CN101373839A - Method and apparatus for removing CO, electrification method and system for fuel battery with proton exchange film - Google Patents
Method and apparatus for removing CO, electrification method and system for fuel battery with proton exchange film Download PDFInfo
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- CN101373839A CN101373839A CNA2007101387717A CN200710138771A CN101373839A CN 101373839 A CN101373839 A CN 101373839A CN A2007101387717 A CNA2007101387717 A CN A2007101387717A CN 200710138771 A CN200710138771 A CN 200710138771A CN 101373839 A CN101373839 A CN 101373839A
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Abstract
The invention relates to a method and a device for removing CO, and a method and a system for generating electricity through a proton exchange membrane battery. The method for removing CO comprises two steps of reaction between reformed hydrogen and methanation catalysts. In the first step of methanation, a first methanation catalyst is adopted to remove CO at the temperature of 330-180 DEG C; the CO2 conversion rate is maintained to be less than 5%, and at the same time the volume percentage of CO is reduced to be less than 0.1%; in the second step of methanation, a second methanation catalyst is adopted to remove CO at the temperature of 220-110 DEG C; the CO2 conversion rate is maintained to be less than 5%, and at the same time the volume percentage of CO is reduced to be less than 30ppm. The invention further provides a device for removing CO by the method, as well as a method and a system for generating electricity through a proton exchange membrane battery by the method. The method ensures high level of CO removal, avoids anode toxicity of PEMFC, and leads to high efficiency because methanation is performed to only a small amount of CO2; furthermore, each methanation reactor has a broad range of operational temperatures, thereby being conducive to the design of the device and the control system.
Description
Technical field
The present invention relates to the CO removal method in fields such as a kind of new forms of energy and Chemical Engineering, particularly relate to CO degree of depth removal method and device and Proton Exchange Membrane Fuel Cells electricity-generating method and system in the integrated hydrogen source system of a kind of and Proton Exchange Membrane Fuel Cells.
Background technology
Along with becoming increasingly conspicuous of contradiction between the appearance of global energy crisis and development and the environmental protection; countries in the world are all being sought and development is efficient, cleaning, cheap regenerative resource and new forms of energy, as solar energy, wind energy, tidal energy, biomass energy, Hydrogen Energy etc.In many new forms of energy, Hydrogen Energy is considered to the most promising energy, also is considered to solve the final way of the energy and environmental problem.
The raw material sources of producing hydrogen are extensive, as fossil fuel, bio-fuel and regenerative resource etc.The method that generally adopts is the reformation of fossil fuel now, and this is most economical, the most practical at present hydrogen preparation method.But, contain the CO about 10% in the reformer hydrogen that reforming process produces, afterwards, still contain the CO of 0.4-2% in the reformer hydrogen, if adopt two sections conversion of high low temperature then contain the CO of 0.4-1% usually through CO transformationreation (WGS).And require at the anode Pt catalyst of the Proton Exchange Membrane Fuel Cells (PEMFC) of 60-80 ℃ of work that CO volume ratio content is lower than 30ppm in the reformer hydrogen, be preferably lower than 10ppm.Therefore, between shift-converter and PEMFC, need the system that the degree of depth is removed CO, CO concentration is reduced to below the 30ppm from the 0.4-2% of shift-converter outlet.
Usually, the method for CO has film separation, methods such as transformation absorption (PSA), CO selective oxidation (PROX) and CO methanation in the degree of depth removal reformer hydrogen.But, for the fixing application apparatus such as power station, automobile power, compact power of small distributed fuel cell, consider limited volume, low actual conditions such as operating pressure, feasible method has only CO selective oxidation and CO methanation.
At present, PROX is the method that the most generally adopts, also is that CO is removed to the most reliable method below the 30ppm, therefore is widely used.But PROX has following shortcoming: the first, and air blast need be set introduce air, system complex, energy consumption are increased; The second, with the simultaneous competitive reaction of PROX---H
2The oxidation meeting consume the fuel H of PEMFC
2, for avoid H as far as possible
2Consumption, need the supply of strict control air, thereby make control system complicated; The 3rd, even accurate control system, H are arranged
2Oxidation also inevitable, cause efficient to reduce; The 4th, the airborne N that introduces
2Can cause H
2Concentration reduces, thereby generating efficiency is reduced.
