U.S. patent application number 11/605695 was filed with the patent office on 2008-02-21 for method for maximizing the value of carbonaceous material.
Invention is credited to Albert Calderon.
Application Number | 20080040975 11/605695 |
Document ID | / |
Family ID | 46328415 |
Filed Date | 2008-02-21 |
United States Patent
Application |
20080040975 |
Kind Code |
A1 |
Calderon; Albert |
February 21, 2008 |
Method for maximizing the value of carbonaceous material
Abstract
A method for pyrolyzing coal to produce a raw hydrogen-rich gas
and a hot char composed of carbon that is divided into two streams,
one gasified to make a second gas and one reacted with steam to
produce hot activated carbon that is divided into a first
sub-stream and a second sub-stream. The hydrogen rich gas, after
cleanup, is converted to methanol which, in turn, is synthesized
into gasoline or synthetic natural gas. The second gas, after
clean-up, fuels a turbine to generate electricity while exhausting
a flue gas (N.sub.2+CO.sub.2) that is reacted with the first
sub-stream of hot activated carbon and with hydrogen for synthesis
into urea (CO(NH.sub.2).sub.2). The urea is mixed with the second
sub-stream of activated carbon to produce a fertilizer which is
introduced into soil to store plant nutrients. This process
produces fuel, electricity, and enhancement of plant growth.
Inventors: |
Calderon; Albert; (Bowling
Green, OH) |
Correspondence
Address: |
Albert Calderon
500 Lehman Ave., P.O. Box 126
Bowling Green
OH
43402
US
|
Family ID: |
46328415 |
Appl. No.: |
11/605695 |
Filed: |
November 30, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11506939 |
Aug 21, 2006 |
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11605695 |
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Current U.S.
Class: |
48/197R |
Current CPC
Class: |
C10J 2300/1659 20130101;
C10J 2300/1668 20130101; C10J 2300/1675 20130101; C10J 2300/1684
20130101; Y02E 20/16 20130101; C10J 2300/093 20130101; C10J
2300/165 20130101; C10J 2300/094 20130101; C10J 2300/1665 20130101;
C10J 2300/0959 20130101; C10J 3/64 20130101 |
Class at
Publication: |
48/197.R |
International
Class: |
C10J 3/00 20060101
C10J003/00 |
Claims
1. A method for maximizing the value of carbonaceous material in an
environmentally acceptable manner comprising the following steps:
pyrolyzing the carbonaceous material in an atmosphere which is
deficient of oxygen to produce a first gas and a hot char which
possesses a cellular structure that is essentially made up of
carbon; dividing said char into two streams comprising a first
stream of char and a second stream of char; gasifying said first
stream of char to produce a second gas; utilizing said first stream
of gas and said second stream of gas as fuels for the formation of
one or more than one subsequent form of energy while emitting a
flue gas containing carbon dioxide (CO.sub.2) into the atmosphere,
said CO.sub.2 being a greenhouse gas and being suspected of causing
global warming; and sequestering said second stream of char in soil
in order to compensate for at least a portion of the CO.sub.2
emitted into the atmosphere while increasing the capability of the
soil to retain nutrients in the cellular structure of the
sequestered char to result in an increase in the yield of plant
growth from said soil, said increase of plant growth being a
greater consumer of CO.sub.2 than if said second stream of char
were not sequestered in the soil.
2. The method as set forth in claim 1 wherein said first gas and
said second gas are cleaned prior to the step of utilizing said
gases as fuels for the formation of one or more subsequent form of
energy.
3. The method as set forth in claim 1 wherein said second stream of
char is activated to convert it to activated carbon by enhancing
the capability of its cellular structure to absorb nutrients.
4. The method as set forth in claim 1 wherein said first gas is a
hydrogen (H.sub.2) rich gas which is suitable for making an
upgraded chemical.
5. The method as set forth in claim 1 wherein the step of utilizing
said first gas and second gas as fuels for the formation of one or
more than one subsequent form of energy is further characterized by
the step of utilizing both gases as fuels for electric power
generation.
6. The method as set forth in claim 4 wherein said upgraded
chemical takes the form of methanol.
7. The method as set forth in claim 4 wherein said upgraded
chemical takes the form of synthetic natural gas.
