U.S. patent number RE33,007 [Application Number 07/153,878] was granted by the patent office on 1989-08-01 for method of vaporizing multicomponent liquids.
This patent grant is currently assigned to American Sterilizer Company. Invention is credited to Mark E. Bier.
United States Patent |
RE33,007 |
Bier |
August 1, 1989 |
Method of vaporizing multicomponent liquids
Abstract
A method of vaporizing a multicomponent liquid, such as a
hydrogen peroxide and water solution, for injection into a vacuum
chamber including the steps of metering successive predetermined
increments of the liquid at a predetermined rate onto a heated
surface in a vaporization chamber. Upon exposure to the heated
surface, each liquid increment is substantially instantaneously
vaporized before the next succeeding liquid increment is metered
onto the heated surface to produce a multi-component vapor
increment having substantially the same weight percent composition
as the multicomponent liquid increment. Each vapor increment is
passed into the vacuum chamber.
Inventors: |
Bier; Mark E. (West Lafayette,
IN) |
Assignee: |
American Sterilizer Company
(Erie, PA)
|
Family
ID: |
26850952 |
Appl.
No.: |
07/153,878 |
Filed: |
February 9, 1988 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
684461 |
Dec 21, 1984 |
04642165 |
Feb 10, 1987 |
|
|
Current U.S.
Class: |
203/12; 203/1;
422/27; 422/29; 203/91; 73/863.12; 203/88; 222/456; 422/28 |
Current CPC
Class: |
A61L
2/20 (20130101); B01D 3/10 (20130101); C01B
15/01 (20130101) |
Current International
Class: |
B01D
3/10 (20060101); A61L 2/20 (20060101); C01B
15/01 (20060101); C01B 15/00 (20060101); B01D
003/06 (); B01D 003/42 () |
Field of
Search: |
;203/12,1,88,91,3,DIG.18
;73/863.12 ;222/454,456,1 ;422/27,28,29 ;239/99,101,102 ;137/1
;202/205 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Manoharan; Virginia
Attorney, Agent or Firm: Kirkpatrick & Lockhart
Claims
What is claimed is:
1. A method of vaporizing a multicomponent liquid comprising:
metering successive predetermined increments of said multicomponent
liquid at a predetermined rate onto a heated surface of a
vaporization chamber;
substantially instantaneously vaporizing each said liquid increment
on said heated surface before the succeeding said liquid increment
is metered onto said heated surface so that each liquid increment
vaporization produces a multicomponent vapor increment having
substantially the same weight percent composition as said
multicomponent liquid increment; and
passing each said vapor increment into a .[.vacuum.]. chamber.
2. A method as recited in claim 1 further comprising heating said
surface at a rate that replaces the heat lost to vaporizing each
liquid increment before said next succeeding liquid increment is
metered onto said surface.
3. A method as recited in claim 1 wherein said multicomponent
liquid is a binary composition having components of significantly
differing volatilities.
4. A method as recited in claim 3 wherein said binary composition
is a hydrogen peroxide, water solution having a hydrogen peroxide
concentration of about 20-50% by weight.
5. A method of vaporizing a multicomponent liquid comprising:
metering a predetermined amount of the multicomponent liquid into a
vaporization chamber;
heating said amount of liquid on a surface of said vaporization
chamber to substantially instantaneously raise the least volatile
component of said multicomponent liquid to its boiling point to
produce a multicomponent vapor having substantially the same
percent composition as said amount of said multicomponent
liquid;
passing said multicomponent vapor into a .[.vacuum.]. chamber;
and
repeating for a predetermined period of time said metering,
heating, and passing steps at a predetermined rate no greater than
that required to substantially completely vaporize one said amount
of liquid before metering the next said amount of liquid.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to methods of vaporizing liquids, and
more particularly, to a method of vaporizing a multicomponent
liquid.
2. Description of the Prior Art
Hawkinson, et al. U.S. Pat. No. 2,491,732 which issued on Dec. 29,
1949, describes a method of vaporizing hydrogen peroxide. The
liquid is sprayed in the form of finely divided droplets onto the
walls of a vaporizer which are coated with a nonvolatile stabilizer
for hydrogen peroxide and heated sufficiently to rapidly and
completely vaporize the liquid sprayed onto the walls. The heated
walls of the vaporizer must be inclined from the horizontal to
ensure formation of a hydrogen peroxide film on the walls of the
vaporizer.
The Hawkinson method is not compatable with sterilizer
applications. A relatively large surface area is required to
provide the desired efficiency. The vapor is transferred to another
location for ultimate use. Although evaporation of the hydrogen
peroxide and water is simultaneous in the vaporizer, the water
vapor travels faster than the hydrogen peroxide vapor, thus the
vapors reaching the area of end use are not in the same
concentration as the initial solution.