And CO selects methanation owing to do not need to introduce in addition reactant, and flow process, control system and reactor are simple, thereby can avoid the problems referred to above.
Batista has studied employing Co/ γ-Al
2O
3Catalyst is removed the method for CO in hydrogen and the CO mist, and the concentration of the CO that it can allow is 1000ppm (volume ratio), and in the method, the conversion ratio of CO can reach 90%.But owing to do not contain CO in the unstripped gas of this method
2, in fact, this method also is not suitable for commercial Application.Because at CO
2Exist down, when carrying out the methanation of CO, CO
2Also can react, and consume a large amount of H
2Takenake finds Ni/ZrO
2And Ru/TiO
2Can be as catalyst at CO
2Under a large amount of situations about existing,, make CO reduce to 20ppm (volume ratio content) from 5000ppm as 25% (volumn concentration), and CO
2Consumption seldom, but the scope of the effecting reaction temperature of above-mentioned catalyst is very narrow, also is not suitable for commercial Application.
United States Patent (USP) 6,207, No. 307, it has announced the reaction of a kind of employing two-part, and first section is adopted selective methanation catalyst, makes CO that methanation take place, and it is characterized in that the concentration of CO in this section outlet reaction mass remained on is enough to suppress CO
2Take place in this section on the concentration of methanation, i.e. CO concentration must be higher than 0.1% in this section outlet reaction mass, is preferably in about 0.8%.Second section is adopted same selective methanation catalyst that the CO concentration in the outlet reaction mass is reduced to below the 40ppm.The reaction temperature of first section high-temperature methanation is 250-350 ℃, and the reaction temperature of second section low temperature methanation remains on below 270 ℃.; this scheme requires first section methanation outlet reaction mass, promptly contains 0.1-1%, 0.8% CO preferably in second section reaction mass that enters the mouth; in fact for reformer hydrogen through the CO transformationreation; CO content wherein is usually in the scope of 0.4-1%, thereby above-mentioned two sections methanation reaction schemes and be not suitable for removing CO through in the reformer hydrogen of CO transformationreation.
In sum, chemical industry and new energy field, especially Proton Exchange Membrane Fuel Cells power station technology field need a kind of simply, reliably, CO degree of depth removal method efficiently.
Summary of the invention
The objective of the invention is to, provide a kind of and have simultaneously that system is simple, removal method and the device thereof of CO in the reformer hydrogen of high reliability and high efficiency characteristics, technical problem to be solved is to make it and keep lower CO in the operating temperature range that has broad
2Under the condition of conversion ratio the CO degree of depth in reformer hydrogen, especially the CO transformationreation outlet reformer hydrogen is removed to the level below the 30ppm.
Another object of the present invention is to, a proton exchanging film fuel battery electricity-generating method and a system is provided, technical problem to be solved is to make its reformer hydrogen that utilizes hydrocarbon such as natural gas as raw material, removes CO through the degree of depth, and keeps CO
2Have lower conversion ratio, thereby effectively utilize reformer hydrogen to carry out fuel cell power generation.
In order to reach the purpose of the invention described above, the inventor studies and screens the activity and the selectivity of various methanation catalysts, and has carried out a large amount of experimental studies to having different activities with the performance of catalyst optionally.At this, the activity of methanation catalyst refers to, CO content and CO in certain inlet reaction mass
2(as CO volumn concentration in the inlet reaction mass is 2% to content, CO
2Volumn concentration is 20%) condition under, the catalyst layer inlet temperature when its CO conversion ratio reaches certain numerical value (as 95%), and the selectivity of methanation catalyst refers to, CO content and CO in certain inlet reaction mass
2(as CO volumn concentration in the inlet reaction mass is 2% to content, CO
2Volumn concentration is 20%) condition under, its CO
2Catalyst layer inlet temperature when conversion ratio reaches certain numerical value (as 5%).Catalyst layer inlet temperature when the CO conversion ratio reaches certain numerical value is low more, and then this activity of such catalysts is just high more, and CO
2Catalyst layer inlet temperature when conversion ratio reaches certain numerical value is high more, and then this selection of catalysts is just high more.
