CA1074117A - Catalytic method for gasification of fossil fuels with steam of increased pressure and temperature - Google Patents
Catalytic method for gasification of fossil fuels with steam of increased pressure and temperatureInfo
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- CA1074117A CA1074117A CA264,031A CA264031A CA1074117A CA 1074117 A CA1074117 A CA 1074117A CA 264031 A CA264031 A CA 264031A CA 1074117 A CA1074117 A CA 1074117A
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Abstract
ABSTRACT OF THE DISCLOSURE
A catalytic method for gasification of fossil fuels with steam at increased pressure and temperature that results in increased reaction rates over known rates at low pressure. The catalysts used being salts and hydroxides of ammonium or alkali and alkaline earth metals. Pressures in the range of 50 to 600 bar and temperatures in the range of 500 to 1100°C can be used.
A catalytic method for gasification of fossil fuels with steam at increased pressure and temperature that results in increased reaction rates over known rates at low pressure. The catalysts used being salts and hydroxides of ammonium or alkali and alkaline earth metals. Pressures in the range of 50 to 600 bar and temperatures in the range of 500 to 1100°C can be used.
Description
~'7'1~
This invention relates to gasifying fossil fuels and more particularly to gasifying such fuels in the presence of a catalyst.
In the early sixties of this century, the energy market was characterized by large amounts of inexpensive crude oils, but the recent energy crisis has again direc-ted attention to coal. The statistics regarding world energy reserves on fossil fuels prove that of the three kinds of fossil fuels, namely, coal, petroleum and natural gas, the coal resources are 5 to 10 times higher than those of petro-leum and natural gas. For various economic systems t the availability of corresponding individual types of energy is also of importance. While large petroleum and natural gas aep~sits exist only in relatively few regions of the world, coal deposits can be found in almost every country. The di~-ferences in reserves of fossil fuels make it clear that with an increasing shortage of petroleum and natural gas, greater reliance will be made on coal. Methods of liquefying or gas-ifying coal in order to convert one primary source of energy into a secondary source of another type will thus aid in re-lieving the demand for petroleum and natural gas.
The recent, steadily increasing prices of liquid and gaseous fuels have given a new incentive ~o the develop-ment of methods for gasifying and liquefying coal. The con-version of coal into a gas rich in methane is especially interesting.
Methane as a substitute for natural gas can be pre-pared from coa]L by one of the following two reactions:
(1) The first method involves three steps: ;
(a) comp]Lete gasification of coal to CO + H2;
. .
;. '-' . '' . :,-, ~ . . : ' ' (b) adjustment of the CO/H2 ratio of 1:3 necessary for methanization by means of CO-conversion; and (c) catalytic methani~a-tion.
The gross reactions upon which the individual steps are based are shown below together with their reaction en-thalpies:
This invention relates to gasifying fossil fuels and more particularly to gasifying such fuels in the presence of a catalyst.
In the early sixties of this century, the energy market was characterized by large amounts of inexpensive crude oils, but the recent energy crisis has again direc-ted attention to coal. The statistics regarding world energy reserves on fossil fuels prove that of the three kinds of fossil fuels, namely, coal, petroleum and natural gas, the coal resources are 5 to 10 times higher than those of petro-leum and natural gas. For various economic systems t the availability of corresponding individual types of energy is also of importance. While large petroleum and natural gas aep~sits exist only in relatively few regions of the world, coal deposits can be found in almost every country. The di~-ferences in reserves of fossil fuels make it clear that with an increasing shortage of petroleum and natural gas, greater reliance will be made on coal. Methods of liquefying or gas-ifying coal in order to convert one primary source of energy into a secondary source of another type will thus aid in re-lieving the demand for petroleum and natural gas.
The recent, steadily increasing prices of liquid and gaseous fuels have given a new incentive ~o the develop-ment of methods for gasifying and liquefying coal. The con-version of coal into a gas rich in methane is especially interesting.
Methane as a substitute for natural gas can be pre-pared from coa]L by one of the following two reactions:
(1) The first method involves three steps: ;
(a) comp]Lete gasification of coal to CO + H2;
. .
;. '-' . '' . :,-, ~ . . : ' ' (b) adjustment of the CO/H2 ratio of 1:3 necessary for methanization by means of CO-conversion; and (c) catalytic methani~a-tion.
The gross reactions upon which the individual steps are based are shown below together with their reaction en-thalpies:
2 C + 2 H2O ~2CO + 2H2 + 56.6 kcal CO -~ H20 ~H2 + C2 ~ 10.1 kcal 2 CO + 3H2 ~CH4 + H20 - ~9.2 kcal 3 2 C + 2H20 ~CH4 + CO2 - 2.7 kcal 4 (II) The second method consists of the following steps:
(a) complete gasification of coal or coke to CO + H2;
(b) conv~rsion of CO to H2; and (c) hydrogenation of fresh coal to CH4 with the aid of the hydrogen generated.
The gross reactions on which the individual steps are based are shown below together with their reaction enthalpies:
C + H20 ~ CO + H2 + 28.3 kcal 5 CO + H20 -~ H2 + C2 ~ 10.1 kcal 6 C + 2H2 ~ CH4 - 20.9 kcal 7 - - :
2C + 2H2O CH4 + CO2 - 2.7 kcal 8 Both methods convert coal into methane as the final product. Therefore, the sum of reaction enthalpies is equal.
In Method II, the heat of formation of methane by hydrogen generated at relatively high temperatures during the course of the gasification is used much more advantageously for the - -total process than the higher value of Method I which is ~
.
, c 2 -4~
liberated at relatively lower temperatures during the methanization step after gasification. Therefore, the effectiveness of Method II is better in practice. Moreover, Method II requires only half as much energy from outside sources as Method I. Considering both methods to be equally efficiant, this means less exchange area for heat transfer and, in autothermic processes, Less oxygen consumption, respectively. It is thus apparent that for the preparation of synthetic gas, one should produce as much methane as 1~ possible by hydrogenation rather than by synthesis from CO ~ 3H2.
