U.S. patent number 3,907,519 [Application Number 05/475,061] was granted by the patent office on 1975-09-23 for gasification of solid carbonaceous materials to obtain high btu product gas.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Robert Paul Sieg, Robert James White.
United States Patent |
3,907,519 |
Sieg , et al. |
* September 23, 1975 |
Gasification of solid carbonaceous materials to obtain high BTU
product gas
Abstract
A process for converting solid carbonaceous material to
combustible gases which comprises: A. heating and reacting the
solid carbonaceous material with reactive gases in a gasification
zone to obtain said combustible gases and withdrawing the
combustible gases from the gasification zone, B. methanating at
least a portion of said combustible gases in a methanation zone to
obtain methanated gases, C. feeding at least a portion of said
methanated gases through the gasification zone thereby increasing
the methane content and BTU value of said combustible gases and
transferring the sensible heat from said methanated gases to said
gasification zone.
Inventors: |
Sieg; Robert Paul (Piedmont,
CA), White; Robert James (Pinole, CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
|
[*] Notice: |
The portion of the term of this patent
subsequent to June 18, 1991 has been disclaimed. |
Family
ID: |
26942325 |
Appl.
No.: |
05/475,061 |
Filed: |
May 31, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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252450 |
May 11, 1972 |
3817725 |
|
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Current U.S.
Class: |
48/202; 48/210;
518/704; 518/712; 48/197R; 518/702; 518/705 |
Current CPC
Class: |
C10J
3/845 (20130101); C10J 3/00 (20130101); C10J
2300/0976 (20130101); C10J 2300/0946 (20130101); C10J
2300/1846 (20130101); C10J 2300/1884 (20130101); C10J
2300/1807 (20130101); C10J 2300/0956 (20130101); C10J
2300/1892 (20130101); C10J 2300/0996 (20130101); C10J
2300/093 (20130101) |
Current International
Class: |
C10J
3/00 (20060101); C10J 003/14 () |
Field of
Search: |
;48/197A,202,210,209,215,197R,206 ;252/372,373 ;260/449M |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Kratz; Peter F.
Attorney, Agent or Firm: Magdeburger; G. F. Davies; R. H. De
Young; J. J.
Parent Case Text
RELATED APPLICATIONS
This application is a continuation-in-part of copending application
Ser. No. 252,450, filed May 11, 1972, now U.S. Pat. No. 3,817,725
the disclosure of which is incorporated herein by reference.
Commonly-assigned application titled "Gasification of Solid
Carbonaceous Waste Material", Ser. No. 252,449, filed May 11, 1972,
now U.S. Pat. No. 3,817,724 is related to this application, the
disclosure of which is incorporated herein by reference.
Claims
What is claimed is:
1. A process for converting solid carbonaceous material to
combustible gases which comprises:
a. heating and reacting the solid carbonaceous material with
reactive gases in a gasification zone to obtain said combustible
gases and withdrawing the combustible gases from the gasification
zone,
b. methanating at least a portion of said combustible gases in a
methanation zone to obtain methanated gases, and
c. feeding at least a portion of said methanated gases through the
gasification zone thereby increasing the methane content and BTU
value of said combustible gases and transferring the sensible heat
from said methanated gases to said gasification zone.
2. A process in accordance with claim 1 wherein the gasification
zone comprises an upright cylindrical gasifier reactor vessel and
the methanated gases are introduced at a central position along the
length of said gasifier, said solid carbonaceous material is
introduced at an upper position along the length of said gasifier,
and heating gases are introduced at a lower position along the
length of said gasifier.
3. A process in accordance with claim 1, which comprises the
further steps of
d. partially or wholly burning a portion of said combustible gases
in a recycle gas combustion zone to obtain hot recycle gas
containing essentially no molecular oxygen, and
e. passing at least a portion of the hot recycle gas into the
gasification zone to supply heat and said reactive gases to the
carbonaceous material.
