U.S. patent application number 14/725727 was filed with the patent office on 2015-12-03 for method and apparatus for decomposing nitrogen oxide.
The applicant listed for this patent is General Electric Company. Invention is credited to Qunjian HUANG, Andrew Philip SHAPIRO, Shizhong WANG, Hai YANG, Hua ZHANG.
Application Number | 20150345035 14/725727 |
Document ID | / |
Family ID | 54481591 |
Filed Date | 2015-12-03 |
United States Patent
Application |
20150345035 |
Kind Code |
A1 |
WANG; Shizhong ; et
al. |
December 3, 2015 |
METHOD AND APPARATUS FOR DECOMPOSING NITROGEN OXIDE
Abstract
A method for decomposing nitrogen oxide includes: contacting a
gas stream comprising nitrogen oxide with a device, the device
comprising: a first electrode, an opposite second electrode, an
electrolyte between the first and the second electrodes, and a
power supply; and applying in a pulse mode an electrical current
from the power supply to the first and the second electrodes to
decompose nitrogen oxide. An associated apparatus is also
described.
Inventors: |
WANG; Shizhong; (Shanghai,
CN) ; HUANG; Qunjian; (Shanghai, CN) ; YANG;
Hai; (Shanghai, CN) ; ZHANG; Hua; (Greenville,
SC) ; SHAPIRO; Andrew Philip; (Niskayuna,
NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
General Electric Company |
Schenectady |
NY |
US |
|
|
Family ID: |
54481591 |
Appl. No.: |
14/725727 |
Filed: |
May 29, 2015 |
Current U.S.
Class: |
205/341 ;
204/229.4 |
Current CPC
Class: |
B01D 2258/01 20130101;
C25B 9/04 20130101; C25B 9/10 20130101; Y02E 60/36 20130101; B01D
2257/404 20130101; C25B 1/00 20130101; B01D 53/323 20130101; B01D
53/56 20130101; C25B 1/02 20130101; B01D 53/8631 20130101; Y02E
60/366 20130101 |
International
Class: |
C25B 9/10 20060101
C25B009/10; C25B 1/00 20060101 C25B001/00; C25B 9/04 20060101
C25B009/04; C25B 1/02 20060101 C25B001/02 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2014 |
CN |
201410239686.X |
Claims
1. A method for decomposing nitrogen oxide, comprising: contacting
a gas stream comprising nitrogen oxide with a device, the device
comprising: a first electrode, an opposite second electrode, an
electrolyte between the first and the second electrodes, and a
power supply; and applying in a pulse mode an electrical current
from the power supply to the first and the second electrodes to
decompose nitrogen oxide.
2. The method of claim 1, wherein the step of applying the
electrical current is at a temperature in a range of from
300.degree. C. to 1000.degree. C.
3. The method of claim 1, wherein in the pulse mode the electrical
current is applied for a time period different from a time period
when the electrical current is stopped.
4. The method of claim 1, wherein in the pulse mode the electrical
current is applied for a time period the same as a time period when
the electrical current is stopped.
5. The method of claim 1, wherein the electrical current is direct
current.
6. The method of claim 1, wherein the first electrode is an
anode.
7. The method of claim 1, wherein the first electrode comprises a
material for oxidizing oxygen ions to oxygen.
8. The method of claim 1, wherein the second electrode is a
cathode.
9. The method of claim 1, wherein the second electrode comprises a
material for decomposing nitrogen oxide.
10. The method of claim 1, wherein the device comprises an
adsorption layer disposed over the second electrode.
11. The method of claim 1, wherein the second electrode comprises
an adsorption material for adsorbing nitrogen oxide.
12. The method of claim 1, wherein the apparatus is of a tubular
configuration or a planar configuration.
13. The method of claim 1, wherein the device comprises a current
collector.
14. An apparatus for decomposing nitrogen oxide, comprising: a gas
source for providing a gas stream comprising nitrogen oxide; and a
device in fluid communication with the gas source and comprising: a
first electrode, an opposite second electrode, an electrolyte
between the first and the second electrodes, and a power supply
comprising a controller for applying in a pulse mode an electrical
current from the power supply to the first and the second
electrodes to decompose nitrogen oxide.