8. The method as set forth in claim 6 wherein said methanol is
converted into a transport fuel.
9. The method as set forth in claim 8 wherein said transport fuel
comprises gasoline.
10. The method as set forth in claim 1 wherein the step of
gasifying said first stream of char to produce a second gas is
further characterized by the step of injecting an oxidant to
implement the step of gasifying said char to produce a hot second
gas at an elevated temperature.
11. The method as set forth in claim 10 wherein steam is injected
in addition to said oxidant.
12. The method as set forth in claim 10 wherein said step of
injecting an oxidant comprises the injecting of air to give said
second gas additional mass and low NO.sub.X formation properties
when it is combusted.
13. The method as set forth in claim 12 further comprising the use
of said second gas with its additional mass to fuel a combustion
turbine to efficiently generate electric power.
14. The method as set forth in claim 13 being further characterized
by said combustion turbine being part of a combined cycle
configuration for the generation of electric power while emitting
an off-gas as a waste flue gas consisting mainly of
N.sub.2+CO.sub.2.
15. The method as set forth in claim 14 wherein said combined cycle
configuration is operated at a full load continuously to generate
the maximum amount of electric power despite off-peak period.
16. The method as set forth in claim 15 wherein the excess electric
power generated during off-peak period is used to electrolyze water
to produce economical H.sub.2 and O.sub.2.
17. The method as set forth in claim 16 wherein said water takes
the form of steam that is electrolyzed in a high-temperature
electrolysis system.
18. The method as set forth in claim 17 wherein said
high-temperature electrolysis comprises the recycling of H.sub.2
with said steam to provide a more efficient electrolysis system in
the production of H.sub.2.
19. The method as set forth in claim 14 wherein said flue gas
consisting of N.sub.2+CO.sub.2 is combined with H.sub.2 generated
via electrolysis to form a mixture of flue gas (N.sub.2+CO.sub.2)
plus hydrogen (H.sub.2).
20. The method as set forth in claim 3 wherein the step of
activating said second stream of char to convert it to activated
carbon is further characterized by the step of sub-dividing said
second stream of char into a "first" sub-stream and a "second"
sub-stream.
21. The method as set forth in claim 20 wherein said "first"
sub-stream is heated in order to create a hot "first" sub-stream of
hot activated carbon (C).
22. The method as set forth in claim 10 wherein said step of
injecting an oxidant to implement the step of gasifying said char
to produce a hot second gas at an elevated temperature is further
characterized by the step of directing said hot second gas to heat
said "first" sub-stream of activated carbon referred to in claim 21
to increase its reactivity.
23. The method as set forth on claim 19 wherein said mixture of
flue gas (N.sub.2+CO.sub.2) plus hydrogen (H.sub.2) is further
combined with said "first" sub-stream of hot activated carbon (C)
referred to in claim 21 to form urea.
24. The method as set forth in claim 23 wherein said urea is
further mixed with said "second" sub-stream of activated carbon (C)
referred to in claim 20 to form an enhanced urea for the vigorous
growth of plant life.
25. The method as set forth in claim 1 wherein said carbonaceous
material is coal.
26. The method as set forth in claim 14 wherein the step of
emitting an off-gas as a waste flue gas consisting mainly of
N.sub.2+CO.sub.2 is further characterized by the step of separating
the N.sub.2 from the CO.sub.2.
27. The method as set forth in claim 26 comprises the reacting of
the CO.sub.2 with ammonia 2(NH.sub.3) to form urea
(NH.sub.2.NH.sub.2.CO) plus water (H.sub.2O).
28. The method as set forth in claim 1 wherein said carbonaceous
material contains sulfur.
29. The method as set forth in claim 1 wherein said first gas and
said second gas are combined, cleaned and utilized to generate
electric power while emitting a flue gas which is suspected to
create a harmful effect to the environment.
30. The method as set forth in claim 2 wherein said first gas and
said second gas are cleaned comprises the removal of mercury from
both gases.
31. The method as set forth in claim 1 wherein said first gas and
said second gas are utilized for the poly-generation of various
products.
