CN101289166B - Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 - Google Patents
Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 Download PDFInfo
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- CN101289166B CN101289166B CN200810114915XA CN200810114915A CN101289166B CN 101289166 B CN101289166 B CN 101289166B CN 200810114915X A CN200810114915X A CN 200810114915XA CN 200810114915 A CN200810114915 A CN 200810114915A CN 101289166 B CN101289166 B CN 101289166B
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Abstract
The invention relates to a method for preparing H2 and CO by the cotransformation of CH4 and CO2 and a device thereof, which belongs to the technical filed of petrochemical industry and coal-chemical industry. The reactant gases CH4 and CO2 are premixed by mole ration of 1:1 to 4:1, sent into a plasma reactor for reaction, separated by a polysulphone membrane H2 separator and then separated by a CO separator, with the left gas sent back to be premixed with feed gas, thereby obtaining H2 and CO by circulative preparation. A gas premixer (1), a plasma reactor (2), an H2 separator (3) and a CO separator (4) are connected in sequence, and the outlet that does not separates gas of the CO separator is connected with the inlet of the premixer. The invention also provides a method and a device that include the steps of reaction-separation-separation-reaction-separation-separation for twice or a plurality of times. The method and the device of the invention avoid terminated reaction caused by catalyst deactivation and realize the preparation of H2 and CO at low temperature, effectively reduce the energy consumption and have high transformation rate of CH4 and CO2 and good product selectivity.
Description
Technical field
The present invention relates to CH under a kind of low temperature
4And CO
2Cotransformation prepares H
2Method and device with CO belong to petrochemical complex and technical field of coal chemical industry.
Background technology
CH
4And CO
2Be main greenhouse gases, CH
4CO
2Chemical conversion when reforming reaction not only can realize the two can prepare a large amount of synthetic gas again and be used for technologies such as fischer-tropsch synthesizes.
This research at present mainly concentrates on the following aspects: thermodynamic study, the research of catalyst cupport metal, carrier and auxiliary agent, carbon distribution behavioral study and reaction kinetics research etc.Can know that according to calculation of thermodynamics this reaction is a strong endothermic reaction, will just have synthetic gas to generate more than 600 ℃ at least, and reach higher CH more than 850 ℃
4And CO
2Transformation efficiency, therefore traditional catalyst methane dry gas reforming reaction is the reaction of a high energy consumption.In hot environment, the carrier of catalyzer need be selected chemical property and the stable material of physical properties under the high temperature for use, and the action mode of he and active ingredient is also to the catalytic activity important influence of catalyzer.Catalytic reforming reaction for methane, the metal of load is that active ingredient mostly is the VIII group 4 transition metal on the catalyzer, the most normal use is metallic nickel, but there is a very big drawback in this type of catalyzer, in catalytic reaction process, be very easy to carbon distribution and cause catalyst deactivation, thereby make reaction terminating, usually adopt some alkaline-earth metal of interpolation or rare-earth oxide to reduce carbon distribution as auxiliary agent, use precious metal can effectively suppress the carbon distribution behavior, but the use of precious metal cause the rising significantly of catalyzer cost as active ingredient.CH
4And CO
2As the high-carbon content material, the two reaction certainly will cause bigger carbon distribution inactivation problem.
There are some researches show that at present the characteristic of utilizing plasma body can realize the CH under the low temperature
4And CO
2Transform, but because the characteristic of plasma body itself, this process is relatively poor and transformation efficiency is limited for product selectivity.
There is following shortcoming in traditional methane dry gas reforming process: reaction at high temperature could take place, and needs high-octane input, causes CO
2The raising of chemical conversion technology cost; Requirement to catalyzer is very high, has both required carrier to have higher thermostability, overcomes the reaction terminating that carbon distribution causes again.
General plasma-catalytic CH
4And CO
2There is following shortcoming in chemical conversion: by the plasma reactor of operation under the normal atmosphere, selectivity of product is very poor, the synthetic gas yield is low and the unstripped gas transformation efficiency is low, some utilize radio frequency or microwave discharge to promote the reactor that transforms to operate under lower negative pressure, not only the requirement raising to equipment has also influenced the treatment capacity of reactor, thereby is unfavorable for the industry amplification.