4. A process in accordance with claim 3 wherein the temperature in
the gasification zone is controlled to below about 2000.degree.F.
by means of adjusting the temperature of, or amount of, said hot
recycle gas to the gasification zone.
5. The process of claim 3 wherein said carbonaceous material is
coal.
6. A process for converting solid carbonaceous material to
combustible gases, said process being free of carbon dioxide
removal stages, which comprises:
a. heating and reacting the solid carbonaceous material with
reactive gases in a gasification zone to obtain said combustible
gases and withdrawing the combustible gases from the gasification
zone,
b. partially or wholly burning a portion of said withdrawn
combustible gases in a recycle gas combustion zone to obtain hot
recycle gas containing essentially no molecular oxygen,
c. passing the hot recycle gas into the gasification zone to supply
heat and at least a portion of said reactive gases to the
carbonaceous material.
d. methanating at least a portion of said combustible gases in a
methanation zone to obtain methanated gases, and
e. feeding a portion of said methanated gases through the
gasification zone thereby increasing the methane content and BTU
value of said combustible gases and transferring the sensible heat
from said methanated gases to said gasification zone.
7. A process in accordance with claim 6 wherein the temperature in
the gasification zone is controlled to below about 2000.degree.F.
by means of adjusting the temperature of or amount of said hot
recycle gas to the gasification zone.
8. The process of claim 6 wherein said carbonaceous material is
coal.
9. A process of claim 1 wherein a portion of the combustible gases
from the gasification zone is combined with a portion of the gases
from the methanation zone to form a net product combustible
gas.
10. A process of claim 5 wherein a portion of the combustible gases
from the gasification zone is combined with a portion of the gases
from the methanation zone to form a net product combustible gas.
Description
BACKGROUND OF THE INVENTION
The present invention relates to gasification of solid carbonaceous
material.
Previous gasification methods for solids mostly fall into the
classifications of eduction processes or partial oxidation
processes.
Eduction type processes are described in U.S. Pat. No. 1,055,344,
Process of Making Gas; U.S. Pat. No. 2,640,014, Oil-Shale Eduction
Process and Apparatus; and U.S. Pat. No. 3,361,644, Shale Retorting
Process.
According to the U.S. Pat. No. 1,055,334, process gas is obtained
from coal by distillation comprising passing the gas-making
material between heated walls in a finely divided condition and
while separated and distributed in a substantially non-oxidizing
medium and distilling the material during such passage and
regulating the motion of the material and said medium by imparting
thereto a vertical motion by jets of heated gas directed along the
heated walls transversely to the direction of passage.
It can be noted, however, that coal distillation is not
gasification. Distillation drives off volatile matter already
present; gasification creates volatiles not originally present.
In the process of U.S. Pat. No. 2,640,014, part of the material
left after eduction of oil from the shale feed is burned to ashes
with the resulting hot gas then being used to educt gas and oil
from the shale feed material.
According to U.S. Pat. No. 3,361,644, gases and oil are educted
from shale by passing oxygen-free hot gas countercurrent to
downflowing shale particles. The hot gas is obtained by heating a
portion of the gas effluent from the eduction zone. Temperature is
maintained below about 1800.degree.F. in the eduction zone to avoid
clinker formation by fusion of ash constituents. The process of
U.S. Pat. No. 3,361,644 is largely a pyrolysis-distillation process
which is not based on a gasification reaction such as reacting
H.sub.2 O with carbonaceous material.
Partial oxidation processes are described, for example, in U.S.
Pat. Nos. 1,977,684; 2,592,377; 2,657,986; 2,633,417; 2,727,812;
2,987,387; 2,657,124; and 3,025,149.
These processes all involve injection of oxygen into the reaction
zone. Also, steam is usually injected into the reaction zone.
U.S. Pat. No. 2,660,521 is directed to partial oxidation of gases
with expansion of the resultant hot gases through a turbine and
thereby generating power and obtaining a cooled synthesis gas.