The inventor has found two phenomenons from result of study, the first: highly active methanation catalyst has lower selectivity usually, and SA methanation catalyst has usually than high selectivity.It two is: when adopting single methanation catalyst, no matter be high activity (promptly low selectivity) methanation catalyst or low activity (being high selectivity) methanation catalyst, all be difficult under the condition of an operating temperature range with practicality, the CO in the reformer hydrogen is reduced to below the 30ppm from 2%.And, can be implemented in degree of depth removal CO under the condition of enough wide operating temperature range by adopting two kinds of methanation catalysts of height collocation on active and selectivity, simultaneously with CO
2Conversion ratio remains on the purpose of acceptable level.More particularly,, under the situation of the CO content lower (being lower than 0.1%) in the inlet reaction mass, can be in enough wide operating temperature range CO be removed to 30ppm and even below the 10ppm if adopt high activity (promptly low selectivity) catalyst, and with CO
2Conversion ratio remains on lower level (below 5%).But, along with the increase of CO content in the inlet reaction mass, with CO be removed to operating temperature range below the 30ppm thereupon narrowing down CO
2Conversion ratio increases thereupon.CO content is increased to 0.4% when above in the inlet reaction mass, and CO is removed to operating temperature range and CO below the 30ppm
2Conversion ratio has just reached and has been difficult to the scope accepted in the practicality, and promptly above-mentioned operating temperature range is less than 20 ℃, CO
2Conversion ratio is greater than 10%, and easy occurrence temperature sharply rises and then phenomenon out of control under higher temperature (greater than 220 ℃).Otherwise, if adopt high selectivity (being low activity) catalyst, even under the situation of the CO content lower (being lower than 0.1%) in the inlet reaction mass, also be difficult in enough wide operating temperature range, CO is removed to below the 30ppm.But, can be in enough wide operating temperature range CO be removed to 100ppm～0.1% from 2%, and simultaneously with CO
2Conversion ratio remains on lower level (below 5%).
In view of the above, the starting point of the present invention is, adopts the method for two sections methanations of high low temperature, and first section methanation adopts the high selectivity methanation catalyst to work under higher temperature, and second section methanation adopts the high activity methanation catalyst to work at a lower temperature.
The object of the invention to solve the technical problems realizes by the following technical solutions.According to the removal method of CO in a kind of reformer hydrogen of the present invention's proposition, described reformer hydrogen is carried out the two-stage catalytic methanation reaction, first methanation catalyst is adopted in first section methanation, removes CO under temperature 330-180 ℃ condition, is keeping CO
2Conversion ratio less than 5% the time, the CO volumn concentration is reduced to below 0.1%; And second section methanation, adopt second methanation catalyst, under temperature 220-110 ℃ condition, remove CO, keeping CO
2Conversion ratio less than 5% the time, CO volume ratio content is reduced to below the 30ppm.
First methanation catalyst of the present invention is the high selectivity methanation catalyst, is 2500h in inlet reaction mass air speed (GHSV) promptly
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is higher than 240 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 300 ℃.First methanation catalyst that is adopted, as long as meet the invention described above to the active catalyst that requires with selectivity, for example, its active metal component can adopt Ru, Rh, noble metals such as Pt, its metal loading can be quality percentage composition 0.1%～2.0%, also can adopt base metals such as Ni, and its metal loading can be quality percentage composition 3%～20%, and then also can adopt non-noble metal mixtures such as noble metals such as Ru and Ni, its carrier can adopt Al
2O
3, ZrO
2, TiO
2, CeO
2Deng, its preparation method can adopt coprecipitation, infusion process etc.That its shape can be is spherical, sheet, column etc.
Second methanation catalyst of the present invention is the high activity methanation catalyst, is 2500h in inlet reaction mass air speed (GHSV) promptly
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is lower than 220 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 200 ℃.Second methanation catalyst that is adopted is as long as meet the invention described above to the active catalyst that requires with selectivity, for example, its active metal component can adopt noble metals such as Ru, Rh, Pt, its metal loading can be quality percentage composition 0.2%～2.0%, and its carrier can adopt Al
2O
3, ZrO
2, TiO
2, CeO
2Deng, its preparation method can adopt coprecipitation, infusion process etc.That its shape can be is spherical, sheet, column etc.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The removal method of aforesaid CO, the inlet temperature of wherein said first section methanation catalyst layer is 330-240 ℃, by reactor is cooled off, the catalyst layer temperature is reduced gradually along the reaction tube axis direction, and the catalyst layer outlet temperature is remained on 290-180 ℃.