Summary of the invention
The objective of the invention is: overcome traditional methane dry gas reforming process high energy consumption, the easily shortcoming of carbon distribution, and the inferior position that plasma body itself is poor to selectivity of product, transformation efficiency is low; Utilize the plasma body self character, can realize CH at low temperatures
4With CO
2Higher chemical conversion rate; Adopt a cover reaction-separation-isolating cyclic process to realize H under the low temperature
2Preparation with CO.
To achieve these goals, the technical scheme of the present invention's proposition is:
CH under a kind of low temperature
4And CO
2Cotransformation prepares H
2Method and device with CO is characterized in that, this method is carried out as follows:
(1) reactant gases CH
4With CO
2Premix;
(2) enter plasma reactor through the mixed gas behind the premix, as coaxial-type dielectric barrier discharge reactor, low temperature, normal atmosphere issue biochemical conversion; In the product gas except CO and H
2The outer CH that does not have reaction in addition
4And CO
2Gas also has a spot of higher hydrocarbons to produce except reaction generates synthetic gas, as C
2H
6, C
2H
4, C
3H
8Deng;
(3) the mixed gas process H that goes out from plasma reactor stream
2Separator, as the polysulfone membrane hydrogen gas segregator, operation pressure reduction is 7～8atm, service temperature is a normal temperature, most H
2Be separated;
(4) step (3) H
2The remaining gas in separated back enters the CO separator again, as utilizes the pressure-swing absorber of copper base CO chemosorbent, and operation pressure reduction is latm, and service temperature is that normal temperature carries out the CO separation; The most CO that CO separates, most of unreacted CO
2With a spot of CH
4Enter in the pyrocarbon stove, as fluid-bed combustion furnace, with the CO gas of excess carbon reaction generation;
(5) to separate remaining gas almost all be CH to step (4) CO
4, remaining CH
4Get back to recycle in the plasma reactor, carry out the next one with unstripped gas and react-separate-partitioning cycle, thereby constantly obtain H
2And CO.
In the aforesaid method step (1), feed gas CH
4With CO
2Mol ratio in 1: 1～4: 1 scopes.
In the aforesaid method, the service temperature of full cycle process is 20 ℃～200 ℃ of low temperature, and working pressure all can be realized in latm～10atm scope.
The invention provides CH under a kind of low temperature
4And CO
2Cotransformation prepares H
2With the device of CO, described device comprises the premixed device (1) that is arranged on before plasma reactor enters the mouth, and reaction of low temperature plasma device (2) is arranged on the H that the reaction of low temperature plasma device exports
2Separator (3) is arranged on H
2The CO separator (4) of separator outlet is arranged on the pyrocarbon stove (5) of CO separator outlet; Gas pre-mixed device (1) pneumatic outlet links to each other with the plasma reactor inlet, reaction of low temperature plasma device (2) outlet and H
2Separator (3) inlet links to each other H
2Separator (3) has H
2The divided gas flow outlet, H
2Separator (3) not divided gas flow outlet links to each other with CO separator (4) gas inlet, and the divided gas flow outlet of CO separator links to each other with pyrocarbon stove (5) inlet mouth, and CO separator not divided gas flow outlet links to each other with the premixed device inlet.
The invention provides CH under a kind of low temperature
4And CO
2Cotransformation prepares H
2With the method for CO, this method can be passed through circulating reaction realization in the single complete equipment of reaction-separation-separation.
In step in the aforesaid method (3), (4), the mixed gas that goes out from plasma reactor stream passes through CO separator and H respectively
2Separator, the order of two separators can be exchanged.CO separator and H in the related device
2The order of two separators of separator is exchanged.
The present invention also provides CH under a kind of low temperature
4And CO
2Cotransformation prepares H
2With the method for CO, this method realizes by circulating reaction in reaction-separation-separation-reaction-separation-separation two covers or the many complete equipments.