Description
BACKGROUND OF THE INVENTION
[0001] This invention relates to a clean and efficient
poly-generation of various valuable products from carbonaceous
materials such as bituminous coal, sub-bituminous coal, lignite,
peat, coke, biomass, etc. This invention which is a
continuation-in-part of the Applicant's pending patent application
bearing Ser. No. 11/506,939 filed on Aug. 21, 2006, relates to the
co-production of enhanced fuels and efficient electric power while
mitigating the ill-effects caused to the environment by utilizing
said carbonaceous materials as combustible fuels, particularly with
respect to emitting carbon dioxide (CO.sub.2) into the atmosphere.
CO.sub.2 is commonly referred to as a "greenhouse gas" and is
suspected of contributing to global warming. Specifically, this
invention is an improvement of the Applicant's issued patent
bearing No. 6,911,058 B2 issued on Jun. 28, 2005; this patent fails
to address the ever-increasing ill effects to the environment
caused by the emission of greenhouse gases, in particular by carbon
dioxide (CO.sub.2).
[0002] Attempts are being made to capture CO.sub.2 where it is
generated and to sequester it by introducing it under pressure into
such places as deep wells and underground reservoirs for permanent
storage--a costly, inefficient and questionable solution, except in
cases wherein it is injected into oil or gas wells in order to
recover residual oil or gas from such wells; however, the
infrastructure related to the piping necessary to transport the
CO.sub.2 to such wells is a major disadvantage; there is no
assurance that CO.sub.2 will not leak out via fissures in such
wells.
[0003] The Applicant has discovered a method herein disclosed that
reduces the formation of CO.sub.2 by being efficient while still
using said carbonaceous fuels, and especially coal, and at the same
time converting CO.sub.2 into a useful by-product such as urea, a
valuable fertilizer that enhances the growth of biomass, a
renewable energy resource in the agriculture sector.
[0004] Before listing the objectives of the instant invention and
proceeding with its description, coal will be used as the energy
resource as an example, since more than four billion tons of coal
are combusted yearly worldwide, but the instant invention is
applicable to the use of carbonaceous materials in general.
OBJECTIVES OF THE INVENTION
[0005] The main object of the instant invention is to maximize the
value of said carbonaceous materials by making their efficient use
possible and yet mitigating the ill-effects that they cause to the
environment.
[0006] Another object of the instant invention is to extract from
the coal via pyrolysis a raw hydrogen rich gas which, after
cleanup, is used as a resource to make valuable and sorely needed
products such as gasoline or synthetic natural gas (SNG) while at
the same time producing a hot char.
[0007] Still another object of the present invention is to gasify a
first stream of the hot char with air preferably, to produce a raw
lean gas which, after cleanup, becomes an excellent fuel for
combustion turbines which, when configured in a combined cycle
mode, generate electric power most efficiently by virtue of mass
and low NO.sub.X formation while emitting a flue gas composed
mainly of nitrogen and carbon dioxide (N.sub.2+CO.sub.2).
[0008] Yet another object of the instant invention is to pass steam
through a second stream of said hot char in order to transform it
to activated carbon.
[0009] Therefore another object of the instant invention is to
divide said activated carbon into two sub-streams wherein a "first"
sub-stream is set aside for export to the agriculture sector for
introduction into soils to stimulate more vigorous growth of crops
by providing a cellular structure to store plant nutrients while at
the same time sequestering carbon in Mother Earth whence it
originated.
[0010] Therefore another object of the instant invention is to
elevate the temperature of the "second" sub-stream of said
activated carbon to enable it to react with nitrogen (N.sub.2) to
thus activate the N.sub.2.
[0011] Further another object of the instant invention is to use
off-peak power to electrolyze water to co-produce hydrogen
(H.sub.2) and oxygen (O.sub.2).
[0012] Further still another object of the instant invention is to
react hot activated carbon (C) with flue gas (N.sub.2+CO.sub.2) and
with hydrogen (H.sub.2) to make urea (CO(NH.sub.2).sub.2) while at
the same time sequestering CO.sub.2 via the formation of urea, such
as CO.sub.2 being produced in the generation of electric power.
[0013] Further yet another object of the instant invention is to
mix activated carbon with urea to make a super-fertilizer.
[0014] Therefore yet another object of the instant invention is to
utilize the O.sub.2 derived from electrolysis to serve as the
oxidant in the pyrolysis of the coal.
