U.S. patent number 3,802,186 [Application Number 05/269,380] was granted by the patent office on 1974-04-09 for generation of power using a rankine-cycle engine with tetrachloroethylene as the working fluid.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Walter Mahler.
United States Patent |
3,802,186 |
Mahler |
April 9, 1974 |
GENERATION OF POWER USING A RANKINE-CYCLE ENGINE WITH
TETRACHLOROETHYLENE AS THE WORKING FLUID
Abstract
Tetrachloroethylene has excellent physical properties as the
working fluid in a Rankine-cycle engine. Thermal degradation of the
working fluid can be reduced to acceptable levels by contacting the
fluid with at least ten sq. cm of ferritic iron per cc of
tetrachloroethylene when at temperatures greater than
200.degree.C.
Inventors: |
Mahler; Walter (Wilmington,
DE) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
26749314 |
Appl.
No.: |
05/269,380 |
Filed: |
July 6, 1972 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
68740 |
Sep 1, 1970 |
|
|
|
|
Current U.S.
Class: |
60/649;
252/400.53 |
Current CPC
Class: |
F01K
25/08 (20130101) |
Current International
Class: |
F01K
25/00 (20060101); F01K 25/08 (20060101); F01k
025/00 (); F01k 003/18 () |
Field of
Search: |
;60/36,38 ;252/67,4R
;260/652.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
The Condensed Chemical Dictionary, 6th Edition, by Arthur Rose et
al., Reinhold Publishing Corp.; N.Y. (Definition of
Perchloroethylene, Page No. (Unknown) Fifth Edition dated
1965..
|
Primary Examiner: Geoghegan; Edgar W.
Assistant Examiner: Burks, Sr.; H.
Parent Case Text
RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 68,740,
filed Sept. 1, 1970, now abandoned.
Claims
The embodiments of the invention in which an exclusive property of
privilege is claimed are defined as follows:
1. The method of generating power in which tetrachloroethylene is
vaporized at a temperature greater than 200.degree.C, the vapor is
expanded and does work and is thereafter condensed and recycled,
wherein liquid tetrachloroethylene is contacted with ferritic iron
in an amount sufficient to provide at least 10 sq. cm. of iron per
cc of tetrachloroethylene while at temperatures greater than
200.degree.C.
Description
BACKGROUND OF THE INVENTION
Rankine cycle, high power, multistage, vapor turbines are well
known as highly efficient heat engines for the production of power.
When steam is employed, it is essential to employ multiple stages
to obtain power at usable speeds and at useful efficiency.
Superheat is also required, since, on expansion, saturated steam
forms a mixture of vapor and liquid water which erodes turbine
blades and is difficult to handle. Accordingly, steam turbines are
generally complex pieces of equipment which are ill adapted to
manufacture and operate on the small scale needed for portable
engines of modest power, i.e., less than 1,000 h.p.
Small engines adapted for portability should preferably employ a
single stage impulse turbine. This requires the use of working
fluids having a higher molecular weight in order to reduce the
efflux velocity at the nozzle and the speed of the turbine for a
single stage. It is also highly desirable to operate below the
critical temperature of the liquid in order to minimize the
pressure requirements.
Many organic liquids have been proposed for use as working fluids
for engines. For example, Fulton U.S. Pat. No. 795,761 has
suggested such fluids as alcohol, ether, carbon disulfide or
chloroform as working fluids. Govers U.S. Pat. No. 870,507 teaches
the use of chlorides of carbon such as carbon tetrachloride,
chloroform, ethylidene chloride or trichloroethane. Norton et al.
U.S. Pat. No. 3,511,049 and Minto U.S. Pat. No. 3,479,817 have
taught the use of chlorofluorohydrocarbons, and McEwan U.S. Pat.
No. 3,516,248 has taught the use of a variety of non-halogenated
organic fluids having the property that the change in entropy from
the maximum saturated enthalpy point on a Mollier diagram to the
entropy of the saturated vapor at atmospheric pressure is less than
0.1 BTU/(lb..degree.F).
Tetrachloroethylene has also been proposed as a working fluid for
Rankine-cycle engines by Paxton U.S. Pat. No. 3,512,357. Although
tetrachloroethylene has desirable thermal properties and is
relatively inexpensive, the thermal stability at elevated
temperatures needed for Rankine-cycle engines is inadequate.