By conducting the reaction in a suitable manner, gasification under pressure in a counter current of coal and g sifying agent or stepwise gasification, the thermodynamic-ally advantageous formation of methane by hydrogenation may be utilized in practice.
The main process steps for the conversion of coal into a gas rich in methane are pretreatment of the coal, gas-~
ification, conversion, methanization and hydrogenation.
The coal is pretreated by separating it from pieces of rocks and granulating it in a manner suitable or gas-ification. An important factor is the coking capacity of the coal which often can be influenced only with difficulty or to an insufficient degree. Granulation and coking capacity of the available coal determine whether gasification can be carried out in a solid bed or in suspension.
Counter-current gasification in a solid bed pro-vides better heat utilization and more favorable kinetic conditions. Gasification of suspended coal dust particles in a fluidized bed working with parallel streams requires more heat and leads tô less favorable kinetic conditions because :~V'~'4~ ~
of the decreasing concentration of carbon and gasifying agent.
In the most important known methods such as the Lurgi pressure gasification, the Hygas process of the Insti-tute of Gas Technology, the Koppers-Totzek process, etc., gasification is carried out at pressures of about 30 bar and temperatures of 800C. to 1100C.or more. The Lurgi process is an economically approved method. The Hygas process which is still under test promises to lower the costs of gas pro-du~tion. The Koppers-Totzek process and the Hygas process work with steam gasification in a fluidized bed while accord-ing to the Lurgi process coal is gasified in a solid bed by countercurrent.
Mixtures of oxygen and steam are employed for gas-ification. Lean gases may also be prepared with mixtures of steam and air. ~y burning part of the coal, the added oxygen provides the reaction temperature and heat required for the endothermic reaction between coal and steam. It is also possi~le to supply the necessary reaction heat from other sources, nuclear heat, for example.
In the Lurgi process, coal is gasified in a descend-ing bed by an ascending stream of oxygen and steam. Ashes are removed by a rotating grid at the bottom of the gasifying zone. The crude gas leaving the head of the gasifier is washed with oil to remove tar, heavy oil and entrained solids.
The gas composition is corrected by modifying the ratio of 2 to steam. After CO2 and H2S have been separated, the gas is methanized to produce a substitute for natural gas.
The Hygas process gasifies coal in two fluidized beds connected in series. Coke residues from the coal gas-ification are used to provide the hydrogen needed for further gasification steps. The crude gas from the reactor is quenche~
to remove oil whereupon it is freed of acidic gases. Then CO
is partially converted and methanized after separation from the CO2 formed. Because of the increased pressure of 75 bar in the reactor and temperatures of 650C and 950C to 1000C, respectively, hydrogenation of the coal plays a noticeable part in this reaction.
According to the Koppers-Totzek process, coal dust and oxygen are gasified with the addition of steam in a "reac-tion flame" in front ofa nozzle. The oxygen serves as a carrier gas for the coal dust. This process is applicable to all kinds of coal, irrespective of their coking capacity.
Gasification is carried out at normal pressure. The reaction flame has a very high temperature so that the C4 content of the crude gas remains under 0.1% C~4. The entire methane concentration required if the gas is to be used as a substitute for natural gas must be formed by methanization.
The crude gases contain varying amounts of carbon monoxide, hydrogen, methane, carbon dioxide, and unreacted steam, depending on the gasifying agent, high concentrations of nitrogen and the process selected. A major part of the !.
sulphur contained in the fuel charge can be found as hydrogen sulphide and, to a lesser extent, as carbon oxide sulphide in the final gas and must be removed by washing.
Carbon dioxide is washed out together with the gas-eous sulphur compounds.
In general, the following reactions are important for gasification:
~7~
,_ .,, ~ .,, o ~ o + ~ ~ ~
O U N O N
U ~ ~ ~ :~
OP~ ~ O ~ ~ ~ O
~:
h O Q~ ~ ~1 ot` ~
,a ,, ~, :r: ~1 ~1 o ~oo ~ n ~D ~J
O
t~ S1) ~ 1~ 1 ~ ~ ~ I CO o d 1;1 ~) K cn N ~r ~1 ~
I + I I + i I
:
E~ ~ 3 ~i ~ ~ rl rl O ~1 "
O ~ ~ ~ ~1 r~ (d a~
h S S ~ S S ,~ ~ ~ S
,:
E~ P~ C m ~
.. ..:.. . .
H OC) C) ~
h ~ h ~ ~ s ~
E~ a~ s ~ ~ h S
:~ ~ O O ~ ~ :
C ~ ~ S O ' O X ~ ~ ~0 0~X.U
r~ Xrl E~
o ~1~1 ~ h ~~D h s S
O O O ~ ~ O O ~
h h h la O h ~ O ::
O X ~~:: X
(a) complete gasification of coal or coke to CO + H2;
(b) conv~rsion of CO to H2; and (c) hydrogenation of fresh coal to CH4 with the aid of the hydrogen generated.
The gross reactions on which the individual steps are based are shown below together with their reaction enthalpies:
C + H20 ~ CO + H2 + 28.3 kcal 5 CO + H20 -~ H2 + C2 ~ 10.1 kcal 6 C + 2H2 ~ CH4 - 20.9 kcal 7 - - :
2C + 2H2O CH4 + CO2 - 2.7 kcal 8 Both methods convert coal into methane as the final product. Therefore, the sum of reaction enthalpies is equal.
In Method II, the heat of formation of methane by hydrogen generated at relatively high temperatures during the course of the gasification is used much more advantageously for the - -total process than the higher value of Method I which is ~
.
, c 2 -4~
liberated at relatively lower temperatures during the methanization step after gasification. Therefore, the effectiveness of Method II is better in practice. Moreover, Method II requires only half as much energy from outside sources as Method I. Considering both methods to be equally efficiant, this means less exchange area for heat transfer and, in autothermic processes, Less oxygen consumption, respectively. It is thus apparent that for the preparation of synthetic gas, one should produce as much methane as 1~ possible by hydrogenation rather than by synthesis from CO ~ 3H2.