[0015] It is yet another object of the present invention to mix
said hydrogen rich gas and said lean gas to create a fuel suitable
to co-produce electric power and urea while sequestering carbon in
the soil.
[0016] It is still another object of the present invention to mix
said hydrogen rich gas and said lean gas to create a fuel suitable
to generate electric power while activated carbon is sequestered in
soil.
[0017] These and other objects of the present invention will become
more apparent to those skilled in the art to which this invention
pertains from the following description and appended claims.
Reference is now being made to the accompanying drawings forming a
part of this specification. It is to be noted that the embodiments
shown herein are for the purpose of description and not
limitation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a process-flow diagram in block form of the
invention with the components and process streams being numerically
identified.
[0019] FIG. 2 is a process-flow diagram in block form of the
invention with the components and process streams being identified
with words.
[0020] Before proceeding with the detailed description of the
invention by making use of the drawings, it is to be noted that for
the sake of clarity reference will be made to the numerals and to
the words to represent the various components and process
streams.
DETAILED DESCRIPTION OF THE DRAWINGS
[0021] Referring to FIG. 1, numeral 10 denotes a pyrolysis chamber
and numeral 11 a char gasifier; numeral 12 denotes a gas clean-up
system for the hydrogen rich gas from pyrolysis, and numeral 18
denotes a gas clean-up system for lean gas made in gasifier 11;
numeral 13 represents a methanol plant and numeral 14 represents a
gasoline conversion plant; numerals 15, 16, and 17 represent a
combined-cycle power generation assembly with numeral 15 denoting a
gas turbine, numeral 16 denoting a heat-recovery steam generator
and numeral 17 denoting a steam turbine; numeral 21 represents a
rectifier to change the power from alternating current to direct
current and numeral 19 represents an electrolysis chamber to split
water into H.sub.2 and O.sub.2. Numeral 20 denotes a urea plant for
synthesizing hot activated carbon, flue gas (N.sub.2+CO.sub.2) and
hydrogen into carbon monoxide and urea--namely
CO+CO(NH.sub.2).sub.2. Numeral 63 is a char activator to make
activated carbon and numeral 64 represents a reheater to reheat the
activated carbon.
[0022] Before describing the operation of the instant invention, it
is to be noted that the various streams incorporated in the method
would include pressure boosting and pressure let-down equipment,
such as compressors, expanders, and miscellaneous valves as
required, depending upon the prevailing conditions to enable the
navigation of the flow of each stream. Since the use of such
equipment is common practice in the field of chemical engineering
and is known in the art to which this invention pertains, the
Applicant has obviated the inclusion of such equipment in the
drawings, even though such equipment will be used in the
application of the instant invention.
Operation
[0023] Assuming that the process is already at steady state and
referring to both FIGS. 1 and 2 in combination, coal denoted by
stream 60 is fed into pyrolysis chamber 10 wherein O.sub.2--stream
22 is injected into it to such an extent as to combust a small
portion of the coal to generate the thermal energy required to
devolatilize the coal to yield a rich raw gas having a high H.sub.2
content--stream 23, which is directed to rich gas cleanup system
12. By controlling the O.sub.2 input into chamber 10, the
conditions within pyrolysis chamber 10 are maintained highly
reducing while converting the coal into a hot char which is divided
into two parts, stream 27 and stream 31. Stream 27 is fed into
gasifier 11 where it is reacted preferably with air, stream 51
which is derived from the compressor (not shown) of gas turbine 15,
thus converting the carbon in the hot char into a hot raw lean
gas--stream 67 and slag--stream 26. Hot char, being mostly carbon
and highly reactive by virtue of its cellular and porous structure,
is efficiently gasified with air.
[0024] Hot char stream 31, the second part of the char from stream
24, is directed to the activator denoted by numeral 63 for
converting the hot char into activated carbon by means of
steam-stream 33; stream 66 denotes the off-gas from activator 63;
stream 55 represents the activated carbon discharged from activator
63. During the activation of the hot char with steam, it loses
temperature by virtue of the water-gas reaction that takes
place.