Temperature in the reaction zone is controlled by carbon dioxide
recycle. The carbon dioxide is a diluent and also lowers
temperature by virtue of the endothermic reaction of carbon dioxide
with hydrocarbon to form carbon monoxide and hydrogen.
Production of hydrogen and other combustible gases from waste
substances produced in the manufacture of paper from wood chips and
the like has been discussed in the literature, as, for example, in
U.S. Pat. No. 3,317,292. In the manufacture of paper, wood chips
are digested, for example, with an aqueous calcium sulfide liquid
thereby forming calcium lignin sulfonate waste product in solution,
leaving wood pulp behind. As disclosed in U.S. Pat. No. 3,317,292,
the waste substances containing ligninderived organic components
can be converted to a gas mixture comprising hydrogen by contacting
the waste material with steam in a reaction zone at an elevated
temperature at least of the order of several hundred degrees
centigrade.
Both U.S. Pat. No. 1,777,449, titled Process of Producing Gas from
Garbage, and U.S. Pat. No. 3,471,275, titled Method of Disposal of
Refuse, are directed to producing combustible gases in an
externally heated retort rather than by introducing hot gases
directly into the retort vessel.
U.S. Pat. No. 2,840,462 relates to the production of high
BTU-content gas from carbonaceous solid fuels such as coal. This
patent basically teaches separation and removal of the methane
formed in the gasification and hydrogenation of carbonaceous
solids. Hydrogen is formed for the hydrogenation reaction using the
classical water-gas shift reaction followed by a CO.sub.2 removal
step. The methane formed is not recycled through the gasifier.
SUMMARY
According to the present invention a process is provided for
converting solid carbonaceous material to combustible gases which
comprises:
a. heating and reacting the solid carbonaceous material with
reactive gases in a gasification zone to obtain said combustible
gases and withdrawing the combustible gases from the gasification
zone,
b. methanating at least a portion of said combustible gases in a
methanation zone to obtain methanated gases, and
c. feeding at least a portion of said methanated gases through the
gasification zone thereby increasing the methane content and BTU
value of said combustible gases and transferring the sensible heat
from said methanated gases to said gasification zone.
The present invention, among other features, is based on the
combination of solids gasification with the methanation and
recycling of a portion of the combustible gas effluent from the
gasification zone. Also, temperature control in the gasification
zone is preferably obtained by partially or wholly burning a second
portion of the effluent gases from the gasification zone and then
recycling the hot gases thus obtained to the gasification zone. It
is critical in the process of the present invention that
gasification reactions are carried out in the gasification zone to
generate hydrogen and carbon oxides from solid hydrocarbonaceous
matter in the gasification zone and also to generate hydrogen from
the H.sub.2 O which is added to the reaction zone via the recycled
hot gases. It is also preferred that the gasification zone be
essentially free of molecular oxygen so as to substantially avoid
any combustion in the gasification zone of the recycled gas or
solid carbonaceous material feed. The present invention is also
based on a critically important third feature or concept which is
that the present process is extremely attractive for the conversion
of solid carbonaceous material, particularly coal, to high BTU
gas.
The term "high BTU gas" is used herein to mean gas having a BTU
value of at least 100 BTU per cubic foot and preferably above 300
BTU per cubic foot. With CO.sub.2 removal from the product gas of
the present invention the BTU content would be closer to 300
BTU/ft.sup.3 ; and with both CO.sub.2 removal from the product gas
and use of purified oxygen (instead of air) for the burning of said
recycled second portion, the BTU content would be about 400-800
BTU/ft.sup.3. Preferably the process is operated without any
CO.sub.2 removal stages.
The term "solid carbonaceous material" is used herein to connote
carbonaceous fuels such as coal, oil shale, and tar sands. A
particularly preferred feed is coal including anthracite,
bituminous and subbituminous coals and lignite.