By conducting the reaction in a suitable manner, gasification under pressure in a counter current of coal and g sifying agent or stepwise gasification, the thermodynamic-ally advantageous formation of methane by hydrogenation may be utilized in practice.
The main process steps for the conversion of coal into a gas rich in methane are pretreatment of the coal, gas-~
ification, conversion, methanization and hydrogenation.
The coal is pretreated by separating it from pieces of rocks and granulating it in a manner suitable or gas-ification. An important factor is the coking capacity of the coal which often can be influenced only with difficulty or to an insufficient degree. Granulation and coking capacity of the available coal determine whether gasification can be carried out in a solid bed or in suspension.
Counter-current gasification in a solid bed pro-vides better heat utilization and more favorable kinetic conditions. Gasification of suspended coal dust particles in a fluidized bed working with parallel streams requires more heat and leads tô less favorable kinetic conditions because :~V'~'4~ ~
of the decreasing concentration of carbon and gasifying agent.
In the most important known methods such as the Lurgi pressure gasification, the Hygas process of the Insti-tute of Gas Technology, the Koppers-Totzek process, etc., gasification is carried out at pressures of about 30 bar and temperatures of 800C. to 1100C.or more. The Lurgi process is an economically approved method. The Hygas process which is still under test promises to lower the costs of gas pro-du~tion. The Koppers-Totzek process and the Hygas process work with steam gasification in a fluidized bed while accord-ing to the Lurgi process coal is gasified in a solid bed by countercurrent.
Mixtures of oxygen and steam are employed for gas-ification. Lean gases may also be prepared with mixtures of steam and air. ~y burning part of the coal, the added oxygen provides the reaction temperature and heat required for the endothermic reaction between coal and steam. It is also possi~le to supply the necessary reaction heat from other sources, nuclear heat, for example.
In the Lurgi process, coal is gasified in a descend-ing bed by an ascending stream of oxygen and steam. Ashes are removed by a rotating grid at the bottom of the gasifying zone. The crude gas leaving the head of the gasifier is washed with oil to remove tar, heavy oil and entrained solids.
The gas composition is corrected by modifying the ratio of 2 to steam. After CO2 and H2S have been separated, the gas is methanized to produce a substitute for natural gas.
The Hygas process gasifies coal in two fluidized beds connected in series. Coke residues from the coal gas-ification are used to provide the hydrogen needed for further gasification steps. The crude gas from the reactor is quenche~
to remove oil whereupon it is freed of acidic gases. Then CO
is partially converted and methanized after separation from the CO2 formed. Because of the increased pressure of 75 bar in the reactor and temperatures of 650C and 950C to 1000C, respectively, hydrogenation of the coal plays a noticeable part in this reaction.
According to the Koppers-Totzek process, coal dust and oxygen are gasified with the addition of steam in a "reac-tion flame" in front ofa nozzle. The oxygen serves as a carrier gas for the coal dust. This process is applicable to all kinds of coal, irrespective of their coking capacity.
Gasification is carried out at normal pressure. The reaction flame has a very high temperature so that the C4 content of the crude gas remains under 0.1% C~4. The entire methane concentration required if the gas is to be used as a substitute for natural gas must be formed by methanization.
The crude gases contain varying amounts of carbon monoxide, hydrogen, methane, carbon dioxide, and unreacted steam, depending on the gasifying agent, high concentrations of nitrogen and the process selected. A major part of the !.
sulphur contained in the fuel charge can be found as hydrogen sulphide and, to a lesser extent, as carbon oxide sulphide in the final gas and must be removed by washing.
Carbon dioxide is washed out together with the gas-eous sulphur compounds.
In general, the following reactions are important for gasification:
~7~
,_ .,, ~ .,, o ~ o + ~ ~ ~
O U N O N
U ~ ~ ~ :~
OP~ ~ O ~ ~ ~ O
~:
h O Q~ ~ ~1 ot` ~
,a ,, ~, :r: ~1 ~1 o ~oo ~ n ~D ~J
O
t~ S1) ~ 1~ 1 ~ ~ ~ I CO o d 1;1 ~) K cn N ~r ~1 ~
I + I I + i I
:
E~ ~ 3 ~i ~ ~ rl rl O ~1 "
O ~ ~ ~ ~1 r~ (d a~
h S S ~ S S ,~ ~ ~ S
,:
E~ P~ C m ~
.. ..:.. . .
H OC) C) ~
h ~ h ~ ~ s ~
E~ a~ s ~ ~ h S
:~ ~ O O ~ ~ :
C ~ ~ S O ' O X ~ ~ ~0 0~X.U
r~ Xrl E~
o ~1~1 ~ h ~~D h s S
O O O ~ ~ O O ~
h h h la O h ~ O ::
O X ~~:: X
3 ~ u~
:, O ~ ':
m ~ m ~ o m u + o + + +
+ ~, O
~ ~ 8 o 8 ~ u m~ m~
o o ~ ~ u . ..,, v o o ....
o ~~ o ~
o ~ ~ m ~ ~ 5 o ~ m ~ ~ m o ~ } o ~ ~
+ + + ~a + +
o ~ o ~ .........
U U:r U C~ V ~
~ .
~a~7~ 7 The above reaction enthalpies refer to coke carbon and differ by about 3Kcal/mol from the standard enthalpy of graphite.
According to Table I J the main reaction of gas-ification, namely the reaction C ~ H2O -~ CO ~ H~, is strony-ly endothermic and proceeds at a practical rate only at temp-eratures above 750C to 800C. The heat required for the reaction may be supplied in the following ways:
a) Burning part of the solid fuel by means of oxygen or air (autothermic gasification);
b) Heating the reactor from the outside by heat transfer through the reactor walls or by means of special heating elements; and c) Circulating solid, liquid or gaseous heat carriers.
