through pipe 25 to spray head 26 to spray
into tray 23 and condense refrigerant vapors thereby in the vapor
span of the crystallizer 18 to be collected in tray 23. The
n-butane emerging from spray heat 26 is at a temperature
substantially lower than 20.degree.F. so that it will readily
condense vapors leaving the crystallization zone in the lower part
of the crystallizer 18 at a temperature between
20.degree.-26.degree.F. Sprayed and condensed n-butane is drawn
from tray 23 through pipe 27 by pump 28. Some of the n-butane from
pipe 27 is passed through pipe 21 to vaporize in the crystallizer
18 and the rest of the n-butane is recycled to the tank 14 through
pipe 29. Thus it may be seen that the heat of ice crystallization
is continuously transferred to the n-butane in tank 14 and this
heat is used to regassify liquified natural gas in heat exchanger
13.
As has been stated, cold sea water is mixed with brine to a 7 per
cent salt content and introduced into crystallizer 18 through pipe
19. As ice crystals form in this feed, an ice-brine slurry is
withdrawn by pump 30 through pipe 31. The slurry is introduced into
wash column 32 in which the ice crystals float to the top to be
washed with a water spray from pipe 33. Pump 34 removes the ice
crystals through pipe 35 to introduce them into ice melter and feed
cooler 36. A brine solution is removed from the wash column 32
through pipe 37. A screen 38 prevents any ice crystals from
entering pipe 37.
Sea water at ambient temperatures enters the melter-cooler 36
through pipe 39. The feed flows downward in the lower half of the
melter-cooler 36 on the staggered plates 40. In the upper half of
the melter-cooler 36 an ice crystal and wash water slurry flows
downward on the staggered plates 41. A given balance of n-butane is
maintained in the melter-cooler 36 so that liquid n-butane is
vaporized on the plates 40 by the feed from pipe 39 to cool the
feed to about 36+F. by the time it is withdrawn through pipe 42 by
pump 43. This cooled feed is mixed with brine withdrawn from wash
column 32 by pipe 37. The feed and brine mixture is then introduced
into crystallizer 18 by pipe 19 in the manner which has been
described.
The center of melter-cooler 36 is defined by an upward facing
baffle 44. Vaporized n-butane rises past baffle 44 to be condensed
by the ice crystals on the plates 41 and melt them. The melted ice
crystals flow as water from plates 41 to be trapped by baffle 44
and be withdrawn through pipe 45. Condensed n-butane floats on the
water trapped by baffle 44 and overflows therefrom onto the plates
40 to be vaporized as described and cool incoming feed. Sufficient
n-butane should be introduced into melter-cooler 36 to make up for
any that may be lost with the fresh water product and the brine
flowing therefrom through pipes 45 and 42, respectively.
Product water from pipe 45 flows into a debutanizer 47 which is
evacuated by pump 48 and packed with solid objects 49 to provide a
large surface area. Pump 50 evacuates fresh product water through
pipe 51 with a hydrocarbon content of less than 0.2 ppm with a
vacuum in debutanizer 47 of 35 mm Hg.
Pipe 52 passes brine to debutanizer 53 packed with objects 54 and
evacuated by pump 55. Pump 56 evacuates a debutanized brine through
pipe 57.
The successful operation of the entire system depends on the design
and operation of the crystallizer 18. Mechanical agitators 20 are
provided to mix the feed with the ice-brine slurry. The sea water
(3.5 per cent salt) is cooled to approximately 23.degree.F. (60 per
cent conversion) and ice crystals are formed and grown. The
resulting brine has a salt content of 8.75 per cent. The heat of
ice crystallization is removed by dispersing cold liquid n-butane
in the bulk of the ice-brine slurry. The liquid n-butane is at a
temperature lower than 23.degree.F. This temperature difference
between the liquid n-butane and the brine should be less than
5.degree.F. and preferrably about 2.degree.F. By maintaining a
pressure in the crystallizer equal to the equilibrium conditions,
the liquid n-butane absorbs the heat of ice crystallization and
evaporates. For example, at 21.degree.F. the pressure is 12 psi.
The n-butane vapors come in direct contact with the very cold
n-butane spray above tray 23 in the upper part of the crystallizer
18. Here the n-butane vapors are condensed and recycled at
21.degree.F. back to the crystallization zone.
The flow of cold n-butane is regulated to maintain a constant
pressure in the crystallizer 18. Since the temperature in the upper
part of the crystallizer 18 may fluctuate substantially, a cascade
control loop (not shown) may be used to control the flow of cold
n-butane from spray head 26. While the forementioned conditions for
temperature and pressure are based on a 60 percent conversion, the
crystallizer 18 can be operated at any desired conversion ratio or
a multi-stage crystallization system could be used.
The percent of ice crystals in the crystallization zone is
controlled by the brine recycle through pipe 37. A 20 percent ice
brine slurry is satisfactory.
The ice melter and feed cooler 36 is operated at a pressure of 16
psia which is the equilibrium pressure at 34.degree.F. for
n-butane. As explained, the water and n-butane separate into two
phases in the baffle section 44 so the water may be removed at
34.degree.F. The liquid n-butane flows over the baffle 44 to come
in direct contact with sea water at 75.degree.F. As the sea water
cools down to 36.degree.F., the n-butane is evaporated to rise into
the upper section and repeat the cycle. This melter-cooler 36 is
less costly than a heat exchanger as no heat transfer surfaces are
required.
Both the wash column 32, the debutanizers 47 and 53, and the heat
exchanger 13 may be conventional pieces of apparatus. If desired,
the novel melter-cooler 36 may be replaced with a conventional
indirect contact heat exchanger so that heat required to melt the
ice cools the feed.
Thus it may be seen that the process of this invention utilizes the
refrigeration potential of liquified natural gas to produce low
cost fresh water from sea water and other salines. While n-butane
has been described as a preferred refrigerant, the system will
operate with other hydrocarbon refrigerants, Freons, and the
like.
* * * * *