The removal method of aforesaid CO, the catalyst layer inlet temperature of wherein said second section methanation is 220-140 ℃, by reactor is cooled off, the catalyst layer temperature is reduced gradually along the reaction tube axis direction, and the catalyst layer outlet temperature is remained on 180-110 ℃ scope.
The removal method of aforesaid CO wherein after first section methanation, before second section methanation, is lowered the temperature to material.
The removal method of aforesaid CO, the CO, the CO that are contained in the wherein said reformer hydrogen
2And CH
4Volumn concentration be respectively CO:0.4-2.0%; CO
2: 15-30%; CH
4: 0-20%, remaining is H
2
The removal method of aforesaid CO, wherein said first methanation catalyst is the high selectivity methanation catalyst, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is higher than 240 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 300 ℃.
The removal method of aforesaid CO, wherein said second methanation catalyst is the high activity methanation catalyst, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is lower than 220 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 200 ℃.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.Removal device according to CO in a kind of reformer hydrogen of the present invention's proposition, it comprises: first section methanator and second section methanator, first section methanator is filled with the high selectivity methanation catalyst, and second section methanator is filled with the high activity methanation catalyst.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.The removal device of CO in the aforesaid reformer hydrogen is provided with heat-exchange device between wherein said first section methanator and second section methanator, is used to reduce the temperature of first section methanator outlet material.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to the removal device of CO in a kind of reformer hydrogen of the present invention's proposition, it comprises: reaction tube is provided with first catalyst bed and second catalyst bed along axis direction in this reaction tube.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.The removal device of CO in the aforesaid reformer hydrogen is provided with the heat exchange bed between wherein said first catalyst bed and second catalyst bed.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to the proton exchanging film fuel battery electricity-generating method that the present invention proposes, it may further comprise the steps:
Hydrocarbon is carried out reforming reaction, with preparation hydrogen;
Gas after the above-mentioned reforming reaction is carried out the CO transformationreation, make CO content wherein be lower than 2.0%;
Gas after the conversion is carried out methanation reaction, make wherein CO volume ratio content less than 30ppm; And
Gas behind the methanation reaction is fed Proton Exchange Membrane Fuel Cells generates electricity,
Above-mentioned methanation reaction is two sections methanation reactions,
First section methanation adopts the high selectivity methanation catalyst to remove CO at 330-180 ℃;
Second section methanation adopts the high activity methanation catalyst to remove CO at 220-110 ℃.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.Aforesaid Proton Exchange Membrane Fuel Cells electricity-generating method wherein after first section methanation, before second section methanation, is lowered the temperature to material.
The present invention also proposes a proton exchanging film fuel battery electricity generation system, and it comprises: reforming reactor, CO shift-converter, CO removal device, and Proton Exchange Membrane Fuel Cells; Described CO removal device comprises: first section methanator and second section methanator.Preferable, between first section methanator and second section methanator, be provided with heat-exchange device, be used to reduce the temperature of first section methanator outlet material.
The present invention also proposes a proton exchanging film fuel battery electricity generation system, and it comprises: reforming reactor, CO shift-converter, CO removal device, and Proton Exchange Membrane Fuel Cells; Described CO removal device comprises: reaction tube is provided with first catalyst bed and second catalyst bed along axis direction in this reaction tube.Preferable, between described first catalyst bed and second catalyst bed, be provided with the heat exchange bed.
By adopting technique scheme, the removal method of CO of the present invention and device thereof and pem cell electricity-generating method and system have following advantage at least:
1, first section methanator inlet temperature is connected mutually with the shift-converter outlet temperature;
2, CO degree of depth height is removed by system, below 30ppm, can reach below the 10ppm always, and minimum reaching below the 1ppm avoided the anode of PEMFC to poison to a great extent;
3, the selectivity height of methanation has only a spot of CO
2Methanation takes place, thereby the efficient height;
4, the operating temperature range broad of every section methanator, thereby system reliability is good, also helps the design of device and control system;
5, do not need to introduce other reactant, flow process, control system are simple, the device design simplification.