U.S. Pat. Nos. 4,169,123 and 4,169,124 to Moore et al. and Forstrom
et al., respectively, describe sterilization techniques using
gaseous hydrogen peroxide. A hydrogen peroxide and water solution
is vaporized in a closed sterilization chamber. The vapors are
permitted to contact the items to be sterilized to achieve
sterilization.
In these prior art sterilizer methods, water is vaporized more
quickly than hydrogen peroxide and thus, the water vapor reaches
the items to be sterilized first and in higher concentrations. The
water vapor becomes an effective barrier to hydrogen peroxide
penetration around small crevices and lumens of the items in the
sterilizer.
When vaporizing multicomponent liquids, particularly those having
components of significantly differing boiling points, the more
volatile liquid will vaporize first. According to Raoult's Law, the
vapor pressure of a component in a binary solution is equal to its
pure vapor pressure multiplied by the mole fraction of a particular
constituent. For nonideal solutions, an activity coefficient must
also be factored in. Thus,
Where
P.sub.A is the vapor pressure of component A;
X.sub.A is equal to the mole fraction of A in the mixture;
P.sub.A .degree. is the vapor pressure of pure A; and
.gamma..sub.A is the activity coefficient for A in the
solution.
Where A is, for example, hydrogen peroxide in a water solution, the
pure vapor pressure of water is greater than that of peroxide,
thus, the vapor pressure of the water component in the binary
solution will be greater than that of the peroxide unless the mole
fraction of peroxide in the solution becomes very large. The
handling requirements for highly concentrated hydrogen peroxide
solutions are so onerous because of the hazardous nature of the
peroxide that maintaining such solutions is impractical.
There is a need for a method of vaporizing multicomponent liquids,
particularly those having components of significantly differing
volatilities, which provides a multicomponent vapor of
substantially the same percent weight composition as the
multicomponent liquid which is compatible with sterilizer practice.
There is a further need for such a method which will permit the use
of safe concentrations of the constituent components.
SUMMARY OF THE INVENTION
The present invention provides a method of vaporizing a
multicomponent liquid by injection into a vaporization chamber in
open communication with a vacuum chamber. The method includes the
step of metering successive predetermined increments of the
multicomponent liquid at a predetermined rate onto a heated surface
of the vaporization chamber wherein each liquid increment is
substantially instantaneously vaporized before the next succeeding
liquid increment is metered onto the heated surface. Each such
liquid increment vaporization produces a multicomponent vapor
increment having substantially the same weight percent composition
as the multicomponent liquid increment. Each vapor increment is
passed into the vacuum chamber.
The method may also include the step of heating the surface of the
vaporization chamber at a rate that replaces the heat lost to
vaporizing each liquid increment before the next succeeding liquid
increment is metered onto the surface.
The surface is preferably made of a relatively high thermal
conducting material and the multicomponent liquid may be a binary
composition, for example hydrogen peroxide and water.
BRIEF DESCRIPTION OF THE DRAWINGS
The FIGURE is a diagrammatic view of an apparatus for use in
carrying out the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the single FIGURE, there is shown in diagrammatic form
apparatus for use in carrying out the method of the present
invention. The apparatus includes a vacuum chamber 10, a
vaporization chamber 30, and a liquid reservoir 20. A valve 25
meters the liquid onto the heated surface 40 of the vaporization
chamber 30. The vaporization chamber 30 is in open communication,
through portal 35 with the vacuum chamber 10.
The present invention can be practiced with any suitable
multicomponent liquid. For purposes of the detailed description,
however, the preferred multicomponent liquid is a binary
composition of hydrogen peroxide (H.sub.2 O.sub.2) and water
(H.sub.2 O). The peroxide constitutes about 20 to 50% by weight of
the composition. Although concentrations of hydrogen peroxide
greater than 50% are possible, the hazardous nature of the material
makes such high concentrations impractical. Lower concentrations of
the peroxide below 20% are generally accompanied by increased
problems with the water.
The method of the present invention minimizes the barrier created
by the more volatile component, water, by metering small, ideally
infinitesimal increments of the multicomponent liquid repeatedly
into the vaporization chamber 30 at such a rate that each liquid
increment is vaporized before the next succeeding liquid increment
is metered into the chamber 30. A homogenous vapor, having a
percent weight composition substantially the same as the
multicomponent liquid is produced and passed through portal 35 into
the vacuum chamber 10. The small vapor increments reach the items
in vacuum chamber 10 and penetrate the crevices and lumens as a
homogenous vapor.