The invention provides CH under the another kind of low temperature
4And CO
2Cotransformation prepares H
2With the device of CO, described device comprises the first gas pre-mixed device (1-a), the first reaction of low temperature plasma device (2-a), a H
2Separator (3-a), a CO separator (4-a), the first pyrocarbon stove (5-a), the second gas pre-mixed device (1-b), second plasma reactor (2-b), the 2nd H
2Separator (3-b), the 2nd CO separator (4-b) the second pyrocarbon stove (5-b); The outlet of the first gas pre-mixed device (1-a) links to each other the outlet of the first reaction of low temperature plasma device (2-a) and a H with first plasma reactor (2-a) inlet
2Separator (3-a) links to each other, a H
2Separator (3-a) has divided gas flow outlet, a H
2The not divided gas flow outlet of separator (3-a) links to each other with a CO separator (4-a) inlet, and the divided gas flow outlet of a CO separator (4-a) links to each other with pyrocarbon stove (5-a) inlet; The not divided gas flow outlet of the one CO separator (4-a) links to each other with the inlet of the second gas pre-mixed device (1-b), the outlet of the second gas pre-mixed device (1-b) links to each other the pneumatic outlet of the second reaction of low temperature plasma device (2-b) and the 2nd H with second plasma reactor (2-b) gas inlet
2Separator (3-b) inlet links to each other the 2nd H
2Separator (3-b) has divided gas flow outlet, the 2nd H
2The not divided gas flow outlet of separator (3-b) connects the inlet of the 2nd CO separator (4-b), the outlet of the 2nd CO separator (4-b) divided gas flow links to each other with second pyrocarbon stove (5-b) gas inlet, and the 2nd CO separator (4-b) not divided gas flow outlet links to each other with first gas pre-mixed device (1-a) gas inlet.Aforesaid device utilizes reaction-separation-separation-reaction-separation-separation round-robin method like this, has realized CH
4And CO
2Height transform, and obtained H
2And CO.
The present invention compared with prior art has the following advantages and the high-lighting effect:
1. avoided utilizing conventional means to realize the required high energy consumption of methane dry gas reformation, and because the catalyst deactivation that carbon distribution causes, and then the reaction terminating that causes.
2. effectively utilize this any special measures of plasma body, realized CH at low temperatures
4And CO
2Efficient conversion, effectively reduced energy consumption.
3. overcome and utilized low-temperature plasma catalyzed conversion CH usually
4And CO
2The time transformation efficiency low, the shortcoming of product selectivity difference utilizes this circulation technology of reaction-separation-separation to realize preparing under the low temperature H
2Preparation with CO.
Description of drawings
Fig. 1 is the schema of the inventive method.
Fig. 2 is the schema of the present invention's another kind method.
Fig. 3 is the synoptic diagram of apparatus of the present invention.Wherein, 1, gas pre-mixed device; 2, reaction of low temperature plasma device; 3, H
2Separator; 4, CO separator; 5, pyrocarbon stove; A, plasma-catalytic converted product mixed gas; B, H
2C, H
2Mixed gas after the separation; D, CO gas; Mixed gas after E, CO separate; G, unstripped gas
Fig. 4 is the synoptic diagram of the another kind of square law device of the present invention.Among the figure: 1-a, the first gas pre-mixed device; 2-a, the first reaction of low temperature plasma device; 3-a, a H
2Separator; 4 one a, a CO separator; 5-a, the first pyrocarbon stove; 1-b, the second gas pre-mixed device; 2-b, the second reaction of low temperature plasma device; 3-b, the 2nd H
2Separator; 4-b, the 2nd CO separator; 5-b, the second pyrocarbon stove; A-1, plasma-catalytic converted product mixed gas; B-1, H
2C-1, H
2Mixed gas after the separation; D-1, CO gas; Mixed gas after E-1, CO separate; A-2, plasma-catalytic converted product mixed gas; B-2, H
2C-2, H
2Mixed gas after the separation; D-2, CO gas; Mixed gas after E-2, CO separate; F, supply unstripped gas; G, unstripped gas
Embodiment
Further describe the present invention below in conjunction with accompanying drawing.
Fig. 1 is the schema of the inventive method.Fig. 3 is the synoptic diagram of apparatus of the present invention.Among Fig. 3,1, gas pre-mixed device; 2, reaction of low temperature plasma device; 3, H
2Separator; 4, CO separator; 5, pyrocarbon stove; A, plasma-catalytic converted product mixed gas; B, H
2C, H
2Mixed gas after the separation; D, CO gas; Mixed gas after E, CO separate; G, unstripped gas.Gas pre-mixed device (1) pneumatic outlet links to each other with the plasma reactor inlet, reaction of low temperature plasma device (2) outlet and H
2Separator (3) inlet links to each other H
2Separator (3) has H
2The divided gas flow outlet, H
2Separator (3) not divided gas flow outlet links to each other with CO separator (4) gas inlet, and the divided gas flow outlet of CO separator links to each other with pyrocarbon stove (5) inlet mouth, and CO separator not divided gas flow outlet links to each other with the premixed device inlet.
