CN103107350B - Temperature control type monomer reactor - Google Patents
Temperature control type monomer reactor Download PDFInfo
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- CN103107350B CN103107350B CN201310038864.8A CN201310038864A CN103107350B CN 103107350 B CN103107350 B CN 103107350B CN 201310038864 A CN201310038864 A CN 201310038864A CN 103107350 B CN103107350 B CN 103107350B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a temperature control type monomer reactor which is preferably made of aluminum alloy or made of stainless steel or copper, and the temperature control type monomer reactor is used for a carbon monoxide preferable methanation reaction of reactant gas which is to be supplied to a fuel battery system and obtained through a fuel reforming reaction. According to the temperature control type monomer reactor provided by the invention, the reaction temperature in the reactor is controlled about 180 DEG C-230 DEG C, preferably 190 DEG C-210 DEG C, and the conversion rate of a carbon dioxide reduction reaction in the carbon monoxide preferable methanation reaction is controlled about 1%-4%; and hydrogen is not largely consumed, the structure is simple, and the cost is low.
Description
Technical field
The present invention relates to a kind of temperature control type monomer reaction device, more specifically, relate to so a kind of temperature control type monomer reaction device, its for be supplied to fuel cell system (such as, low-temperature protonic exchange film fuel battery system), the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction.
Background technology
It is known that in the field of fuel cell system, there is the multiple fuel type for the preparation of hydrogen, such as alkanes (methane, ethane etc.), alcohols (methyl alcohol, ethanol etc.), gasoline, diesel oil etc.These fuel (mainly comprise carburretion reforming reaction, fuel autothermal reforming reaction and fuel meat oxyreforming reaction three kinds of reformation modes by fuel reforming reaction usually, wherein carburretion reforming reaction is the most conventional) produce hydrogen, such as, the reaction equation of methyl alcohol vaporizing reforming reaction is CH
3oH+H
2o → CO
2+ 3H
2, the reaction equation of partial oxidation reaction of methane is CH
4+ 0.5O
2→ CO+2H
2.
But, while obtaining hydrogen by fuel reforming reaction, also can carry out the steam displacement reaction (CO generating carbon monoxide
2+ H
2→ CO+H
2o).Thus, final reacting gas can comprise the carbon monoxide of carbon dioxide, about 1%-5% and the methane of less than 2% of hydrogen, the about 15%-25% of about 65%-75% usually.
But, above-mentioned reacting gas is being transported to fuel cell system (especially, low-temperature protonic exchange film fuel battery system) before, in order to meet basic demanded fuel, usually need, by hydrogen purification method, the content of carbon monoxide is reduced to 10/1000000ths (10ppm) below, guarantee that hydrogen content can not obviously reduce, to ensure hydrogen production efficiency simultaneously.
A kind of known hydrogen purification method is in reactor assembly, carry out carbon monoxide preferential methanation reaction (usually adopting ruthenium to be catalyst), and wherein, Carbon monoxide reduction reacts---namely, and reaction A:CO+3H
2→ CH
4+ H
2o---be preferential reaction; Carbon dioxide reduction reaction---namely, reaction B:CO
2+ 4H
2→ CH
4+ 2H
2o---be the reaction (being called " suppressing reaction ") that need suppress.
Therefore, reaction A is preferentially carried out in order to suppress reaction B, namely, preferentially carry out the reaction A of removal CO and suppress the reaction B consuming H2 equally, need reaction temperature to control in a suitable scope, make carbon monoxide content to be reduced to below 10ppm, even lower, can guarantee that again hydrogen can not be made to pass through reaction B to be consumed in a large number because temperature is too high simultaneously.