In sum, the removal method of CO of the present invention and device thereof and pem cell electricity-generating method and system, it has above-mentioned many advantages and practical value, and in like product, do not see have similar design to publish or use and really genus innovation, it is had large improvement technically, and has produced handy and practical effect, and has the multinomial effect of enhancement than the removal method of existing C O, thereby be suitable for practicality more, and have the extensive value of industry.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Description of drawings
Fig. 1 is the device flow chart of Proton Exchange Membrane Fuel Cells electricity generation system of the present invention.
Fig. 2 is the generalized section of the methanator of CO removal device of the present invention
Fig. 3 is the generalized section of another embodiment of CO removal device of the present invention.
Fig. 4 is the flow chart of the proton exchanging film fuel battery electricity-generating method that proposes of the present invention.
Embodiment
Below in conjunction with accompanying drawing and preferred embodiment, the removal method of the CO that foundation the present invention is proposed and embodiment, structure, feature and the effect thereof of device and Proton Exchange Membrane Fuel Cells electricity-generating method and system thereof thereof, describe in detail as after.
Fig. 1 is the device flow chart of Proton Exchange Membrane Fuel Cells electricity generation system of the present invention.This electricity generation system comprises successively: reforming reactor 10, it is a raw material with hydrocarbons such as natural gases, carries out reforming reaction therein and generates H
2, CO and CO
2CO shift-converter 20, the concentration of reduction CO in this reactor; CO removal device 30; Further reduce the concentration of CO therein by methanation reaction, make the content of CO meet the requirement of the anode Pt of Proton Exchange Membrane Fuel Cells (PEMFC) reformation gas CO content; Proton Exchange Membrane Fuel Cells 40, its exit gas with methanator 30 is a fuel, carries out the electrochemistry generating.Above-mentioned reforming reactor 10, CO shift-converter 20 and Proton Exchange Membrane Fuel Cells 40 all adopt scheme of the prior art, do not repeat them here.
Above-mentioned CO removal device 30 comprises: first section methanator 31, and adopt the high selectivity methanation catalyst under higher reaction temperature, to react, the CO content reduction with high concentration makes CO simultaneously
2Methanation reaction does not take place substantially; Second section methanator 32 under the temperature lower than first section methanator, adopts high activated catalyst to come CO in the first section methanator outlet in the degree of depth place to go reaction mass, makes it reach the requirement of Proton Exchange Membrane Fuel Cells to CO content.Because two sections methanation methods of high low temperature of the present invention make the degree of depth of CO remove and are able to carry out under lower temperature, so also have only very a spot of CO second section methanation
2Methanation reaction takes place.So, this CO removal device can either reduce the concentration (the volume ratio content of CO less than 30ppm, and even less than 10ppm) of CO in the reformation gas, can guarantee to have only very a spot of CO again
2Methanation (CO takes place
2Conversion ratio less than 5%).
In the present invention, first and second sections methanators adopt fixed bed reactors.Fig. 2 is the generalized section of first section methanator 31 of the present invention, it comprises stainless steel reaction pipe 100, reaction tube 100 1 ends are provided with baffle plate 130, it on baffle plate catalyst bed 120, be used for the filling catalyst, it on catalyst bed 120 inert material bed 110, be used for the filling inert material (as, corundum ball etc.), on the reaction tube axis, be provided with thermocouple sheath 140, be provided with at least one thermocouple 150 therein, preferable, the quantity of thermocouple is 3, lays respectively at the two ends and the centre of catalyst layer 120, thereby can accurately measure the Temperature Distribution of catalyst layer 120.Among the present invention, second section methanator 32 adopts the structure identical with first section methanator 31.
Another preferable CO removal device of the present invention is for to be provided with heat-exchange device 33 between first section methanator 31 and second section methanator 32, be used to reduce the temperature of first section methanator, 31 outlet reaction masses, make it satisfy the requirement of second section methanator 32 working temperature.
Preferable, CO removal device of the present invention can be combined as a device.See also shown in Figure 3, the CO removal device comprises stainless steel reaction pipe 100, reaction tube 100 1 ends are provided with baffle plate 130, on baffle plate second section catalyst bed 170, be used for second section methanation catalyst layer of filling, being provided with heat exchange bed 160 on this catalyst bed 170, being provided with heat exchange structure 161 at this heat exchange bed, for example is coil pipe; On cooling bed 160 first section catalyst bed 120, be used for first section methanation catalyst of filling, on this first section catalyst bed 120 is inert material bed 110, be used for filling inert material (as corundum ball etc.), on the reaction tube axis, be provided with thermocouple sheath 140, be provided with at least one thermocouple 150 at each catalyst layer, preferable, the quantity of each catalyst layer thermocouple is 3, lay respectively at the two ends and the centre of each catalyst layer, thereby can accurately measure the Temperature Distribution of each catalyst layer.