The term "methanation" is used herein to mean conversion of carbon
oxides and H.sub.2 to methane by reaction of the carbon oxides with
H.sub.2. For example:
Co + 3h.sub.2 .fwdarw.ch.sub.4 + h.sub.2 o
co.sub.2 + 4h.sub.2 .fwdarw.ch.sub.4 + 2h.sub.2 o
the methanation reaction is exothermic, and this exothermic heat of
reaction is integrated into the process of the present invention to
supply a portion of the heat required for the endothermic reactions
in the gasification zone. In the process of the present invention
the temperatures in the gasification zone are highly advantageously
controlled by means of adjusting the temperature and/or amount of
methanated gases recycled to the gasification zone and preferably
also by means of adjusting external to the gasification zone the
temperature and/or amount of a second hot recycle gas stream to the
gasification zone.
Thus, the temperatures in the gasification zone can be controlled
pursuant to the present invention by controlling both the amount of
each hot recycle gas stream and the temperature of each recycle
gas. Usually all four of these variables will be adjusted to an
optimum level for the process of the present invention so as to
achieve desired reaction rates of solids in the gasification zone
at minimum energy requirement for recycle gas compression, but yet
to maintain temperatures in the gasification zone below about
2000.degree.F.
One of the particular advantages of the present invention is that
the recycle of methanated gases allows an added means for
temperature control in the gasification zone. Usually the main
means of heat input and temperature control in the gasification
zone is by the second hot recycle gas stream.
In the process of the present invention, the advantageous services
which are afforded by the integrated methanation step include the
following:
1. Increased BTU value of product gas by raising CH.sub.4 content
of product gas
2. Provide heat input source for gasification reaction
3. Provide temperature control for gasification reaction.
To reduce the amount of reversal of the methanation reaction when
the recycled methanated gases are introduced to the gasification
reactor, it is preferable to introduce the methanated gases to
about the middle of the reactor where the temperature is about
800.degree.-1200.degree.F. versus about 1600.degree.-2000.degree.F.
at the bottom and 200.degree.-600.degree.F. at the top. Thus,
according to a preferred embodiment of the present invention
wherein the gasification zone comprises an upright cylindrical
gasifier reactor, the methanated gases are introduced at a central
position along the length of said gasifier, feed material is
introduced at an upper position along the length of said gasifier
and heating gases are introduced at a lower position along the
length of said gasifier.
The gases obtained from the gasification zone are preferably cooled
and cleansed by a water quence. This water in part finds its way
back to the gasification zone via that portion of the gases which
are recycled to supply heat and reactive gases to the gasification
zone. Additional water is supplied to the gasification zone from
the solids fed to the gasification zone, as the solids fed
invariably will have at least some moisture content. Additional
water and carbon dioxide are produced by partial burning of the
recycle gas. Thus, there will be H.sub.2 O and CO.sub.2 present in
the gasification zone for conversion of carbon and hydrocarbons
into hydrogen and carbon monoxide according to well known reactions
such as
C + H.sub.2 O.fwdarw.H.sub.2 + CO and C + CO.sub.2 .fwdarw. 2CO
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a schematic process flow diagram illustrating a
preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE DRAWING
Referring more particularly to the drawing, a solid carbonaceous
material, such as coal, is introduced via line 1 to gasification
zone 2. Carbonaceous solid waste materials are also suitable as
feed materials as discussed in our copending application, Ser. No.
252,450, filed May 11, 1972.
The solids can be considered to undergo a series of steps or
reactions in the gasification zone including, for example, H.sub.2
O distillation, oil distillation, pyrolysis, and gasification
reactions such as previously mentioned. In the present invention
there must be gasification reactions in the gasification zone.
Ashes are withdrawn from the bottom of the gasification zone as
indicated via line 3.
A gaseous stream is withdrawn from the gasification zone as
indicated by line 4. This gas stream is quenched and scrubbed by
water to remove particles introduced to quench drum 6 via line 7
and recycle line 8. Makeup water and preferably an alkali carbonate
catalyst is introduced via line 5. The water serves to quench the
gasifier effluent, and the hot gasifier effluent gases serve to
heat water for efficient subsequent use in the gasifier. The heated
water is ultimately recycled via lines 9 and 10 to gasifier 2.