The vaporization chamber 30 may be constructed from passivated
stainless steel, aluminum, or alloys of aluminum which are
compatable with hydrogen peroxide. When other multicomponent
liquids are vaporized, different materials may be suitable. Chamber
30 is structured to ensure contact between each metered liquid
increment and the heated surface 40. A vaporizer having a 25 cm
long chamber made from 1/8 inch pipe in a horizontal position, was
found to be one suitable size.
The surface 40 of the chamber 30 may be heated by any suitable
known means. The surface 40 must be made of a relatively high
thermal conducting material and must be supplied with sufficient
heat to replace the heat lost with each liquid increment
vaporization before the next succeeding liquid increment is metered
onto surface 40. The vaporization process consumes about 95% of the
required heat. A typical energy requirement for a hydrogen peroxide
sterilizer is at least 40 watts to vaporize 30% peroxide solution
at a rate of 15 microliters per second. The temperature of the
surface 40 is preferably maintained at around 90.degree. to
130.degree. C. for a hydrogen peroxide sterilizer having a
sterilization chamber temperature of about 55.degree. C.
Metering the multicomponent liquid from reservoir 20 to the
vaporization chamber 30 may be achieved by means of a three way
ball valve 25. The valve 25 must be modified to deliver discrete
increments of liquid at a predetermined rate onto the surface 40.
Any suitable valve which can meter the desired amounts of liquid at
the desired rate will suffice. A typical increment of hydrogen
peroxide and water may be between about 0.1 to 10 .mu.l for each
revolution of the ball valve 25. The rate of delivery may be about
1/2 to 5 revolutions of the ball valve 25 per second. For a
sterilization process, the total delivery of the required amount of
vapor may be completed in about five minutes. The small delivery of
the multicomponent liquid per unit time allows continuous rapid
homogenous vaporization.
Alternative apparatus structure, increment size, rate of delivery
and temperatures may vary, provided a suitable combination of the
following parameters is achieved: vaporization rates of the
components, atmospheric pressure inside the vacuum chamber, heat
availability, surface area to volume ratio of the liquid to contact
the heated surface, the conductivity of the heated surface, the
temperature of the heated surface and the rate of liquid injection
onto the surface.
The rate at which the components vaporize determines how rapidly
the liquid can be introduced into the vaporizer. The rate of
vaporization increases with increasing temperature, increasing
contact surface area, and decreasing gas pressure. The present
method intends that each increment of liquid is completely
vaporized before the next increment is delivered to the heated
surface. The vaporization rate of the least volatile component is
the rate-limiter.
The vacuum chamber pressure can affect the vaporization rate and
the rate at which vapor transfers from the vaporization area to the
vacuum chamber. In the hydrogen peroxide sterilizer, the pressure
of air needs to be as low as possible. With the peroxide
sterilizer, a sufficiently low air pressure is less than or equal
to about 30% of the total pressure arising from injected peroxide
and water. The amount of peroxide solution injected should not
exceed the saturation level, or about 35 mm Hg at 55.degree. C.
Thus, for the peroxide sterilizer application, the initial air
pressure should be 10 mm Hg or less.
Heat is required to heat the liquid to the flashing temperature,
and to vaporize the liquid. As stated above, the vaporization
process consumes about 95% of the required heat. In order to
maintain rapid vaporization, heat consumed by vaporization must be
replaced before the temperature of the liquid falls significantly.
The design of the vaporizer must assure intimate contact between
the incoming liquid and the heated surface.
The greater the surface area of a liquid, the more evaporation
sites there are. The thinner the film of liquid on a heated
surface, the more rapidly the heating of the liquid proceeds. Thus,
the larger the surface area to volume ("S/V") ratio of the liquid
on a heated surface, the more rapid the vaporization rate. The
concept of the present invention ensures a large S/V ratio by
injecting small increments into the vaporization chamber. Several
increments will not combine into larger, lower S/V ratio amounts,
because each increment is allowed to vaporize before the next
increment is injected. Typical increment sizes for a peroxide
sterilizer may range from 0.1 to 10 microliters.
The heated surface available for contact by the liquid must be
large relative to the vacant space in the vaporization chamber
tube, to ensure that no liquid traverses the chamber without being
vaporized. For a tubular design, this means that the path length
must be large relative to the diameter and/or that the path must be
tortuous. One simple, yet successful, configuration for a peroxide
sterilizer is 25 cm long, 5 mm ID tube oriented horizontally. The
path is definitely non-tortuous, but flow is apparently turbulent
enough to ensure sufficient liquid contact with the vaporizer
surface. Other more complicated designs could be used.