The above possibilities have all been tested and tried in practice. Autothermic gasification with o~ygen and steam is widely employed. A method of supplying high temp-erature nuclear heat by means of outer heating elements is still in the experimental stage. Special attention has also been given to increasing the throughput rate. While the known Lurgi pressure gasifier works under pressures of 30 bar and at temperatures of 700C to 1000C, new efforts in the United States aim at carrying out the gasification under the pres-sures re~uired for feeding the gas into a long distance pipe line, i.e. under 70 bar or moreipressure.
Gasification under higher steam pressures does, how-ever, generally result in lower reaction rates. ~or this rea-~; son, the use of higher steam pressures was not previously con-sidered to be useful.
_ 7 -.
The present invention provides novel methods where-in selected compounds are added -to the steam which dissolve in the steam and catalyze the reaction between coal and steam so that at elevated steam pressures reaction rates are obtainable which are even higher than the known rates at low pressures and the same temperature. Preferably, the amount of catalyst in th~ steam corresponds to or approaches the saturation point.
The catalysts employed in accordance with the pre-sent invention are alkali salts which are easily soluble in high pressure steam. The most preferred are alkali and alka-line earth metal hydroxides, borates, (including tetraborates), carbonates and bicarbonates. The reaction can also be accel-erated with alkali halides, especially chlorides. Carbonates and hydroxides of potassium are most preferred since they com-bine good results with favorable economics. For instance, 0.007 grams of potassium hydroxide per 1000 grams of water will dis-solve in the steam at 825C. and 150 bar. Although the amount of salt dissolved in the steam under these circumstances is very small, the throughput is increased by the factor 4 com-pared to gasification under a steam pressure of 30 bar. Theincrease in reaction rate achieved by adding the catalysts in accordance with the present invention corresponds to that which can be obtained by raising the temperature by about 150C to 200C. The alkali compounds, mainly silicates, which are pre-.. ~ ,.. . .
sent in the coal ash rather inhibit the xeaction.
The foregoing provisions and advantages of the in-vention may be ac~ieved by recourse to a method of gasifying fossil fuels by contacting the fuels with steam at an elevated temperature and pressure in the presence of catalytic amounts of at least one of, ammonium, alkali and alkaline earth salts ; and hydroxides which are soluble in the steam.
~? 8 -~7~ 7 Surprisingly, it has been found that the method of the present invention leads to a change in the composition of the crude gas since more hydrogen and carbon dioxide and less carbon monoxide than usual are formed during the reaction. The carbon monoxide content of the crude gas drops to less than 2 vol. %. Thus, the c~ude gas is especially suited for pre-paring synthetic gas in accordance with the thermodynamically more advantageous Method II. Apart from this fact, the method of the present invention permitsp without loss in gasification capacity, the use of the high gasification pressures desired for further utilization of the finished product. Furthermore, the heat balance of the gasifier is improved since Reaction 7 is preferred over Reaction 3.
According to the present invention, in a gasifier working ~ith a counter current of coal and gasifying agent, high steam pressures will prevail in the lower part where the gasifying agent is introduced and the catalyst will be dissol-ved in the gaseous phase. As the reaction progresses the as-cending gas streamwill contain less steam, thereby increasing the concentration of the salts in the gas stream. Ultimately, the entrainedcatalysts precipitate and deposit in very finely divided form on the coal. The coal carries the catalyst back into zones of high partial steam pressures where the catalyst again dissolves. The method of the present invention,thus, results in circulation of the catalyst. The only catalyst which needs to be replaced is that lost through adsorption on ash or by entrainment in the form of dust in the crude gas stream. The loss in catalyst through adsorption on or reaction with ash can be minimized by adding lime to the coal.
The finely divided catalyst precipitated onto the F~ 9-7 4 r~
fresh coal is also effective in catalyzing the reaction be-tween coal and steam.
The following non-limiting examples are given by way of illustration only. Unless stated o~herwise, all per-centages given are by volume.
Steam saturated with potassium hydroxide is reacted with ground lignite briquettes in an autoclave under a pressure of 600 bar and a temperature of 660C. After remov~l of the steam, 4 liters NTP of a gas per literofIignite charge per minute are obtained, the gas containing 23% methane, 0.7%
ethane, 34% hydrogen and 42% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification at the same temperature and under a pressùre of 70 bar results, per minute and per liter of lignite charge, in 2.5 liters NTP of a gas containing 46% of hydrogen, 6% of carbon monoxide, 11% of methane and 37% of CO2.
Steam saturated with potassium hydroxide (about 0.6 grams/100 grams of H2O) is reacted with ground lignite in an autoclave under a pressure of 400 bar at a temperature of 630C. Per liter of lignite charge and per minute, 2.5 lit-ers ~TP of a gas are obtained which, after removal of the steam, contain 20% methane, 3~% hydrogen, 41% carbon dio~ide and 1% ethane. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification at the same temp~
erature and under a pressure of 70 bar leads to 2 liters NTP
of a gas per minute and per liter of lignite charge, the gas .' ' ,.' ..
- 1 0 - ' ~ ' ~)743 ~'~
containing 4% methane, 61% hydrogen, 34% carbon dioxide and 1% carbon monoxide.
Steam saturated with sodium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a temperature of 750"C. Per liter coke charge and per minute, 1.9 liters MTP of a gas are obtained which, after condensation of the steam, contain 1% methane, 65% hydrogen and 33~ carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without sodium hydroxide at the same temperature and under a pressure o~ 70 bar results, per minute and per liter o~ coke charge, in 0.4 liters NTP of a gas containing 3% methane, 59~ hydrogen, 11~ carbon monoxide and 27% carbon dioxide.
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a temperature of 770C. Per minute and per liter coke charge, 6.1 liters NTP of a gas are obtained which, after condensation of the steam, contain 5~ methane, 60% hydrogen and 35~ carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and under a pres- -sure of 300 bar results in 0.5 liters NTP of a gas per minute and per liter coke charge. The gas contains 4% methane, 58%
hydrogen, 26% carbon dioxide and 12% carbon monoxide.