[0025] Activated carbon stream 55 is, in turn, further divided into
sub-stream 58 and sub-steam 61, with sub-stream 58 being fed into
reheater 64 where the temperature of the activated carbon is raised
by making use of the elevated temperature of the hot, raw lean
gas-stream 67, by directly contacting the activated carbon
contained in reheater 64. The partially cooled raw lean gas leaves
reheater 64 as stream 25 and is directed to lean gas cleanup 18. In
both cleanup systems 12 and cleanup 18, the sulfur in the gases is
removed, and it leaves cleanup 12 via stream 28 and cleanup 18 via
stream 29; these two sulfur streams join to form stream 44.
[0026] The cleaned rich gas which essentially is CO+2H.sub.2 leaves
cleanup 12 via stream 46 and is directed to methanol plant 13 where
the rich gas is converted to methanol which, in turn, is directed
as stream 47, to gasoline plant 14 where the methanol is converted
to gasoline via Exxon Mobil's process known as "MTG" for short. The
clean lean gas which essentially is N.sub.2+CO leaves cleanup 18
via stream 30 to which CO--stream 48, is added to form stream 32
which fuels gas turbine 15; air to combust stream 32 is furnished
by stream 52 which is compressed prior to entering the combustion
chamber (not shown) of gas turbine 15. The flue gas exhausting from
the gas turbine is passed through heat recovery steam generator 16
to raise steam which is directed to steam turbine 17 via stream 50.
Both gas turbine 15 and steam turbine 17 are each followed by a
generator (not shown) to generate electric power most efficiently
via the combined cycle mode which power leaves as streams 37 and
38, respectively, to form stream 39. The flue gas leaving
heat-recovery steam generator 16, which is made up of nitrogen and
carbon dioxide (N.sub.2+CO.sub.2) is denoted by stream 34. A
portion of the steam generated in heat-recovery steam generator 16
is withdrawn as a side stream which is denoted by numeral 36; this
side stream of steam together with H.sub.2 stream 49 form stream 53
which is directed to high-temperature electrolysis system 19 in
order to increase the efficiency of H.sub.2 generation. It is to be
noted that side stream 36 may also be withdrawn from steam turbine
17.
[0027] An alternating electric current stream denoted by numeral 40
is directed to rectifier 21 where it is converted to direct
electric current to form streams 42 and 43 which are introduced
into electrolysis system 19 in order to electrolyze the steam
contained in stream 53 to yield a larger output of H.sub.2-stream
56 and also producing O.sub.2 as stream 22; this larger output of
H.sub.2 is directed to synthesis system 20, while the O.sub.2,
after being compressed (not shown), is directed to pyrolysis
chamber 10 as stream 22.
[0028] Referring now to the flue gas, stream 34 (N.sub.2+CO.sub.2)
is split to create a bleed of flue gas to maintain system balance
denoted by numeral 35, to result in stream 57 which joins H.sub.2
stream 45 (the net H.sub.2 produced in electrolysis system 19) to
form stream 65. The activated carbon (C)--stream 68 and the flue
gas (N.sub.2+CO.sub.2) together with the H.sub.2--stream 65 are
respectively introduced into urea plant 20 to produce urea
(CONH.sub.2).sub.2)+CO as stream 69. The CO, as stream 48, is
separated from stream 69 to result in the formation of urea as
stream 59 whence this stream joins activated carbon sub-stream 61
to form a super-fertilizer for export denoted by stream 62.
[0029] It is to be noted that the hot activated carbon may be
reacted with the flue gas by itself in a reactor to form CO and
cyanogen (C.sub.2N.sub.2), and the H.sub.2 may then be added in a
subsequent reaction to form the urea. Further, the formation of
urea may also occur via the ammonia (NH.sub.3) route by reacting
N.sub.2 with 3H.sub.2 to make 2NH.sub.3 and subsequently reacting
the 2NH.sub.3 with CO.sub.2 to form CO(NH.sub.2).sub.2+H.sub.2O,
the conventional method of making urea.
[0030] The step of making urea may be obviated by making use of the
method to make activated carbon from a portion of the char,
activating such portion, and sequestering it in the soil to enhance
it by introducing cellular structure to store plant nutrients and
to provide time release of such nutrients to result in causing the
vigorous growth of plant life.