15. The apparatus of claim 14, wherein the first electrode is an
anode.
16. The apparatus of claim 14, wherein the second electrode is a
cathode.
17. The apparatus of claim 14, wherein the second electrode
comprises an adsorption material for adsorbing nitrogen oxide.
18. The apparatus of claim 14, wherein the device comprises an
adsorption layer disposed over the second electrode.
19. The apparatus of claim 14, wherein the device comprises a
current collector.
20. The apparatus of claim 14, wherein the gas source is an exhaust
gas source.
Description
BACKGROUND
[0001] Embodiments of the present invention relate generally to
methods and apparatuses for decomposing nitrogen oxide.
[0002] Nitrogen oxide (NOx, including NO and/or NO2) is undesirable
for the environment and has to be controlled. Some approaches have
been proposed to decompose nitrogen oxide into nitrogen and oxygen.
However, some approaches use hazardous compound such as ammonia,
and/or cause secondary pollution by producing ammonium sulfate,
besides being complex and expensive. Other approaches consume a
relatively large amount of power while applying electricity in
decomposing nitrogen oxide.
[0003] Therefore, while some of the proposed approaches have
general use in various industries, it is desirable to provide new
methods and apparatuses for decomposing nitrogen oxide.
BRIEF DESCRIPTION
[0004] In one aspect, the invention relates to a method for
decomposing nitrogen oxide, comprising: contacting a gas stream
comprising nitrogen oxide with a device, the device comprising: a
first electrode, an opposite second electrode, an electrolyte
between the first and the second electrodes, and a power supply;
and applying in a pulse mode an electrical current from the power
supply to the first and the second electrodes to decompose nitrogen
oxide.
[0005] In another aspect, the invention relates to an apparatus for
decomposing nitrogen oxide, comprising: a gas source for providing
a gas stream comprising nitrogen oxide; and a device in fluid
communication with the gas source and comprising: a first
electrode, an opposite second electrode, an electrolyte between the
first and the second electrodes, and a power supply comprising a
controller for applying in a pulse mode an electrical current from
the power supply to the first and the second electrodes to
decompose nitrogen oxide.
DRAWINGS
[0006] These and other features, aspects, and advantages of the
present invention will become better understood when the following
detailed description is read with reference to the accompanying
drawings, wherein:
[0007] FIG. 1 illustrates a schematic cross sectional view of an
apparatus of a first embodiment of the invention;
[0008] FIG. 2 illustrates a schematic cross sectional view of an
apparatus of a second embodiment of the invention;
[0009] FIG. 3 illustrates a schematic cross sectional view of an
apparatus of a third embodiment of the invention;
[0010] FIG. 4 illustrates a schematic cross sectional view of an
apparatus of a fourth embodiment of the invention;
[0011] FIG. 5 shows the NO conversion percentage of a gas stream
(80 ml/min, 400 ppm NO balanced with He) in the reactor using a
La0.6Sr0.4Ni0.3Mn0.703--Zr0.89Sc0.1Ce0.01O2-x layer as the cathode
at 600.degree. C. as a function of time applied with and stopped
from 50 mA of direct current; and
[0012] FIG. 6 illustrates the NO conversion percentage of a gas
stream (80 ml/min, 400 ppm NO balanced with He) at 600.degree. C.
in reactors using a NiO--Zr0.89Sc0.1Ce0.01O2-x layer and a
La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x layer as cathodes
before applying and 5 hours after stopping 50 mA of electrical
current, respectively.
DETAILED DESCRIPTION
[0013] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of ordinary skill in the art to which this disclosure belongs. The
terms "first", "second", and the like, as used herein do not denote
any order, quantity, or importance, but rather are used to
distinguish one element from another. The use of "including",
"comprising" or "having" and variations thereof herein are meant to
encompass the items listed thereafter and equivalents thereof as
well as additional items.
[0014] Approximating language, as used herein throughout the
specification and claims, may be applied to modify any quantitative
representation that could permissibly vary without resulting in a
change in the basic function to which it is related. Accordingly, a
value modified by a term or terms, such as "about" is not to be
limited to the precise value specified. In some instances, the
approximating language may correspond to the precision of an
instrument for measuring the value. Here and throughout the
specification and claims, range limitations may be combined and/or
interchanged; such ranges are identified and include all the
sub-ranges contained therein unless context or language indicates
otherwise.