Fig. 4 is the flow chart of a kind of pem cell electricity-generating method of proposing of the present invention.This electricity-generating method may further comprise the steps: natural gas is carried out steam reformation S10, with preparation hydrogen; Gas after the above-mentioned reformation is carried out CO transformationreation S20, make CO volumn concentration wherein be lower than 2%, be preferably lower than 1%.Gas after the conversion is carried out methanation reaction S30, make wherein CO volume ratio content less than 30ppm; And the gas behind the methanation reaction fed the Proton Exchange Membrane Fuel Cells S40 that generates electricity.Above-mentioned methanation reaction S30 is two sections methanation reactions, and first section methanation reaction S31 adopts the high selectivity methanation catalyst to remove CO at 330-240 ℃; Second section methanation reaction S32 adopts the high activity methanation catalyst to remove CO at 220-140 ℃.Preferable, after first section methanation, before second section methanation, material is carried out heat exchange S33, make temperature of charge remain on 200-150 ℃.The CO of above-mentioned methanation reaction
2Conversion ratio less than 5%.Above-mentioned CO removal method and embodiment are applicable to the CO degree of depth removal step in the Proton Exchange Membrane Fuel Cells electricity-generating method of the present invention.
Experimental technique
Adopt above-mentioned CO removal device to carry out the removal experiment of CO in the reformer hydrogen.
In experiment, the analog gas that adopts reformer hydrogen is as reactant, and it is high-purity component gas CO, CH with commercialization
4, CO
2And H
2Mix, flow simulation natural gas via steam reformation by controlling each component and the reformer hydrogen after the CO conversion, its classical group becomes (volumn concentration): 20% CO
2, 5% CH
4, 0.1～2% CO, surplus is H
2, and import the water vapour of volumn concentration 25% to mixed gas.Adopt gas-chromatography (GC6820, Agilent Technologies) that raw material and product are carried out composition analysis before and after the reaction with thermal conductivity cell detector (TCD) and hydrogen flame detector (FID).The loadings of catalyst is 30 milliliters (the catalyst bed layer height is 80 millimeters), is provided with K type thermocouple on the reaction tube axis, is used for the detection reaction temperature.Before the reaction, use N
2: H
2For the gaseous mixture of 1:1 (volume ratio) 300 ℃ of prereduction catalyst 3 hours.In order to control the temperature gradient in the methanator, be provided with the cooling air interlayer at the reactor outer wall, other experimental detail is the known technology of those skilled in the art, does not repeat them here.
Embodiment 1
Present embodiment is about a kind of typical embodiment of the present invention.Present embodiment adopts the catalyst HS1 of inventor's preparation as first section methanation catalyst, and the catalyst HA1 that adopts inventor's preparation is as second section methanation catalyst.Catalyst HS1 is for adopting the Ru0.5%-Al of immersion process for preparing
2O
3The high selectivity methanation catalyst is 2500h in inlet reaction mass air speed (GHSV)
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and it is 250 ℃ that its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature, and CO
2It is 330 ℃ that conversion ratio reaches 5% o'clock catalyst layer inlet temperature.Catalyst HA1 is for adopting the Ru1.5%-Al of immersion process for preparing
2O
3The high activity methanation catalyst is 2500h in inlet reaction mass air speed (GHSV)
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and it is 200 ℃ that its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature, and CO
2It is 210 ℃ that conversion ratio reaches 5% o'clock catalyst layer inlet temperature.
It is CO 2% that the dry gas of the inlet reaction mass of first section methanation of present embodiment is formed (volumn concentration); CO
220%; CH
45%; H
273%, the water vapour volumn concentration of its moisture is 25%, and dry gas air speed (GHSV) is 2500h
-1, 340～230 ℃ of catalyst layer inlets, 280～180 ℃ of outlets, experimental result is asked for an interview table 1.When the catalyst layer inlet temperature was 340～250 ℃, the CO of first section methanation outlet reaction mass was reduced to below 0.1%, and when the catalyst layer inlet temperature is 330～240 ℃, the CO of first section methanation
2Conversion ratio is less than 5%.Therefore, for catalyst HS1, it is keeping CO
2Conversion ratio less than 5% the time, the operating temperature range that the CO volume percent content is reduced to below 0.1% is 330～250 ℃, 80 ℃ of Wen Kuanwei promptly work.