Mol ratio is 1: 1～4: 1 CH
4And CO
2Gas mixture enters in the reaction of low temperature plasma device 2, CH
4With CO
2Be ionized, form plasma atmosphere, wherein contain a large amount of active groups and metastable state ion, thereby make the two that chemical reaction take place, but the two transformation efficiency is limited, and because the non-directional combination of active group makes resultant gas not only contain CO and H
2Also has a spot of C
2H
6, C
2H
4, C
3H
8Deng the carbon hydro carbons, mixed gas A enters H
2In the separator 3, the H of the overwhelming majority
2Separated going out, thus prepare hydrogen B, through H
2The remaining mixed gas C of separator enters CO separator 4, most CO and CO
2And a spot of CH
4And H
2Separated going out, this divided gas flow enter the CO gas D that 5 calcinations of pyrocarbon stove are produced, and the main ingredient of separating remaining gas E is CH
4, it enters in the premixed device 1 with raw material supply gas G, returns through premix and carries out circulating reaction in the reaction of low temperature plasma device 2.
Fig. 2 is the schema of the present invention's another kind method.Fig. 4 is the synoptic diagram of the another kind of square law device of the present invention.Among Fig. 4: 1-a, the first gas pre-mixed device; 2-a, the first reaction of low temperature plasma device; 3-a, a H
2Separator; 4-a, a CO separator; 5-a, the first pyrocarbon stove; 1-b, the second gas pre-mixed device; 2-b, the second reaction of low temperature plasma device; 3-b, the 2nd H
2Separator; 4-b, the 2nd CO separator; 5-b, the second pyrocarbon stove; A-1, plasma-catalytic converted product mixed gas; B-1, H
2C-1, H
2Mixed gas after the separation; D-1, CO gas; Mixed gas after E-1, CO separate; A-2, plasma-catalytic converted product mixed gas; B-2, H
2C-2, H
2Mixed gas after the separation; D-2, CO gas; Mixed gas after E-2, CO separate; F, supply unstripped gas; G, unstripped gas.The outlet of the first gas pre-mixed device (1-a) links to each other the outlet of the first reaction of low temperature plasma device (2-a) and a H with first plasma reactor (2-a) inlet
2Separator (3-a) links to each other, a H
2Separator (3-a) has divided gas flow outlet, a H
2The not divided gas flow outlet of separator (3-a) links to each other with a CO separator (4-a) inlet, and the divided gas flow outlet of a CO separator (4-a) links to each other with pyrocarbon stove (5-a) inlet; The not divided gas flow outlet of the one CO separator (4-a) links to each other with the inlet of the second gas pre-mixed device (1-b), the outlet of the second gas pre-mixed device (1-b) links to each other the pneumatic outlet of the second reaction of low temperature plasma device (2-b) and the 2nd H with second plasma reactor (2-b) gas inlet
2Separator (3-b) inlet links to each other the 2nd H
2Separator (3-b) has divided gas flow outlet, the 2nd H
2The not divided gas flow outlet of separator (3-b) connects the inlet of the 2nd CO separator (4-b), the outlet of the 2nd CO separator (4-b) divided gas flow links to each other with second pyrocarbon stove (5-b) gas inlet, and the 2nd CO separator (4-b) not divided gas flow outlet links to each other with first gas pre-mixed device (1-a) gas inlet.
Mol ratio is 1: 1～4: 1 CH
4And CO
2Gas mixture enters among the reaction of low temperature plasma device 2-a, CH
4With CO
2Be ionized, form plasma atmosphere, wherein contain a large amount of active groups and metastable state ion, thereby make the two that chemical reaction take place, but the two transformation efficiency is limited, and because the non-directional combination of active group makes resultant gas not only contain CO and H
2Also has a spot of C
2H
6, C
2H
4, C
3H
8Deng the carbon hydro carbons, mixed gas A-1 enters H
2Among the separator 3-a, the H of the overwhelming majority
2Separated going out, thus prepare hydrogen B-1, through H
2The remaining mixed gas C-1 of separator enters CO separator 4-a, most CO and CO
2And a spot of CH
4And H
2Separated going out, this divided gas flow enter the CO gas D-1 that pyrocarbon stove 5-a calcination is produced, and the main ingredient of separating remaining gas E-1 is CH
4, it enters among the premixed device 1-b with raw material supply gas F, enters into reaction of low temperature plasma device 2-b through premix and proceeds reaction, CH
4With CO
2Be ionized and react, the mixed gas A-2 of generation enters H
2Among the separator 3-b, the H of the overwhelming majority
2Separated going out, thus prepare hydrogen B-2, through H
2The remaining mixed gas C-2 of separator enters CO separator 4-b, most CO and CO
2And a spot of CH
4And H
2Separated going out, this divided gas flow enter the CO gas D-2 that pyrocarbon stove 5-b calcination is produced, and the main ingredient of separating remaining gas E-2 is CH
4, it enters among the premixed device 1-a with raw material supply gas G, returns among the reaction of low temperature plasma device 2-a through premix and carries out circulating reaction.