[0015] In the specification and the claims, the singular forms "a",
"an" and "the" include plural referents unless the context clearly
dictates otherwise. Moreover, the suffix "(s)" as used herein is
usually intended to include both the singular and the plural of the
term that it modifies, thereby including one or more of that
term.
[0016] As used herein, the term "or" is not meant to be exclusive
and refers to at least one of the referenced components (for
example, a material) being present and includes instances in which
a combination of the referenced components may be present, unless
the context clearly dictates otherwise.
[0017] Reference throughout the specification to "some
embodiments", and so forth, means that a particular element (e.g.,
feature, structure, and/or characteristic) described in connection
with the invention is included in at least one embodiment described
herein, and may or may not be present in other embodiments. In
addition, it is to be understood that the described inventive
features may be combined in any suitable manner in the various
embodiments.
[0018] Embodiments of the present invention relate to methods and
apparatuses for decomposing nitrogen oxide.
[0019] As used herein the term "nitrogen oxide" or the like refers
to a gas comprising molecules including both oxygen and nitrogen,
for example, nitrogen monoxide, nitrogen dioxide, or a combination
thereof.
[0020] Please refer to FIGS. 1, 2, 3 and 4, an apparatus 10, 20,
30, 40 of embodiments of the invention includes a gas source 11,
21, 31, 41 for providing a gas stream 12, 22, 32, 42 comprising
nitrogen oxide and a device 100, 200, 300, 400 in fluid
communication with the gas source 11, 21, 31, 41.
[0021] The gas stream comprising nitrogen oxide may be from a
variety of gas sources. In some embodiments, the gas sources are
exhaust gas sources from gas turbines, internal combustion engines,
or combustion devices. In some embodiments, the gas source
comprises a conduit, a channel, or a tube for the passage of the
gas stream.
[0022] In some embodiments, the device 100, 200, 300, 400 includes
a first electrode 101, 201, 301, 401, an opposite second electrode
102, 202, 302, 402, an electrolyte 103, 203, 303, 403 between the
first and the second electrodes, and a power supply 104, 204, 304,
404 having a controller 114, 214, 314, 414 for applying in a pulse
mode an electrical current from the power supply 104, 204, 304, 404
to the first and the second electrodes to decompose nitrogen
oxide.
[0023] In some embodiments, nitrogen oxide can be directly
decomposed in the device 100, 200, 300, 400 before an electrical
current is applied. When a gas stream comprising nitrogen oxide is
contacted with the device, nitrogen oxide is decomposed in the
cathode in a reaction such as: NO=1/2N2+1/2O2.
[0024] However, as can be seen from examples described hereafter,
when the electrical current is applied, besides the direct
decomposition of NO described above, nitrogen oxide can also be
decomposed in the cathode in an electrochemical reaction of
NO+2e.fwdarw.1/2N2+O2--. The oxygen ions produced thereby travel
from the cathode through the electrolyte into the anode to be
oxidized into oxygen in a reaction of O2-2e.fwdarw.1/2O2. A total
reaction in the device is: NO=1/2N2+1/2O2. The decomposition rate
of nitrogen oxide increases and after the electrical current is
stopped, the conversion (decomposition) rate of nitrogen oxide is
still higher for a long time period than the conversion rate of
nitrogen oxide before applying the electrical current.
[0025] Therefore, by applying an electrical current in a pulse
mode, the decomposition of nitrogen oxide can be achieved at a
higher conversion rate than without applying an electrical current
and with less power consumption than continuously applying an
electrical current.
[0026] The decomposition of nitrogen oxide may be at any suitable
temperature. In some embodiments, the step of applying the
electrical current is at a temperature in a range from about
300.degree. C. to about 1000.degree. C.
[0027] As used herein, the term "pulse mode" refers to
intermittently applying and removing electric current, in contrast
to a continuous application of current during service. The manner
and duration of respectively applying and removing the electrical
current in the pulse mode may be dependent upon the specific
apparatus, the specific gas stream, and the decomposition
environment, as long as the conversion rate of nitrogen oxide and
the power consumption are satisfactory in the specific
circumstance.