The material of the vaporizer surface must have a sufficiently high
thermal conductivity to deliver heat to liquid at a rate which will
balance or exceed the heat consumed by vaporization. Stainless
steel, aluminum, or aluminum alloys are suggested.
The temperature of the liquid depends on the initial temperatures
of the liquid and the heated surface, the heat capacity of the
liquid, and the balance between heat consumed by vaporization and
the rate at which heat flows to the contact area from remote
locations in the surface material.
The initial temperature of the surface should be high enough to
instantaneously raise the temperature of the incoming liquid to the
boiling temperature of the least volatile component, to provide a
sufficiently rapid rate of vaporization, and to provide a vapor
which is higher in temperature than the sterilizer chamber to which
it is sent. It must not be so high, however, that the degradation
of any component (e.g. hydrogen peroxide) is significant. For the
peroxide sterilizer, the range of useful temperatures could be from
about 80.degree. to 130.degree. C.
The permissable rate of liquid injection is dependant on all of the
above parameters. It cannot be faster than the system can vaporize
one injection increment. The smaller the size of the injection
increment the thinner the film of liquid can be and the more rapid
the vaporization will be. The other parameters of the system can be
designed to handle the desired injection rate. For a peroxide
sterilizer with a tubular vaporization chamber, injection rates of
0.1 to 1 ml per minute have proved to be useful during trial
runs.
Several experimental vaporization runs are reported below. Because
of the interdependence of the several operating parameters, the
ranges for any one parameter described below are illustrative only,
and are not intended as limitations. Furthermore, the entire stated
range of any one parameter may not necessarily be the best choice
for every combination of the other parameters. Those skilled in the
art will recognize that several optimum combinations can be
achieved and that a particular value for any parameter can be
predetermined with a minimum amount of effort.
The general experimental setup was a cylindrical tube, wrapped with
an electric heating tape, and connected to a hole in the sterilizer
door. A variable voltage transformer provided power to the heating
tape. A thermocouple monitored the temperature of the vaporization
chamber tube wall. This configuration was very flexible. The
parameters which were varied include initial temperature, heat
available to the tube (and to the incoming liquid), rate of
injection of liquid, and the length, wall thickness, internal
diameter (ID) and material of the tube. The experimental system did
not allow accurate estimation of the respective fractions of the
heater energy that were delivered to the vaporizer surface and lost
to the environment. Thus, the heat energy is not given in any of
the tables below. Instead, the electrical voltage applied to the
heater is given, to permit qualitative comparison of the heat
available to the vaporizers.
The relative success of vaporization chamber configurations was
assessed by determination of the penetration of peroxide vapors to
the center of 2 mm ID, 32 cm long glass tubes. The peroxide
reaching the center of the tube was absorbed in a paper strip.
Later the peroxide was extracted from the strip and measured
colorimetrically.
Penetration of tubes is sensitive to the amount of peroxide
reaching the tube and to interference by other vapors reaching the
tube before peroxide. Thus, it is a measure of the combined effects
of completeness of flashing the liquid, the degree of peroxide
degradation, and the homogeneity of the vaporization of the liquid
peroxide/water mixture.
The availability of heat to the injected liquid is the summarizing
quality of a successful vaporizer. It results from the combination
of the other parameters. In Table 1 the influence of heater voltage
is demonstrated with two vaporizers of different geometries and
materials. In both cases, the higher heater power effects better
penetration. The rate and completeness of vaporization is improved
when greater heat is available. The first vaporizer requires a
higher heater voltage than the second to accomplish the same
penetration. The first vaporizer is thin-walled, small in diameter,
and has a low heat capacity. Less heat can be stored in the
vaporizer prior to injection. More heat must be supplied by the
heater during the injection. The second vaporizer is very
.[.thickwalled,.]. .Iadd.thick-walled, .Iaddend.can store more
heat, has a larger ID, and was at a higher temperature at the time
of injection. Although the two vaporizers differ greatly, heating
conditions were found for each which resulted in similar
penetration levels.
TABLE 1 ______________________________________ Effect of Heat
Availability on Vaporizer Efficiency INITIAL FINAL TEMP., TEMP.,
HEATER PENETRATION .degree.C. .degree.C. VOLTAGE .mu.g H.sub.2
O.sub.2 ______________________________________ STAINLESS STEEL
TUBE, 13 cm long, 3 mm OD, 2 mm ID: 90 102 30-60 20-30 90 100 70
34-55 90 115 140 65-79 ALUMINUM CYLINDER, 13 cm long, 50 mm OD, 10
mm ID: 90 -- 35 19-59 102 -- 40 48-68 90 102 100 74-86 110 114 100
67-86 110 115 100 76-88 ______________________________________
Injection: 0.25 ml 90% peroxide at 10 .mu.l/2 sec,
The effects of injection time and initial temperature of the
flasher are shown by Table 2. The flasher used here was very short.