Table 1 inlet reaction mass CO content is first section methanation experimental result of 2% o'clock employing HS1
It is CO 0.1% that the dry gas of the inlet reaction mass of second section methanation of present embodiment is formed (volumn concentration); CO
22 0%; CH
45%; H
2About 75%, the water vapour volumn concentration of its moisture is 25%, and dry gas air speed (GHSV) is 2500h
-1, 230～130 ℃ of catalyst layer inlets, 190～100 ℃ of outlets, experimental result is asked for an interview table 2.When the catalyst layer inlet temperature was 220～140 ℃, the CO of second section methanation outlet reaction mass was reduced to below the 30ppm, and when the catalyst layer inlet temperature is 220～130 ℃, the CO of second section methanation
2Conversion ratio is less than 5%.Therefore, for catalyst HA1, it is keeping CO
2Conversion ratio less than 5% the time, making the CO volume ratio be reduced to the following operating temperature range of 30ppm is 220～140 ℃, 80 ℃ of Wen Kuanwei promptly work.
Table 2 inlet reaction mass CO content is second section methanation experimental result of 0.1% o'clock employing HA1
Comparative example 1
Comparative example 1 is the experiment example that compares for one section methanation method with two sections methanation methods of the present invention and public technology, and the catalyst of employing is above-mentioned catalyst HA1.
It is CO0.4% that the dry gas of the methanation inlet reaction mass of this comparative example is formed (volumn concentration); CO
220%; CH
45%; H
274.6%, the water vapour volumn concentration of its moisture is 25%, and dry gas air speed (GHSV) is 2500h
-1, 230～130 ℃ of catalyst layer inlets, 190～100 ℃ of outlets.By the experimental result of table 3 as seen, when the catalyst layer inlet temperature was 210～200 ℃, the CO of one section methanation outlet reaction mass had been reduced to below the 30ppm, and promptly working, temperature is wide only to be 10 ℃.
Table 3 inlet reaction mass CO content is one section methanation experimental result of 0.4% o'clock employing HA1
| Inlet temperature ℃ | 230 | 220 | 210 | 200 | 190 | 180 | 160 | 140 | 130 |
| Outlet temperature ℃ | 190 | 180 | 170 | 170 | 160 | 150 | 130 | 110 | 100 |
| Outlet CO content (volume ratio content) ppm | 65.0 | 42.0 | 27.2 | 25.4 | 45.0 | 100 | 1000 | 1700 | 2000 |
| CO 2Conversion ratio % | 8.0 | 4.0 | 2.0 | 1.0 | <1 | <1 | <1 | <1 | <1 |
Unless otherwise indicated, the content of each gas component of the present invention is volumn concentration.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (17)
1. the removal method of CO in the reformer hydrogen is characterized in that:
Described reformer hydrogen is carried out the two-stage catalytic methanation reaction,
First methanation catalyst is adopted in first section methanation, removes CO under the condition of 330～180 ℃ of temperature, is keeping CO
2Conversion ratio less than 5% the time, the CO volume percent content is reduced to below 0.1%; And
Second methanation catalyst is adopted in second section methanation, removes CO under the condition of 220～110 ℃ of temperature, is keeping CO
2Conversion ratio less than 5% the time, CO volume ratio content is reduced to below the 30ppm.
2. the removal method of CO in the reformer hydrogen according to claim 1, the inlet temperature that it is characterized in that wherein said first section methanation catalyst layer is 330～240 ℃, by reactor is cooled off, the catalyst layer temperature is reduced gradually along the reaction tube axis direction, and the catalyst layer outlet temperature is remained on 270～180 ℃ scope.
3. the removal method of CO in the reformer hydrogen according to claim 1, the catalyst layer inlet temperature that it is characterized in that wherein said second section methanation is 220～140 ℃, by reactor is cooled off, the catalyst layer temperature is reduced gradually along the reaction tube axis direction, and the catalyst layer outlet temperature is remained on 180～110 ℃ scope.