The water preferably carries alkali carbonate catalyst to the
gasifier to catalyze the reaction of the solids in gasifier 2 as is
further described in U.S. Pat. No. 3,759,677 in regard to the
gasification of solid waste material.
Heavy sludge material and water is withdrawn from quench drum 6 via
line 9 and passed to settler 11 via line 9. Oily sludge material,
water, and preferably alkali catalyst is passed to gasifier 2 via
line 10 from the settler. A clarified oil stream is withdrawn from
an intermediate point from settler 11 via line 12.
The hot gases withdrawn from gasifier 2 via line 4 are introduced
to the quench drum at a temperature of about 600.degree.F., and the
water scrub in the quench drum cools the gases to a temperature of
350.degree.F. before they are removed via line 13.
The gaseous material in line 13 is then split into two streams; a
first stream 14 for recycle back to the gasification zone, and a
second stream 15 which can be referred to as a product gas
stream.
Preferably a portion of the recycle gases from quench drum 6 are
passed to the recycle combustor via recycle compressor 22 and then
line 23. Compressed air or pressurized oxygen is introduced to
recycle combustor 24 via line 20. Recycle combustor 24 is
preferably an in-line burner device. The partially combusted
recycle gas is withdrawn from recycle combustor 24 usually at a
temperature of about 2000.degree.F. and passed via line 25 to the
bottom of gasification zone 2 to supply reactive gases and
temperature control as well as heat for gasification zone 2.
In the present invention it is critical to methanate a portion of
the recycle gases. Thus recycle gas is passed via lines 23 and 27
to methanation zone 28. In the methanation zone methane is formed
by reacting carbon oxides with hydrogen. The carbon oxides and
hydrogen are present in the recycle gas due to gasification
reactions in gasifier 2. Preferably the methanation reaction is
carried out catalytically over a methanation catalyst. Such
catalysts are known in the art and typically contain nickel.
If the methanation catalyst is sulfur sensitive, sulfur removal
should be effected before the recycle gases are introduced to the
methanator. Sulfur compounds can be removed by many known methods,
such as by use of a bed of solid particles containing zinc
oxide.
Usually the gases fed to the methanation zone will be preheated to
about 500.degree.-700.degree.F., and, due to the exothermic heat of
the methanation reaction, the methanated gases leave the methanator
at about 650.degree.-1000.degree.F. One of the advantageous
features of the present invention is the utilization of this
exothermic heat of reaction in the gasification reaction zone. Thus
the methanated gases are passed via lines 25 and 31 to gasifier
2.
Previously product gas stream 15 was mentioned. Stream 15 can be
the entire product stream, but advantageously a portion or all of
the product gases are withdrawn, after methanation, from
methanation zone 28 via lines 29, 31 and 33. Gases withdrawn from
the methanation step have a higher BTU content than the gases in
line 15, and thus the process of the present invention has the
advantage of adjustable BTU content for the product gas by, e.g.,
blending various portions of stream 15 with stream 33. The product
high BTU gas can be used as "town gas" in residential gas burning
appliances or as a fuel gas for industrial furnaces.
Heat recovery zone 32 connotes recovery of heat from product gases
withdrawn from the methanation step; this heat recovery step is
advantageously integrated into the process of the present invention
as a heat input source for the feed gas to methanation zone 28.
Although various embodiments of the invention have been described,
it is to be understood that they are meant to be illustrative only
and not limiting. Certain features may be changed without departing
from the spirit or scope of the present invention. It is apparent
that the present invention has broad application to gasification of
solids with methanation of recycle gases to the gasification zone.
Accordingly, the invention is not to be construed as limited to the
specific embodiments discussed, but only as defined in the appended
claims or substantial equivalents of the claims.
* * * * *