SUMMARY OF THE INVENTION
The present invention is directed to a method of generating power
wherein tetrachloroethylene is vaporized at a temperature greater
than 200.degree.C, the vapor is expanded and does work, and is
thereafter condensed and recycled, wherein the tetrachloroethylene
is stabilized in the liquid phase by contacting the liquid with
ferritic iron in an amount sufficient to provide a surface of
ferritic metal/volume of liquid tetrachloroethylene of at least 10
cm.sup..sup.-1.
THE DRAWINGS AND DETAILED DESCRIPTION OF THE INVENTION
It has long been known that tetrachloroethylene has relatively low
stability. Stabilizers suitable for stabilizing this compound have
been described in many patents including U.S. Pat. Nos. 2,492,048;
2,997,507; 2,947,792; 2,094,367 and 2,096,735. While such
stabilizers are effective for moderate temperatures such as those
employed in dry cleaning, they are not effective in preventing the
degradation of tetrachloroethylene at higher temperatures such as
246.degree.C (475.degree.F) employed in external combustion
engines, even in sealed systems. Surprisingly, it has been found
that the degradation of tetrachloroethylene can be inhibited by the
presence of ferrous metals in the system. The term "ferrous metal"
refers to metals or alloys in which metallic iron is the major
component such as 1020 steel, 1018 steel, 303 stainless steel and
the like. While stainless steel suffers the least corrosion and
does effect some degree of stabilization, best results are obtained
with ferritic steels such as 1018 steel or ordinary iron. The
amount required to achieve significant stabilization should provide
at least 10 sq cm of surface per cubic centimeter of liquid
tetrachloroethylene and should be in contact with the liquid. This
amount is greater than is found in conventional boilers. For
example, a tube-type boiler with tubes having an inside diameter of
0.5 inches provides surface/volume ratio of 3:1 cm.sup..sup.-1.
Accordingly, it is preferred to pack the boiler with steel wool or
to employ iron metal grids or fine iron metal powder to achieve the
desired stabilization.
Table I shows the results of tests wherein 1018 cold rolled steel,
430 stainless steel (17% Cr) and P11 steel (a low alloy steel
containing 1.3% Cr and 0.5% Mo) are heated to 300.degree.C for 28
days in sealed glass tubes with tetrachloroethylene.
TABLE I
Decomposition of Tetrachloroethylene and Corrosion in the Presence
of
---------------------------------------------------------------------------
Ferrous Metals: 28 days at 300.degree.C
1018 Steel Corrosion Other Corrosion % C.sub.2 Cl.sub.4 S/V
cm.sup.-.sup.1 Mg/cm.sup.2 S/V cm.sup..sup.-1 Mg/cm.sup.2 after
test 0.8 260 0 1.5 129 0 3.0 33 14.7 6.0 11 23.8
P11
1.7 85 17.0 2.4 68 5.1 0.8 100 1.7 54 41.7 1.5 12 1.7 53 20.7 3.0
10 1.7 42 23.9 6.0 6 1.7 24 27.9 12.0 4 3.4 7 46.6
430 SS
1.15 11.4 13.2 2.65 7.5 12.4 5.3 5.8 21.1 3.1 6.8 12.2 0.8 165 1.15
7.1 4.6 1.5 42 1.15 6.0 10.4 3.0 46 1.15 10.4 8.4 6.0 16 1.15 5.5
35.0 12.0 5 2.3 1.8 75.6 12.8 10 5.6 1.2 75.8
__________________________________________________________________________
in another experiment 0.3 gm of iron powder having an estimated
surface area of 700 cm.sup.2 was combined with 0.3 cc. of
tetrachloroethylene in a 2 cc tube and heated for 28 days at
300.degree.C. At the end of this period the tetrachloroethylene was
analyzed by gas chromatography and found to be 99.1% pure.
The reason for the stabilizing action of iron is not known and it
is possible that a compound derived from iron such as FeCl.sub.2
rather than the metal itself is the effective stabilizer.
In the accompanying drawings:
FIG. 1 shows the entropy-temperature diagram which has been
determined for tetrachloroethylene.
FIG. 2 is a schematic view of a turbine power generator adapted for
use with tetrachloroethylene as a working substance.