~ _ 11-EXAMPLE S
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure o~
70 bar and a temperature of 750C. Per liter coke charge and per minute, 1.6 liters NTP of a gas are obtained which, after condensation of the steam, contain 1% methane, ~4% hydrogen, 2% carbon monoxide and 32% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temper-ature and under a pressure of 70 bar results in 0.4 liters NTPof a gas per minute and per liter coke charge, the gas con-taining 3% methane, 59% hydrogen, 11% carbon monoxide and 27%
carbon dioxide.
- EXAMP~E 6 Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 150 bar and a temperature of 8~5C. Per minute and per liter of coke charge, 5.1 liters NTP of a gas are obtained which, after condensation of the steam, contain 1.5% methane, 64%
hydrogen, 2% carbon monoxide and 32.5% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and a pressure of 150 bar results in 1.2 liters NTP of a gas per minute and per liter coke charge, the gas containing 2% of methane, 61% hydrogen, 11% carbon mon-oxide and 26% carbon dioxide.
. . .
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and at a temperature of 825~. Per liter coke charge and per minute, 10.3 liters NTP of a gas are obtained which, .
~)7~
after condensation of the steam, contain 1.8% methane, 64%
hydrogen, 1.55~ carbon monoxide and 32.7% carbon dioxide.
Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and a pressure of 300 bar results in 1.6 liters NTP of a gas per minute and per liter coke charge, the gas containing 2.5% methane, 62% hydrogen, 6~ carbon mono-xide and 29.5% carbon dioxide.
An ~queous ammonia solution containing 11% by weight of N~3 is reacted with ground lignite in an autoclave under a pressure of 600 bar and a temperature of 620~C. Per liter lignite charge and per minute, 0.85 liters NTP of a gas are obtained which contain 38% hydrogen, 42% carbon dioxide, 14~
methane and 6% ethane. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without ammonia at the same temperature and pressure results in 0.5 liters NTP of a gas per minute and per liter lignite charge, 20 the gas containing 32% hydrogen, 43% carbon dioxide and 25 methane.
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclav,e under a pressure of 300 bar and a tlemperature of 1050C. Per liter coke charge and per minute, 61 liters NTP of a gas are obtained/ the gas containing after condensation of the steam 1.8% me~hane, 62%
hydrogen, 4% carbon monoxide and 32% carbon dioxide. By way 30 of comparison, repeating the process a~ the same temperature .''~' ' .
.
. . .-, ., . .- . : . . , ~L~7~
and under the same pressure but without potassium hydroxide results, per minute and per liter of ground coke charge, in 19 liters NTP of a gas containing 3~ methane, 60~ hydrogen,
:, O ~ ':
m ~ m ~ o m u + o + + +
+ ~, O
~ ~ 8 o 8 ~ u m~ m~
o o ~ ~ u . ..,, v o o ....
o ~~ o ~
o ~ ~ m ~ ~ 5 o ~ m ~ ~ m o ~ } o ~ ~
+ + + ~a + +
o ~ o ~ .........
U U:r U C~ V ~
~ .
~a~7~ 7 The above reaction enthalpies refer to coke carbon and differ by about 3Kcal/mol from the standard enthalpy of graphite.
According to Table I J the main reaction of gas-ification, namely the reaction C ~ H2O -~ CO ~ H~, is strony-ly endothermic and proceeds at a practical rate only at temp-eratures above 750C to 800C. The heat required for the reaction may be supplied in the following ways:
a) Burning part of the solid fuel by means of oxygen or air (autothermic gasification);
b) Heating the reactor from the outside by heat transfer through the reactor walls or by means of special heating elements; and c) Circulating solid, liquid or gaseous heat carriers.
The above possibilities have all been tested and tried in practice. Autothermic gasification with o~ygen and steam is widely employed. A method of supplying high temp-erature nuclear heat by means of outer heating elements is still in the experimental stage. Special attention has also been given to increasing the throughput rate. While the known Lurgi pressure gasifier works under pressures of 30 bar and at temperatures of 700C to 1000C, new efforts in the United States aim at carrying out the gasification under the pres-sures re~uired for feeding the gas into a long distance pipe line, i.e. under 70 bar or moreipressure.
Gasification under higher steam pressures does, how-ever, generally result in lower reaction rates. ~or this rea-~; son, the use of higher steam pressures was not previously con-sidered to be useful.
_ 7 -.
The present invention provides novel methods where-in selected compounds are added -to the steam which dissolve in the steam and catalyze the reaction between coal and steam so that at elevated steam pressures reaction rates are obtainable which are even higher than the known rates at low pressures and the same temperature. Preferably, the amount of catalyst in th~ steam corresponds to or approaches the saturation point.
The catalysts employed in accordance with the pre-sent invention are alkali salts which are easily soluble in high pressure steam. The most preferred are alkali and alka-line earth metal hydroxides, borates, (including tetraborates), carbonates and bicarbonates. The reaction can also be accel-erated with alkali halides, especially chlorides. Carbonates and hydroxides of potassium are most preferred since they com-bine good results with favorable economics. For instance, 0.007 grams of potassium hydroxide per 1000 grams of water will dis-solve in the steam at 825C. and 150 bar. Although the amount of salt dissolved in the steam under these circumstances is very small, the throughput is increased by the factor 4 com-pared to gasification under a steam pressure of 30 bar. Theincrease in reaction rate achieved by adding the catalysts in accordance with the present invention corresponds to that which can be obtained by raising the temperature by about 150C to 200C. The alkali compounds, mainly silicates, which are pre-.. ~ ,.. . .
sent in the coal ash rather inhibit the xeaction.
The foregoing provisions and advantages of the in-vention may be ac~ieved by recourse to a method of gasifying fossil fuels by contacting the fuels with steam at an elevated temperature and pressure in the presence of catalytic amounts of at least one of, ammonium, alkali and alkaline earth salts ; and hydroxides which are soluble in the steam.