Peroxide was injected downward, perpendicular to the tube axis, so
the liquid splashed initially against one location on the wall of
the tube. Heater voltages were lower and initial temperatures were
higher than those in Table 1, because the heating tape was wrapped
in several layers around the short flasher. The heater voltages
tabulated here were required to maintain the starting
temperatures.
The first entry in Table 2 shows that a 3-second injection period
was too short to flash the liquid as effectively as longer periods.
With the short flasher length, sufficient heat was not available.
Some of the liquid may have passed to the sterilizer chamber
without being vaporized. The second entry shows that spreading the
injection over a 30-second period improved the flashing efficiency
at the same initial temperature and heater voltage. The final two
table entries demonstrate that similar efficiency can be achieved
with shorter time periods and higher initial temperatures. The wide
range of temperatures used in the successful tests suggests the
degradation of the peroxide is not a factor here. If it were, the
higher temperatures would have caused a noticeable decrease in the
amount of peroxide penetrating the tubes.
TABLE 2 ______________________________________ Effect of Injection
Time and Temperature on Vaporizer Effeciency INITIAL INJECTION
TEMP., HEATER PERIOD, PENETRATION .degree.C. VOLTAGE sec .mu.g
H.sub.2 O.sub.2 ______________________________________ 120 45 3 57
= 10 120 45 30 73 = 2 155 50 15 83 = 10 205 60 10 79 = 6
______________________________________ Vaporizer stainless steel
Tec. 5 cm long, 6 mm ID. Injection = 0.25 ml 90% peroxide.
Penetration entries are the mean of 5 results = .sigma..
Too rapid an injection can result in a puddle of liquid forming in
the vaporizer. As long as a puddle is present, water will be
preferentially vaporized and peroxide will remain in the liquid
phase. Subsequent liquid increments entering the vaporizer and
joining the puddle will promote continuation of the inhomogeneous
vaporization.
The data shown in Table 1 and Table 2 resulted from injections of
90% peroxide solutions. A more dramatic demonstration of the effect
of puddle formation results from injections of weaker solutions. A
30% peroxide solution was used in tests summarized in Table 3.
Injection of 0.7 ml of 30% peroxide in one second must have caused
a puddle in the vaporizer, resulting in inhomogeneous vaporization,
water vapors preceding the peroxide vapors to the tubes, and poor
penetration of the tubes by peroxide. In contrast, incremental
injection over a 150-second period (10 .mu.l/2 sec), provided small
bursts of homogeneous vapors, and resulted in much better
penetration. Similar penetration has been achieved by incremental
injection of 30% peroxide into a 25 cm long stainless steel
vaporizer.
TABLE 3 ______________________________________ Puddle Injection
Compared to Incremental Injection INITIAL INJECTION TEMP., HEATER
PERIOD, PENETRATION .degree.C. VOLTAGE sec .mu.g H.sub.2 O.sub.2
______________________________________ 88 100 1 19 .+-. 2 88 100 1
24 .+-. 1 88 100 150 38 .+-. 3 88 100 150 34 .+-. 5 88 100 150 34
.+-. 4 ______________________________________ Vaporizer = glass
tube, 10 cm long, 3 mm ID, in stainless steel sheath. Injection =
0.7 ml 30% peroxide. Penetration entries are the mean of 5 results
.+-. .sigma..
The penetration levels in Table 3 are lower than those in preceding
tables, because the concentration of peroxide in the injection
solution is much lower. Even with homogeneous vaporization, a 30%
peroxide solution contains enough water to lower the concentration
of peroxide which penetrates the tubes. However, even these lower
concentrations are an improvement over those achieved by other
methods.
Effective vaporization has been demonstrated with a variety of
vaporizer tubes and operating conditions. Successful tube
dimensions ranged from 5 to 25 cm in length, 2 to 10 mm ID, and 3
to 50 mm OD. Vaporizer materials were stainless steel, glass, and
aluminum. Temperatures ranged from 90.degree. to 205.degree. C.
Heater voltages ranged from 45 to 140 V. Injection periods ranged
from 10 to 150 seconds. These are nonrestrictive examples of useful
ranges for these parameters. Conditions outside of these ranges
might also be effective. However, the success of a vaporizer
depends on a proper combination of the several parameters. Not
every combination of the parameters within these ranges will
necessarily be successful.
* * * * *