Referring now to FIG. 1, the critical temperature of
tetrachloroethylene is 662.9.degree.F and the critical pressure is
568.75 psia. The value of ds/dT for the saturated vapor line is
very slightly positive, i.e., the change in entropy in passing from
the critical temperature to the boiling point is less than 0.02
BTU/(lb..degree.F). Accordingly, vapor produced by expansion of
saturated vapor from a temperature below the critical temperature
to the pressure of the condenser will be only slightly superheated
so that an efficient Rankine-cycle engine can be operated without
the problems encountered with vapor/liquid mixtures after
expansion, e.g., at the turbine wheel, while the degree of
superheat after expansion is so slight that it can be neglected.
Thus, regenerative cooling of the vapor prior to condensation is
unnecessary.
A typical cycle employed in Rankine cycle engines is shown in FIG.
1. The vapor is produced essentially saturated at a temperature of
475.degree.F corresponding to point 1 of FIG. 1 at a pressure of
178.4 psia. The gas is expanded essentially isentropically to a
pressure of 3 psia, the condenser pressure, and cooling to a
temperature of 205.degree.F indicated by point 2 in FIG. 1
whereupon the gas does work in, for example, a turbine. The gas is
then cooled to 160.degree.F (3) and condensed to a liquid at
160.degree.F (4) in the condenser. The condensed liquid is pumped
back to the boiler and heated to 475.degree.F (5) at which
temperature the liquid is vaporized to vapor at 475.degree.F and
178.4 psia, thus completing the cycle. With the above cycle, the
Rankine cycle efficiency is 26.6%. The small amount of superheat
can be recovered by a heat exchanger or regenerator and employed to
heat the boiler feed. However, with 70% regeneration, the
efficiency is only increased to 27.4 %.
FIG. 2 is a schematic diagram of a turbine engine operating on the
cycle described above in connection with FIG. 1 using
tetrachloroethylene as the working fluid. The boiler indicated by
10 heats the liquid and vaporizes it to saturated vapor. The vapor
is expanded in the nozzles of turbine 11 and cooled, the expanded
vapor doing work on the blades of the turbine. The vapor at about
205.degree.F is transferred to the condenser 12, cooled and
condensed and the liquid pumped back to the boiler 10 by pump 13.
In addition to the substantial efficiency which can be obtained in
a Rankine cycle engine as described above, tetrachloroethylene has
other desirable properties.
Molecular Weight
The molecular weight of tetrachloroethylene is 166. Since the
efflux velocity on expansion in a nozzle is roughly in inverse
proportion to the square root of the molecular weight, sufficiently
low efflux velocities can be achieved to render a single stage
impulse turbine feasible. The low efflux velocities and the
relatively low operating temperatures make the use of light metals
such as aluminum or even plastics feasible for construction of the
turbine blades.
Melting Point and Boiling Point
The melting point of tetrachloroethylene of -19.degree.C
(0.degree.F) makes the use of the liquid as a working fluid
feasible even when relatively low ambient temperatures are
encountered. The boiling point of 121.degree.C (250.degree.F)
provides reasonably efficient condensing with gaseous or liquid
coolants at ambient temperatures.
Liquid Density
In the copending commonly assigned applications of William A.
Doerner, U.S. Ser. No. 110,478 filed Jan. 28, 1971 as a
continuation-in-part of U.S. Ser. No. 25,857 filed Apr. 6, 1970 and
now abandoned, U.S. Ser. No. 231,232 filed Mar. 2, 1972 and U.S.
Ser. No. 227,902 filed Feb. 22, 1972; also U.S. Pat Nos. 3,590,786
and 3,613,368 to William A. Doerner there are disclosed rotary
engines, rotary boilers and rotary regenerators for low-pressure
application. In the case of the rotary boilers and regenerators,
high density liquids are particularly desirable to minimize the
speed of rotation required to maintain a film of liquid in the
desired uniform condition. Tetrachloroethylene liquid has a density
of 1.61 at 25.degree.C and is well suited for use in such high
density, low weight equipment.
Flammability
Tetrachloroethylene is not flammable and therefore presents no fire
or explosion hazard, in the event of damage to the heated
engine.
Toxicity
In the event of leakage or in the case of accident when the power
fluid escapes from the heat engine, low toxicity is highly
desirable. Tetrachloroethylene has low toxicity: inhalation of the
vapor at a concentration of 100 ppm per 8 hour day is permissible.
Tetrachloroethylene is not considered a contributory cause of
smog.
The foregoing detailed description has been given for clarity of
understanding only and no unnecessary limitations are to be
understood therefrom. The invention is not limited to the exact
details shown and described for obvious modifications will be
apparent to those skilled in the art.
* * * * *