~? 8 -~7~ 7 Surprisingly, it has been found that the method of the present invention leads to a change in the composition of the crude gas since more hydrogen and carbon dioxide and less carbon monoxide than usual are formed during the reaction. The carbon monoxide content of the crude gas drops to less than 2 vol. %. Thus, the c~ude gas is especially suited for pre-paring synthetic gas in accordance with the thermodynamically more advantageous Method II. Apart from this fact, the method of the present invention permitsp without loss in gasification capacity, the use of the high gasification pressures desired for further utilization of the finished product. Furthermore, the heat balance of the gasifier is improved since Reaction 7 is preferred over Reaction 3.
According to the present invention, in a gasifier working ~ith a counter current of coal and gasifying agent, high steam pressures will prevail in the lower part where the gasifying agent is introduced and the catalyst will be dissol-ved in the gaseous phase. As the reaction progresses the as-cending gas streamwill contain less steam, thereby increasing the concentration of the salts in the gas stream. Ultimately, the entrainedcatalysts precipitate and deposit in very finely divided form on the coal. The coal carries the catalyst back into zones of high partial steam pressures where the catalyst again dissolves. The method of the present invention,thus, results in circulation of the catalyst. The only catalyst which needs to be replaced is that lost through adsorption on ash or by entrainment in the form of dust in the crude gas stream. The loss in catalyst through adsorption on or reaction with ash can be minimized by adding lime to the coal.
The finely divided catalyst precipitated onto the F~ 9-7 4 r~
fresh coal is also effective in catalyzing the reaction be-tween coal and steam.
The following non-limiting examples are given by way of illustration only. Unless stated o~herwise, all per-centages given are by volume.
Steam saturated with potassium hydroxide is reacted with ground lignite briquettes in an autoclave under a pressure of 600 bar and a temperature of 660C. After remov~l of the steam, 4 liters NTP of a gas per literofIignite charge per minute are obtained, the gas containing 23% methane, 0.7%
ethane, 34% hydrogen and 42% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification at the same temperature and under a pressùre of 70 bar results, per minute and per liter of lignite charge, in 2.5 liters NTP of a gas containing 46% of hydrogen, 6% of carbon monoxide, 11% of methane and 37% of CO2.
Steam saturated with potassium hydroxide (about 0.6 grams/100 grams of H2O) is reacted with ground lignite in an autoclave under a pressure of 400 bar at a temperature of 630C. Per liter of lignite charge and per minute, 2.5 lit-ers ~TP of a gas are obtained which, after removal of the steam, contain 20% methane, 3~% hydrogen, 41% carbon dio~ide and 1% ethane. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification at the same temp~
erature and under a pressure of 70 bar leads to 2 liters NTP
of a gas per minute and per liter of lignite charge, the gas .' ' ,.' ..
- 1 0 - ' ~ ' ~)743 ~'~
containing 4% methane, 61% hydrogen, 34% carbon dioxide and 1% carbon monoxide.
Steam saturated with sodium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a temperature of 750"C. Per liter coke charge and per minute, 1.9 liters MTP of a gas are obtained which, after condensation of the steam, contain 1% methane, 65% hydrogen and 33~ carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without sodium hydroxide at the same temperature and under a pressure o~ 70 bar results, per minute and per liter o~ coke charge, in 0.4 liters NTP of a gas containing 3% methane, 59~ hydrogen, 11~ carbon monoxide and 27% carbon dioxide.
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a temperature of 770C. Per minute and per liter coke charge, 6.1 liters NTP of a gas are obtained which, after condensation of the steam, contain 5~ methane, 60% hydrogen and 35~ carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and under a pres- -sure of 300 bar results in 0.5 liters NTP of a gas per minute and per liter coke charge. The gas contains 4% methane, 58%
hydrogen, 26% carbon dioxide and 12% carbon monoxide.
~ _ 11-EXAMPLE S
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure o~
70 bar and a temperature of 750C. Per liter coke charge and per minute, 1.6 liters NTP of a gas are obtained which, after condensation of the steam, contain 1% methane, ~4% hydrogen, 2% carbon monoxide and 32% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temper-ature and under a pressure of 70 bar results in 0.4 liters NTPof a gas per minute and per liter coke charge, the gas con-taining 3% methane, 59% hydrogen, 11% carbon monoxide and 27%
carbon dioxide.
- EXAMP~E 6 Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 150 bar and a temperature of 8~5C. Per minute and per liter of coke charge, 5.1 liters NTP of a gas are obtained which, after condensation of the steam, contain 1.5% methane, 64%
hydrogen, 2% carbon monoxide and 32.5% carbon dioxide. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and a pressure of 150 bar results in 1.2 liters NTP of a gas per minute and per liter coke charge, the gas containing 2% of methane, 61% hydrogen, 11% carbon mon-oxide and 26% carbon dioxide.
. . .
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and at a temperature of 825~. Per liter coke charge and per minute, 10.3 liters NTP of a gas are obtained which, .
~)7~
after condensation of the steam, contain 1.8% methane, 64%
hydrogen, 1.55~ carbon monoxide and 32.7% carbon dioxide.
Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without potassium hydroxide at the same temperature and a pressure of 300 bar results in 1.6 liters NTP of a gas per minute and per liter coke charge, the gas containing 2.5% methane, 62% hydrogen, 6~ carbon mono-xide and 29.5% carbon dioxide.
An ~queous ammonia solution containing 11% by weight of N~3 is reacted with ground lignite in an autoclave under a pressure of 600 bar and a temperature of 620~C. Per liter lignite charge and per minute, 0.85 liters NTP of a gas are obtained which contain 38% hydrogen, 42% carbon dioxide, 14~
methane and 6% ethane. Minor amounts of higher hydrocarbons are also formed. By way of comparison, gasification without ammonia at the same temperature and pressure results in 0.5 liters NTP of a gas per minute and per liter lignite charge, 20 the gas containing 32% hydrogen, 43% carbon dioxide and 25 methane.
Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclav,e under a pressure of 300 bar and a tlemperature of 1050C. Per liter coke charge and per minute, 61 liters NTP of a gas are obtained/ the gas containing after condensation of the steam 1.8% me~hane, 62%
hydrogen, 4% carbon monoxide and 32% carbon dioxide. By way 30 of comparison, repeating the process a~ the same temperature .''~' ' .
.
. . .-, ., . .- . : . . , ~L~7~
and under the same pressure but without potassium hydroxide results, per minute and per liter of ground coke charge, in 19 liters NTP of a gas containing 3~ methane, 60~ hydrogen,
4% carbon monoxide and 33% carbon dioxide.
Steam saturated with lithium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 3~0 bar and at a temperature of 825C. Per liter coke charge and per minute, 2.1 liters NTP of a gas are obtained which contain 2~ methane, 63% hydrogen, 31% carbon dioxide, and 4~
carbon monoxide aftex removal of the steam. If the process is repeated at the same temperature and under the same pressure but without lithium hydroxide, 1.6 liters NTP of a gas are obtained per minute and per liter of ground coke charge, the gas containing 2.5~ methane, 62~ hydrogen, 6% carbon monoxide and 29.5% carbon dioxide.
.
Steam saturated with calcium hydroxide is reacted with ground lignite coke in an autoclave under a pressure of 140 bar and a temperature of 750~C. Per liter coke charge and per minute, 22 liters NTP of a gas are obtained which contain 42~ of hydrogent 15~ methane, 3% ethane, 34% carbon dioxide and 6% carbon monoxide after removal of the steam. If the process is repeated without calcium hydroxide at the same temperature and under the same pressure, 15 liters NTP of a gas are obtained per minute and per liter of ground lignite coke, the gas containing 45~ hydrogenl 13% methane, 2% ethane, 35~ carbon dioxide and 5% carbon monoxide.
"~ ' ~ . . , ~ 14 -.
1~'74~
Steam saturated with potassium hydroxide is reacted with ground plt coal coke in an autoclave under a pressure of 70 bar and a temperature of 890C. Per liter of coke charge and per minute, 21 liters NTP of a gas are obtained which contain 2% methane, 64% hydrogen, 3% carbon monoxide and 31%
carbon dioxide after removal of the steam. If the process is repeated at the same temperature and under the same pressure but without potassium hydroxide, 6.3 liters NTP o~ a gas are obtained per minute and per liter of ground pit coal coke, the gas containing 3~ methane, 61% hydrogen, 6~ carbon monoxide and 30% carbon dioxide.
EXAMæLE 13 Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 150 bar and a temperature of 1200C. Per liter of coke charge and per minute, 110 liters NI~P of a gas are obtained which con-tain 2~ methane, 61% hydrogen, 5% car~on monoxide and 32%
carbon dioxide after removal of the steam. If the process is repeated at the same temperature and under the same pressure but without potassium hydroxide, 90 liters NTP of a gas are obtained per minute and per liter of ground pit coal coke, the gas containing 3% methane, Ç0% hydrogen, 8% car~on monoxide and 29% carbon dioxide.
EX~MPLE 14 Steam saturated with potassium hydroxide is reacted with ground lignite coke which has been admixed with 1% by weight of ground limestone in an autoclave at a pressure of ~(~7~
140 bar and at a temperature of 750C. Per liter of coke charge and per minute, 29 liters NTP of a gas are obtained which contain 15% methane, 42% hydrogen, 3~% carbon dioxide, 3% ethane and 6% carbon monoxide. If the process is repeated under the same conditions but without adding ground limestone, 25.5 liters of a gas are obtained per minute and per liter of ground lignite coke, the ~as containing 11% methane, 45%
hydrogen, 6% carbon monoxide, 0.5% ethane and 38% carbon dioxide.
Steam saturated with rubidium carbonate is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and at a temperature of 755C. Per liter of coke charge and per minute, 1.3 liters NTP of a gas are obtained which contain 1.5% methane, 64% hydrogen, 1.5% carbon monoxide and 33~ carbon dioxide. If the process is repeated at the same temperature and under the same pressure but without the presence of rubidium carbonate, 0.5 liters NTP of a gas are obtained per minute and per liter of ground pit coal coke, the gas containing ~% methane, 60% hydrogen, 3~ carbon monoxide and 33% carbon dioxide.
Steam saturated with potassium borate is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a tlemperature of 750~C. Per minute and per liter coke charge, 2.2 liters NTP of a gas are obtained which, after condensation of the steam, contain 5% methane, 60~ hydrogen and 35~ carbon dioxide. Minor amounts o~ higher hydrocarbons .. ~ :. ..
, . . ~-- . . ..
~L0~7~
are also formed. By way of comparison, gasification without potassium borate at the same temperature and under a pressure of 300 bar results in 0.4 liters NTP of a gas per minute and per liter coke charge which contain 4% methane, 58% hydrogen, 12~ carbon monoxide and 26~ carbon dioxide.
Steam saturated with lithium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 3~0 bar and at a temperature of 825C. Per liter coke charge and per minute, 2.1 liters NTP of a gas are obtained which contain 2~ methane, 63% hydrogen, 31% carbon dioxide, and 4~
carbon monoxide aftex removal of the steam. If the process is repeated at the same temperature and under the same pressure but without lithium hydroxide, 1.6 liters NTP of a gas are obtained per minute and per liter of ground coke charge, the gas containing 2.5~ methane, 62~ hydrogen, 6% carbon monoxide and 29.5% carbon dioxide.
.
Steam saturated with calcium hydroxide is reacted with ground lignite coke in an autoclave under a pressure of 140 bar and a temperature of 750~C. Per liter coke charge and per minute, 22 liters NTP of a gas are obtained which contain 42~ of hydrogent 15~ methane, 3% ethane, 34% carbon dioxide and 6% carbon monoxide after removal of the steam. If the process is repeated without calcium hydroxide at the same temperature and under the same pressure, 15 liters NTP of a gas are obtained per minute and per liter of ground lignite coke, the gas containing 45~ hydrogenl 13% methane, 2% ethane, 35~ carbon dioxide and 5% carbon monoxide.