CH
4With CO
2With 1: 1 ratio charging of mol ratio, reactor operating pressure is 7atm, in the reaction of low temperature plasma device, and CH
4Transformation efficiency reaches 50%, CO
2Transformation efficiency reaches 27%, and the selectivity of CO is about 60%, H
2Selectivity about 80%, remaining gas is C
2H
6, C
2H
4, C
3H
8Deng the high-carbon hydro carbons, this mixed gas together enters H
2Separator, most H
2Separated going out, purity reaches 90%-95%, and residual gas enters the CO separator again, most CO and a part of CO
2All separated going out also has a spot of CH
4With remaining H
2Also separated going out, they together enter the pyrocarbon stove again and carry out calcination, and obtain purity and reach CO gas more than 95%, be CH through the overwhelming majority in the remaining gas of CO separator
4, small part is CO
2, they together get back in the reaction of low temperature plasma device with unstripped gas together, carry out next one reaction-separation-separating technology.
CH
4With CO
2With 4: 1 ratio charging of mol ratio, reactor operating pressure is 7atm, in the reaction of low temperature plasma device, and CH
4Transformation efficiency reaches 14%, CO
2Transformation efficiency reaches 42%, and the selectivity of CO is about 80%, H
2Selectivity about 60%, remaining gas is C
2H
6, C
2H
4, C
3H
8Deng the high-carbon hydro carbons, this mixed gas together enters H
2Separator, most H
2Separated going out, purity reaches 90%-95%, and residual gas enters the CO separator again, whole CO and whole CO
2All separated going out also has a spot of CH
4With remaining H
2Also separated going out, they together enter the pyrocarbon stove again and carry out calcination, obtain purity and reach CO gas more than 95%, through almost all being CH in the remaining gas of CO separator
4, they together get back in the reaction of low temperature plasma device with unstripped gas together, carry out next one reaction-separation-separating technology.
CH
4With CO
2With 2: 1 ratio charging of mol ratio, reactor operating pressure is 7atm, in the reaction of low temperature plasma device, and CH
4Transformation efficiency reaches 22%, CO
2Transformation efficiency reaches 32%, and the selectivity of CO is about 64%, H
2Selectivity about 70%, remaining gas is C
2H
6, C
2H
4, C
3H
8Deng the high-carbon hydro carbons, this mixed gas together enters H
2Separator, most H
2Separated going out, purity reaches 90%-95%, and residual gas enters the CO separator again, whole CO and whole CO
2All separated going out also has a spot of CH
4With remaining H
2Also separated going out, they together enter the pyrocarbon stove again and carry out calcination, obtain purity and reach CO gas more than 95%, through almost all being CH in the remaining gas of CO separator
4, they together get back in the reaction of low temperature plasma device with unstripped gas together, carry out next one reaction-separation-separating technology.
Claims (8)
1.CH
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, this method is carried out as follows:
(1) reactant gases CH
4With CO
2Enter premix in the gas pre-mixed device;
(2) enter the plasma reactor reaction through the mixed gas behind the premix;
(3) the mixed gas process H that goes out from plasma reactor stream
2Separator is with H
2Separate;
(4) H in the step (3)
2The remaining gas in separated back enters the CO separator again and carries out the CO separation; The gas of separating generates target CO gas by the pyrocarbon stove with the reaction of pyrocarbon stove excess carbon;
(5) to separate remaining gas almost all be CH to step (4) CO
4With remaining CH
4By getting back to recycle in the plasma reactor, carry out the next one with new raw material gas and react-separate-partitioning cycle, thereby constantly obtain H with the unstripped gas premix
2And CO;
Described feed gas CH
4With CO
2Mol ratio be 1: 1～4: 1;
The service temperature of entire method process is 20 ℃～200 ℃, and working pressure is 1atm～10atm.