[0028] In some embodiments, in the pulse mode the electrical
current is applied and removed alternately. In some embodiments, in
the pulse mode the electrical current is applied for a time period
different from a time period when the electrical current is
stopped. In some embodiments, in the pulse mode the electrical
current is applied for a time period the same as a time period when
the electrical current is stopped.
[0029] The electrical current may be any electrical current that
can be used to decompose nitrogen oxide at a conversion rate higher
than that of before an electrical current is applied. In some
embodiments, the electrical current is direct current. In some
embodiments, the electrical current is applied by jumping to the
designed value directly. In some embodiments, the electrical
current is applied by sweeping to the designed value slowly.
[0030] The controller 114, 214, 314, 414 may be any mechanism that
controls the on and off and/or increasing and decreasing of the
electrical current. In some embodiments, the controller is a switch
for turning on and off the electrical current.
[0031] In some embodiments, the first electrode 101, 201, 301, 401
is an anode. The anode may include any material that oxidizes
oxygen ions to oxygen, and any other materials that can be used in
the anode. In some embodiments, the anode comprises a manganite,
such as lanthanum strontium manganite (LSM), a non-limiting
exemplary composition of which includes (La0.8Sr0.2)0.95MnO3; a
combination of platinum and yttria stabilized zirconia; a
combination of platinum and gadolinium-doped ceria; or any
combination thereof.
[0032] In some embodiments, the second electrode 102, 202, 302, 402
is a cathode. The cathode may include any material that decomposes
nitrogen oxide to nitrogen and oxygen ions, and any other materials
that can be used in the cathode.
[0033] In some embodiments, the cathode includes catalysts
catalyzing the decomposition of nitrogen oxide. In some
embodiments, the cathode comprises catalysts catalyzing the
decomposition of nitrogen oxide with little or no impact by the
presence of oxygen. The oxygen coexisting with nitrogen oxide may
be discharged from the cathode.
[0034] In some embodiments, the cathode has adsorption materials
that adsorb nitrogen oxide. Examples of the adsorption material
include, but are not limited to, magnesium oxide, calcium oxide,
sodium oxide, potassium oxide, barium oxide, and strontium
oxide.
[0035] In some embodiments, the cathode comprises a manganite, such
as lanthanum strontium nickel manganite (LSNM), an exemplary
composition of which includes, but is not limited to,
La0.6Sr0.4Ni0.3Mn0.7O3; nickel oxide (NiO); a combination of LSNM
and gadolinium doped ceria (GDC, e.g., Gd0.1Ce0.9O1.95); a
combination of LSNM and scandia stabilized zirconia (SSZ, e.g.,
Zr0.89Sc0.1Ce0.01O2-x) (such as in a 50 wt % ratio); a combination
of LSNM, NiO and SSZ (such as, a ratio of 40 wt %, 30 wt %, and 30
wt %); a combination of NiO and SSZ (such as in a 50 wt % ratio); a
combination of platinum with yttria-stabilized zirconia; a
combination of platinum with GDC; or any combination thereof.
[0036] In some embodiments, as is shown in FIGS. 3 and 4, the
device 30, 40 comprises an adsorption layer 305, 405 disposed over
the second electrode 302, 402, either directly, or with one or more
intermediate layers therebetween. The adsorption layer may comprise
any adsorption material that adsorbs nitrogen oxide, such as those
described previously. The adsorption material may be distributed
inside the cathode without forming an extra layer.
[0037] In some embodiments, the apparatus comprises a current
collector (not shown). The current collector may be made of any
electrically conductive materials such as metals or metal alloys
and be in any forms suitable for use in supplying or withdrawing
electrical current from the electrodes. In some embodiments, the
current collector is made of nickel. In some embodiments, the
current collector is in the form of mesh, porous film, foam, or any
combination thereof. In some embodiments, the current collector is
nickel foam. In some embodiments, a porosity of a porous metallic
current collector is in a range from about 25% to about 99%.
[0038] In some embodiments, the current collector is a mechanical
support for the first and the second electrodes.