But, multiple reactor is normally carried out notch cuttype series connection (such as, needing to be realized by modes such as human weld) by conventional reactor assembly, and usually needs to adopt more than one heat abstractor to dispel the heat to whole reactor assembly, structure is too complicated, and cost is high.And, even if having employed notch cuttype series design, still local overheating phenomenon is easily there is when reaction gas flow changes greatly in whole reactor assembly, although the reactor assembly of routine often also can make the conversion ratio of reaction A reach 100%, but too high temperature can cause catalyst activity reduction and make reaction B aggravate (making reaction B have the conversion ratio of roughly about 5%-about 40%), this causes a large amount of hydrogen to be consumed, and significantly reduces hydrogen production efficiency.
Therefore, pole needs a kind of novel reactor to solve the problems referred to above.
Summary of the invention
The object of the present invention is to provide a kind of temperature control type monomer reaction device, for be supplied to fuel cell system, the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, this temperature control type monomer reaction device comprises:
A housing;
An entrance, is arranged on the housing, to introduce described reacting gas;
An outlet, is arranged on the housing, to discharge described reacting gas;
The main line of multiple hollow, for placing catalyst, described multiple main line to be encapsulated in described housing and with described entrance and described outlet, each main line is preferably furnished with the aluminium alloy vane of one or more lamination shape within it;
A temperature control device, comprising:
Multiple radiating component, stacked up and down with described multiple main line, wherein radiating component and main line are alternately stacking, and be arranged in described housing in the mode of a side on the other, each radiating component is formed by the aluminium alloy vane of one or more lamination shape substantially;
At least one pair of Cooling Holes, arranges relative to one another on the housing, is communicated with respectively with radiating component, and for being communicated with the cooling system of at least one outside;
Wherein, the reaction temperature in described main line controls at about 180 DEG C-230 DEG C by described temperature control device, preferably controls at about 190 DEG C-210 DEG C.
Above-mentioned novel temperature control type monomer reaction device, effectively reaction temperature can be controlled between about 180 DEG C to about 230 DEG C, preferably control at about 190 DEG C-210 DEG C, thus keep the activity of catalyst, make its reaction time long, the conversion ratio reacted making Carbon monoxide reduction is while 100%, suppress the conversion ratio of carbon dioxide reduction reaction, it is roughly controlled at about 1%-4%, guarantee that hydrogen can not be consumed in a large number thus, and structure is simple, cost is low.
The present invention also provide a kind of utilize above-mentioned temperature control type monomer reaction device carry out to be supplied to fuel cell system, the method for the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, the reaction temperature of carbon monoxide preferential methanation reaction controls at about 180 DEG C-230 DEG C by the method, preferably controls at about 190 DEG C-210 DEG C.Thus, by the conversion rate control of carbon dioxide reduction reaction at about 1%-4%.
Accompanying drawing explanation
With reference to the following drawings, can understand the present invention better in conjunction with hereafter unrestriced exemplary, in the accompanying drawings, identical reference number represents identical parts or part.Should be understood that these accompanying drawings are nonrestrictive, may not draw in proportion, and some feature may be not shown.
In the accompanying drawings:
Fig. 1 is the schematic perspective view of temperature control type monomer reaction device according to an embodiment of the invention;
Fig. 2 is the front view of the monomer reaction of temperature control type shown in Fig. 1 device;
Fig. 3 is the schematic perspective view of the internal structure in the monomer reaction of temperature control type shown in Fig. 1 device, described internal structure comprises main line that is stacked, alternately stacked arrangement and radiating component up and down, wherein main line is hollow, or can have the aluminium alloy vane of lamination shape in it;
Fig. 4 is the sectional view of internal structure shown in Fig. 3;
Fig. 5 is the schematic diagram of gas flow when there is carbon monoxide preferential methanation reaction in display temperature control type monomer reaction device in internal structure shown in Fig. 3;
Fig. 6 is the stacked up and down schematic diagram of single main line and the radiating component that formed by a lamination shape aluminium alloy vane;
Fig. 7 A is the schematic diagram according to another embodiment, wherein single main line and the stacked up and down schematic diagram of the radiating component that formed by multiple lamination shape aluminium alloy vane interlaced arrangement;
Fig. 7 B is the schematic diagram that the part of Fig. 7 A is amplified;
Fig. 8 A is the schematic diagram according to another embodiment, wherein single main line and arrange the schematic diagram that the radiating component that formed is stacked up and down each other at angle by multiple lamination shape aluminium alloy vane;
Fig. 8 B is the schematic diagram that the part of Fig. 8 A is amplified;
Fig. 9 is the schematic perspective view of the temperature control type monomer reaction device according to a further embodiment of the invention; And
Figure 10 is the front view of the monomer reaction of temperature control type shown in Fig. 9 device.