4. according to the removal method of CO in each described reformer hydrogen of claim 1～3, it is characterized in that after first section methanation, before second section methanation, material is lowered the temperature.
5. the removal method of CO is characterized in that the CO, the CO that are contained in the wherein said reformer hydrogen in the reformer hydrogen according to claim 1
2And CH
4Volumn concentration be respectively CO:0.4～2.0%; CO
2: 15～30%; CH
4: 0～25%, remaining is H
2
6. the removal method of CO in the reformer hydrogen according to claim 1 is characterized in that wherein said first methanation catalyst is the high selectivity methanation catalyst, is 2500h in inlet reaction mass air speed (GHSV)
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is higher than 240 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 300 ℃.
7. the removal method of CO in the reformer hydrogen according to claim 1 is characterized in that wherein said second methanation catalyst is the high activity methanation catalyst, is 2500h in inlet reaction mass air speed (GHSV)
-1Condition under, the volumn concentration of CO is 2% in the inlet reaction mass, CO
2Volumn concentration is 20% o'clock, and its CO conversion ratio reaches 95% o'clock catalyst layer inlet temperature and is lower than 220 ℃, and CO
2Conversion ratio reaches 5% o'clock catalyst layer inlet temperature and is higher than 200 ℃.
8. the removal device of CO in the reformer hydrogen, it is characterized in that it comprises: first section methanator and second section methanator, first section methanator is filled with the high selectivity methanation catalyst, and second section methanator is filled with the high activity methanation catalyst.
9. the removal device of CO in the reformer hydrogen according to claim 8 is characterized in that being provided with heat-exchange device between described first section methanator and second section methanator, is used to reduce the temperature of first section methanator outlet material.
10. the removal device of CO in the reformer hydrogen, it is characterized in that it comprises: reaction tube is provided with first catalyst bed and second catalyst bed along axis direction in this reaction tube.
11. the removal device of CO in the reformer hydrogen according to claim 10 is characterized in that being provided with the heat exchange bed between first catalyst bed and second catalyst bed.
12. a proton exchanging film fuel battery electricity-generating method is characterized in that it may further comprise the steps:
Hydrocarbon is carried out reforming reaction, with preparation hydrogen;
Gas after the above-mentioned reforming reaction is carried out the CO transformationreation, make CO content wherein be lower than 2.0%;
Gas after the conversion is carried out methanation reaction, make wherein CO volume ratio content less than 30ppm; And
Gas behind the methanation reaction is fed Proton Exchange Membrane Fuel Cells generates electricity,
Above-mentioned methanation reaction is two sections methanation reactions,
First section methanation adopts the high selectivity methanation catalyst to remove CO at 330～180 ℃;
Second section methanation adopts the high activity methanation catalyst to remove CO at 220～110 ℃.
13. Proton Exchange Membrane Fuel Cells electricity-generating method according to claim 12 is characterized in that after first section methanation, before second section methanation, material is lowered the temperature.
14. a proton exchanging film fuel battery electricity generation system is characterized in that it comprises: reforming reactor, CO shift-converter, CO removal device, and Proton Exchange Membrane Fuel Cells; Described CO removal device comprises: first section methanator and second section methanator.
15. Proton Exchange Membrane Fuel Cells electricity generation system according to claim 14, it is characterized in that between first section methanator and second section methanator, being provided with heat-exchange device, be used to reduce the temperature of first section methanator outlet material.
16. a proton exchanging film fuel battery electricity generation system is characterized in that it comprises: reforming reactor, CO shift-converter, CO removal device, and Proton Exchange Membrane Fuel Cells; Described CO removal device comprises: reaction tube is provided with first catalyst bed and second catalyst bed along axis direction in this reaction tube.
17. Proton Exchange Membrane Fuel Cells electricity generation system according to claim 16 is characterized in that being provided with the heat exchange bed between described first catalyst bed and second catalyst bed.
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| GB9620287D0 (en) * | 1996-09-28 | 1996-11-13 | Johnson Matthey Plc | Carbon monoxide removal |
| CN1069687C (en) * | 1998-07-03 | 2001-08-15 | 李群柱 | Process for purification to obtain high-purity synthetic gas by adsorption |
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