2. CH according to claim 1
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, described plasma reactor is a coaxial-type dielectric barrier discharge reactor.
3. CH according to claim 1
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, described H
2Separator is the polysulfone membrane hydrogen gas segregator.
4. CH according to claim 1
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, described CO separator is the pressure-swing absorber that utilizes copper base CO chemosorbent.
5. CH according to claim 1
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, described pyrocarbon stove is a fluid-bed combustion furnace.
6. CH according to claim 1
4And CO
2Cotransformation prepares H
2Method with CO is characterized in that, this method comprises reaction-separation-separation-reaction-separation-separation plural process.
7.CH
4And CO
2Cotransformation prepares H
2Device with CO is characterized in that, described device comprises gas pre-mixed device (1), reaction of low temperature plasma device (2), H
2Separator (3), CO separator (4), pyrocarbon stove (5);
Gas pre-mixed device (1) pneumatic outlet links to each other with reaction of low temperature plasma device inlet, reaction of low temperature plasma device (2) outlet and H
2Separator (3) inlet links to each other H
2Separator (3) has H
2The divided gas flow outlet, H
2Separator (3) not divided gas flow outlet links to each other with CO separator (4) gas inlet, and the divided gas flow outlet of CO separator links to each other with pyrocarbon stove (5) inlet mouth, and CO separator not divided gas flow outlet links to each other with gas premixed device inlet.
8.CH
4And CO
2Cotransformation prepares H
2Device with CO is characterized in that, described device comprises the first gas pre-mixed device (1-a), the first reaction of low temperature plasma device (2-a), a H
2Separator (3-a), a CO separator (4-a), the first pyrocarbon stove (5-a), the second gas pre-mixed device (1-b), the second reaction of low temperature plasma device (2-b), the 2nd H
2Separator (3-b), the 2nd CO separator (4-b), the second pyrocarbon stove (5-b);
The outlet of the first gas pre-mixed device (1-a) links to each other the outlet of the first reaction of low temperature plasma device (2-a) and a H with the first reaction of low temperature plasma device (2-a) inlet
2Separator (3-a) links to each other, a H
2Separator (3-a) has divided gas flow outlet, a H
2The not divided gas flow outlet of separator (3-a) links to each other with a CO separator (4-a) inlet, and the divided gas flow outlet of a CO separator (4-a) links to each other with the first pyrocarbon stove (5-a) inlet; The not divided gas flow outlet of the one CO separator (4-a) links to each other with the inlet of the second gas pre-mixed device (1-b), the outlet of the second gas pre-mixed device (1-b) links to each other the pneumatic outlet of the second reaction of low temperature plasma device (2-b) and the 2nd H with second reaction of low temperature plasma device (2-b) gas inlet
2Separator (3-b) inlet links to each other the 2nd H
2Separator (3-b) has divided gas flow outlet, the 2nd H
2The not divided gas flow outlet of separator (3-b) connects the inlet of the 2nd CO separator (4-b), the outlet of the 2nd CO separator (4-b) divided gas flow links to each other with second pyrocarbon stove (5-b) gas inlet, and the 2nd CO separator (4-b) not divided gas flow outlet links to each other with first gas pre-mixed device (1-a) gas inlet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810114915XA CN101289166B (en) | 2008-06-13 | 2008-06-13 | Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810114915XA CN101289166B (en) | 2008-06-13 | 2008-06-13 | Process and device for preparing H2 and CO by co-transformation of CH4 and CO2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101289166A CN101289166A (en) | 2008-10-22 |
| CN101289166B true CN101289166B (en) | 2011-09-14 |
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| DE102012010542A1 (en) * | 2011-12-20 | 2013-06-20 | CCP Technology GmbH | METHOD AND APPARATUS FOR GENERATING SYNTHESEGAS |
| EP2866930A1 (en) * | 2012-06-29 | 2015-05-06 | Basf Se | High-pressure process for carbon dioxide reforming of hydrocarbons in the presence of iridium-containing active masses |
| CN107161947A (en) * | 2017-06-20 | 2017-09-15 | 中国科学院山西煤炭化学研究所 | Carbon dioxide and hydrogen sulfide gaseous mixture convert the method and device of producing synthesis gas |
| CN113620240B (en) * | 2021-06-29 | 2022-08-19 | 东北大学 | Method for determining technological parameters for preparing hydrogen-based reducing gas |
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