[0039] In some embodiments, the device comprises a current
collector disposed over the second electrode, either directly, or
with one or more intermediate layers therebetween.
[0040] The electrolyte may include any material that has a suitable
level of oxygen ion conductivity and any other suitable material.
In some embodiments, the electrolyte comprises GDC, such as
Gd0.1Ce0.9O1.95; SSZ, such as Zr0.89Sc0.1Ce0.01O2-x; oxide
materials from the barium-zirconium-cerium-yttrium (BZCY) family,
such as BaZr0.7Ce0.2Y0.1O3; or any combination thereof. In some
embodiments, the electrolyte includes bismuth oxide, zeolite,
alumina, silica, aluminum nitride, SiC, nickel oxide, iron oxide,
copper oxide, calcium oxide, magnesium oxide, zinc oxide, aluminum,
yttria stabilized zirconia, scandia stabilized zirconia, perovskite
oxides, lanthanum strontium calcium manganese, lanthanum silicate,
Nd9.33(SiO4)6O2, AlPO4, B2O3, and R2O (R stands for an alkaline
metal), AlPO4--B2O3--R2O glass which carries out the main component
of Na and the K, porous SiO2--P2O5 system glass, Y addition BaZrO3,
Y addition SrZrO3 and Y addition SrTiO3, strontium doping lanthanum
manganite, a lanthanum strontium cobalt iron oxide (La--Sr--Co--Fe
system perovskite type oxide), a La--Sr--Mn--Fe system perovskite
type oxide, a Ba--Sr--Mn--Fe system perovskite type oxide, or any
combination thereof.
[0041] A dense electrolyte is, in an embodiment, used for
mitigating the mixing of the gases of the cathode and the anode and
reducing the ohmic resistance of the electrolyte. Low ohmic
resistance is in an embodiment preferred for energy saving in the
NOx reduction process.
[0042] Each of the electrode, the electrolyte, the current
collector, and the adsorption layer may be a single layer or
comprise more than one layer depending on the needed flexibility,
gas diffusion capability, and porosity. Multiple layers may be the
same as or different from each other and connected in suitable
ways. In each single layer, the composition may be the same or
different through at least one dimension thereof.
[0043] The device may be of any configuration suitable for
decomposing nitrogen oxide. In some embodiments, as is shown in
FIGS. 1 and 3, the device 100, 300 is of a planar configuration. In
some embodiments, as is shown in FIGS. 2 and 4, the device 200, 400
is of a tubular configuration and comprises a space 206, 406
therein.
[0044] The device described herein may be prepared by providing a
current collector and applying sequentially different layers on
both sides thereof, or providing any of other layers and laminating
different layers on either/both sides thereof. The layers may be
formed/applied/laminated by any suitable means such as extruding,
dip coating, spraying and printing.
EXAMPLES
[0045] The following examples are included to provide additional
guidance to those of ordinary skill in the art in practicing the
claimed invention. These examples do not limit the invention as
defined in the appended claims.
Example 1
La0.6Sr0.4Ni0.3Mn0.7O3 Synthesis
[0046] La2O3, SrCO3, Mn(AC)2.4H2O and NiO were ball milled in EtOH
and calcined at 1300.degree. C. for 8 hours to prepare
La0.6Sr0.4Ni0.3Mn0.7O3. X-ray diffraction (XRD) analyses confirmed
that a pure phase of La0.6Sr0.4Ni0.3Mn0.7O3 was obtained.
Example 2
Reactor Preparation
[0047] Two 7.5 cm long one-end open (La0.8Sr0.2)0.95MnO3 tubes were
fabricated by extruding. The outer diameter of each tube was about
1 cm, and the inner diameter was about 0.7 cm.
[0048] A dense Zr0.89Sc0.1Ce0.01O2-x electrolyte film was coated on
each (La0.8Sr0.2)0.95MnO3 tube and was co-sintered with the
(La0.8Sr0.2)0.95MnO3 tube at 1250.degree. C.