[0031] In summation, it is submitted that the method described
herein for maximizing the benefits derived from a carbonaceous
material such as coal which contains sulfur in an environmentally
acceptable manner while co-producing liquid fuel, electric power
and urea is comprised of pyrolyzing the coal with oxygen to produce
a raw hydrogen (H.sub.2) rich gas and a hot char which is cellular
in structure and substantially composed of carbon (C). The hot char
so produced is divided into two streams, with the first stream
being directed to a gasifier that is air blown to make a raw lean
gas which is made up of nitrogen and carbon monoxide (N.sub.2+CO)
and a second stream being activated with steam to produce activated
carbon that is further divided into a "first" sub-stream of
activated carbon and a "second" sub-stream of activated carbon
whose use will be described hereinafter.
[0032] Subsequent to the cleaning of the H.sub.2 rich gas and the
lean gas, including the removal of mercury from these gases, the
cleaned H.sub.2 rich gas (syngas) may be converted to one or more
chemicals, but preferably to methanol which, in turn, is converted
to a transportation fuel such as gasoline, a most valuable liquid
fuel. The cleaned lean gas fuels a gas turbine that is part of a
combined-cycle system to generate electric power most efficiently
by virtue of its large N.sub.2 content which contributes a large
mass flow of gases through the gas turbine while exhausting an
off-gas (flue gas) made up of N.sub.2+CO.sub.2. This flue gas which
is reacted with activated carbon and H.sub.2, is synthesized with
2H.sub.2 to produce urea which is characterized chemically as
NH.sub.2.NH.sub.2.CO or CO(NH.sub.2).sub.2 plus CO. Alternatively,
the formation of the urea may be the conventional route of making
urea by first forming ammonia (NH.sub.3) and, in turn, reacting two
molecules of NH.sub.3 with CO.sub.2 to form CO(NH.sub.2).sub.2, and
H.sub.2O as by-product; in this case, the N.sub.2 in the flue gas
is separated from the CO.sub.2 prior to reacting with the
NH.sub.3.
[0033] Preferably during off-peak periods, the excess of the
electric power that can be generated for which there is no demand,
such power is utilized to electrolyze steam in a high-temperature
electrolysis system to generate H.sub.2 and O.sub.2, with the
H.sub.2 produced being the source for the H.sub.2 needed in
synthesizing the N.sub.2+CO.sub.2 (with the aid of hot activated
carbon) into urea. Preferably, some of the H.sub.2 produced via
electrolysis is recycled with the steam fed to the electrolysis
system to enhance the production of H.sub.2. The O.sub.2 which is
co-produced via electrolysis is used in the pyrolysis of the coal
mentioned above.
[0034] The "first" sub-stream of activated carbon serves to
activate N.sub.2 in the flue gas (N.sub.2+CO.sub.2) to make
possible the formation of urea according to the following chemical
reaction:
(N.sub.2+CO.sub.2)+C+2H.sub.2.fwdarw.CO+CO(NH.sub.2).sub.2, wherein
the CO is separated from the urea and is added to the lean gas to
become part of the fuel for the gas turbine mentioned above.
[0035] The urea so formed is mixed with the "second" sub-stream of
activated carbon, mentioned above, to produce a super-fertilizer
which is put into the soil, not only for the sequestration of
carbon (C) directly and carbon dioxide (CO.sub.2) indirectly via
the urea, but also to provide storage for plant nutrients in the
abundant cellular structure of the activated carbon, thus: [0036]
Contributing to the efficient use of plant nutrients via their
storage in the cells of activated carbon: [0037] Increasing plant
yield via the conservation of the nutrients; and, [0038] Reducing
CO.sub.2 emissions by converting the CO.sub.2 in the flue gas into
a component of the super-fertilizer while at the same time
sequestering a portion of the carbon from the coal back into the
soil. From an economic standpoint, the formation of a
super-fertilizer made from low-cost carbon (char from coal
pyrolysis), low-cost hydrogen (electrolyzing steam with off-peak
power), and flue gas (a waste off-gas) can be sold to the farming
community at a very attractive price when compared to urea made
from natural gas, thus helping produce abundant plant life to
retain water in the soil that will increase forest land and
abundant food for mankind.
* * * * *