"~ ' ~ . . , ~ 14 -.
1~'74~
Steam saturated with potassium hydroxide is reacted with ground plt coal coke in an autoclave under a pressure of 70 bar and a temperature of 890C. Per liter of coke charge and per minute, 21 liters NTP of a gas are obtained which contain 2% methane, 64% hydrogen, 3% carbon monoxide and 31%
carbon dioxide after removal of the steam. If the process is repeated at the same temperature and under the same pressure but without potassium hydroxide, 6.3 liters NTP o~ a gas are obtained per minute and per liter of ground pit coal coke, the gas containing 3~ methane, 61% hydrogen, 6~ carbon monoxide and 30% carbon dioxide.
EXAMæLE 13 Steam saturated with potassium hydroxide is reacted with ground pit coal coke in an autoclave under a pressure of 150 bar and a temperature of 1200C. Per liter of coke charge and per minute, 110 liters NI~P of a gas are obtained which con-tain 2~ methane, 61% hydrogen, 5% car~on monoxide and 32%
carbon dioxide after removal of the steam. If the process is repeated at the same temperature and under the same pressure but without potassium hydroxide, 90 liters NTP of a gas are obtained per minute and per liter of ground pit coal coke, the gas containing 3% methane, Ç0% hydrogen, 8% car~on monoxide and 29% carbon dioxide.
EX~MPLE 14 Steam saturated with potassium hydroxide is reacted with ground lignite coke which has been admixed with 1% by weight of ground limestone in an autoclave at a pressure of ~(~7~
140 bar and at a temperature of 750C. Per liter of coke charge and per minute, 29 liters NTP of a gas are obtained which contain 15% methane, 42% hydrogen, 3~% carbon dioxide, 3% ethane and 6% carbon monoxide. If the process is repeated under the same conditions but without adding ground limestone, 25.5 liters of a gas are obtained per minute and per liter of ground lignite coke, the ~as containing 11% methane, 45%
hydrogen, 6% carbon monoxide, 0.5% ethane and 38% carbon dioxide.
Steam saturated with rubidium carbonate is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and at a temperature of 755C. Per liter of coke charge and per minute, 1.3 liters NTP of a gas are obtained which contain 1.5% methane, 64% hydrogen, 1.5% carbon monoxide and 33~ carbon dioxide. If the process is repeated at the same temperature and under the same pressure but without the presence of rubidium carbonate, 0.5 liters NTP of a gas are obtained per minute and per liter of ground pit coal coke, the gas containing ~% methane, 60% hydrogen, 3~ carbon monoxide and 33% carbon dioxide.
Steam saturated with potassium borate is reacted with ground pit coal coke in an autoclave under a pressure of 300 bar and a tlemperature of 750~C. Per minute and per liter coke charge, 2.2 liters NTP of a gas are obtained which, after condensation of the steam, contain 5% methane, 60~ hydrogen and 35~ carbon dioxide. Minor amounts o~ higher hydrocarbons .. ~ :. ..
, . . ~-- . . ..
~L0~7~
are also formed. By way of comparison, gasification without potassium borate at the same temperature and under a pressure of 300 bar results in 0.4 liters NTP of a gas per minute and per liter coke charge which contain 4% methane, 58% hydrogen, 12~ carbon monoxide and 26~ carbon dioxide.
Claims (9)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A method of gasifying fossil fuels by contact-ing said fuels with steam at an elevated temperature and pres-sure in the presence of catalytic amounts of at least one of, ammonium, alkali and alkaline earth salts and hydroxides which are dissolved in said steam.
2. A method according to Claim 1 in which the steam pressure is from 50 to 600 bar.
3. A method according to Claim 2 in which the pressure is 70 to 300 bar.
4. A method according to Claim 1 wherein the catalysts are alkali metal borates, carbonates or hydroxides.
5. A method according to Claim 4 in which the alkali metal is potassium.
6. A method according to Claim 1 wherein the catalysts are ammonium hydroxide, borates or carbonates.
7. A method according to Claim 1 in which the fuel to be gasified is admixed with lime.
8. A method according to Claim 1 in which gas-ification is carried out at a temperature of from 500°C to 1100°C.
9. A method according to Claim 8 in which gas-ification is conducted at from 600°C to 900°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA264,031A CA1074117A (en) | 1976-10-25 | 1976-10-25 | Catalytic method for gasification of fossil fuels with steam of increased pressure and temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA264,031A CA1074117A (en) | 1976-10-25 | 1976-10-25 | Catalytic method for gasification of fossil fuels with steam of increased pressure and temperature |
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| Publication Number | Publication Date |
|---|---|
| CA1074117A true CA1074117A (en) | 1980-03-25 |
Family
ID=4107109
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA264,031A Expired CA1074117A (en) | 1976-10-25 | 1976-10-25 | Catalytic method for gasification of fossil fuels with steam of increased pressure and temperature |
Country Status (1)
| Country | Link |
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| CA (1) | CA1074117A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5019135A (en) * | 1987-10-13 | 1991-05-28 | Battelle Memorial Institute | Method for the catalytic conversion of lignocellulosic materials |
| US5616154A (en) * | 1992-06-05 | 1997-04-01 | Battelle Memorial Institute | Method for the catalytic conversion of organic materials into a product gas |
| US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
-
1976
- 1976-10-25 CA CA264,031A patent/CA1074117A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5630854A (en) * | 1982-05-20 | 1997-05-20 | Battelle Memorial Institute | Method for catalytic destruction of organic materials |
| US5019135A (en) * | 1987-10-13 | 1991-05-28 | Battelle Memorial Institute | Method for the catalytic conversion of lignocellulosic materials |
| US5616154A (en) * | 1992-06-05 | 1997-04-01 | Battelle Memorial Institute | Method for the catalytic conversion of organic materials into a product gas |
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