[0049] A layer of La0.6Sr0.4Ni0.3Mn0.7O3 and Zr0.89Sc0.1Ce0.01O2-x
(La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x layer, 50 wt %
ratio) and a layer of NiO and Zr0.89Sc0.1Ce0.01O2-x
(NiO--Zr0.89Sc0.1Ce0.01O2-x layer, 50 wt % ratio) were respectively
deposited on the Zr0.89Sc0.1Ce0.01O2-x electrolyte films and
sintered at around 900-1100.degree. C. to obtain two reactors. The
active area of each of
La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x and
NiO--Zr0.89Sc0.1Ce0.01O2-x layers was about 10 cm2.
[0050] A layer of porous platinum paste was applied to each of
La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x and
NiO--Zr0.89Sc0.1Ce0.01O2-x layers to form a porous metallic current
collector.
[0051] The microstructures of the reactors were analyzed. As a
typical example, SEM images of the cross section of the
(La0.8Sr0.2)0.95MnO3/Zr0.89Sc0.1Ce0.01O2-x/NiO--Zr0.89Sc0.1Ce0.01O2-x
reactor show that the (La0.8Sr0.2)0.95MnO3 layer had a porous
structure with a low porosity, the Zr0.89Sc0.1Ce0.01O2-x layer had
a dense structure, while the NiO--Zr0.89Sc0.1Ce0.01O2-x layer had a
porous structure with a high porosity.
Example 3
Decomposition of Nitrogen Oxide
[0052] The reactors were each put inside an alumina tube. The inner
diameter of the alumina tube was about 2 cm. A gas stream (400 ppm
NO balanced with He, 80 ml/min) was fed into the alumina tube
passing through the outer surface of the reactor at a temperature
of 600.degree. C. Direct current (DC) of 50 mA was applied on each
reactor for about 900 minutes before being stopped.
[0053] The La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x layer and
the NiO--Zr0.89Sc0.1Ce0.01O2-x layer were assigned as cathodes,
where the direct decomposition of NO and electrochemical NO
reduction took place. The (La0.8Sr0.2)0.95MnO3 layer was the anode,
where the oxidation of oxygen ions took place. The corresponding
voltage between anode and cathode was in the range of 1-1.5 V. Gas
chromatography equipped with a PQ column and a RAE7800 gas sensor
were used to detect NO and NO2 with an accuracy of 1 ppm and 0.1
ppm, respectively.
[0054] FIG. 5 shows the NO conversion percentage of the reactor
using the La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x layer as
the cathode layer at 600.degree. C. increased gradually from about
5% to about 40% in about 900 minutes after applying the direct
current of 50 mA. The 5% NOx conversion rate before applying the DC
is the direct catalytic NOx decomposition activity of the reactor.
After the electrical current was stopped, the NO conversion rate
gradually decreased to about 20% after 300 minutes, which is much
higher than the initial 5% conversion rate before applying the
electrical current. This suggests that the DC activated the reactor
for the NOx decomposition. Therefore, this experiment demonstrates
that nitrogen oxide may be decomposed at a higher conversion rate
by applying and stopping the electrical current alternately in a
pulse mode than without applying an electrical current.
[0055] NO conversion rates before applying and about 5 hours after
stopping 50 mA of direct current in the reactors using the
NiO--Zr0.89Sc0.1Ce0.01O2-x layer and the
La0.6Sr0.4Ni0.3Mn0.7O3--Zr0.89Sc0.1Ce0.01O2-x layer respectively as
cathode layers are shown in FIG. 6. Both of the two reactors show
much improved NO conversion rate after stopping the 50 mA of
electrical current than before applying the electrical current. The
high NO conversion rate after stopping the electrical current might
be related to the reduction of Ni species in NiO and Ni and Mn
species in La0.6Sr0.4Ni0.3Mn0.7O3 while applying the electrical
current, which could generate oxygen vacancies. These vacancies are
potential active centers for the adsorption and further
decomposition of NOx. This experiment further indicates that
nitrogen oxide can be decomposed at a high conversion rate with
less power consumption in a pulse mode of applying and stopping
electrical current alternately than continuously applying an
electrical current.
[0056] While only certain features of the invention have been
illustrated and described herein, many modifications and changes
will occur to those skilled in the art. It is, therefore, to be
understood that the appended claims are intended to cover all such
modifications and changes as fall within the true spirit of the
invention.
* * * * *