Embodiment
In the present invention, as illustrated without other, then the degree of each component by volume percentage calculation in admixture of gas.
In the present invention, " carbon monoxide preferential methanation reaction " is interpreted as in the system (also can also have other composition) comprising hydrogen, carbon dioxide, carbon monoxide, methane, water, preferentially realize Carbon monoxide reduction reaction, suppress the process of carbon dioxide reduction reaction simultaneously.Therefore, as long as in the system (also can also have other composition) comprising hydrogen, carbon dioxide, carbon monoxide, methane, water, realize this two objects simultaneously, all should be understood to belong to " carbon monoxide preferential methanation reaction " of the present invention.
Temperature control type monomer reaction device of the present invention is preferably made up of aluminium alloy, but also can make with copper, stainless steel or other materials be applicable to, for to be supplied to fuel cell system, the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, this temperature control type monomer reaction device comprises:
A housing;
An entrance, is arranged on the housing, to introduce described reacting gas;
An outlet, is arranged on the housing, to discharge described reacting gas;
The main line of multiple hollow, for placing catalyst, described multiple main line to be encapsulated in described housing and with described entrance and described outlet, each main line is preferably furnished with the aluminium alloy vane of one or more lamination shape within it;
A temperature control device, comprising:
Multiple radiating component, stacked up and down with described multiple main line, wherein radiating component and main line are alternately stacking, and be arranged in described housing in the mode of a side on the other, each radiating component is formed by the aluminium alloy vane of one or more lamination shape substantially;
At least one pair of Cooling Holes, arranges relative to one another on the housing, is communicated with respectively with radiating component, and for being communicated with the cooling system of at least one outside;
Wherein, the reaction temperature in described main line controls at about 180 DEG C-230 DEG C by described temperature control device, preferably controls at about 190 DEG C-210 DEG C.Thereby, it is possible to by the conversion rate control of described carbon dioxide reduction reaction at about 1%-4%.
In the present invention, in carbon monoxide preferential methanation reaction, Carbon monoxide reduction reaction (hereafter also can be described as " reaction A ")---namely, CO+3H
2→ CH
4+ H
2o---be preferential reaction; Carbon dioxide reduction reaction (hereafter also can be described as " reaction B ")---namely, CO
2+ 4H
2→ CH
4+ 2H
2o---for needing the reaction suppressed.
In the present invention, fuel reforming reaction mainly comprises carburretion reforming reaction (hereafter also referred to as " reaction I "), fuel autothermal reforming reaction (hereafter also referred to as " reaction II ") and fuel meat oxidation reaction (hereafter also referred to as " reaction III "), and reaction expression is recorded as follows:
Reaction I:C
xh
yo
z+ (2x-z) H
2o → xCO
2+ (2x-z+y/2) H
2;
Reaction II:C
xh
yo
z+ (x-z-j) H
2o+(j/2) O
2→ (x) CO+ (x-z-j+y/2) H
2;
Reaction III:C
xh
yo
z+ 0.5(x-z) O
2→ (x) CO+ (y/2) H
2.
Should be understood that while carrying out all kinds of reforming reaction, also can carry out the steam displacement reaction (hereafter also referred to as " reaction IV ") generating carbon monoxide, that is, CO
2+ H
2→ CO+H
2o.
Should be understood that the fuel for hydrogen manufacturing can be alkanes (such as, methane or ethane), alcohols (such as, methyl alcohol or ethanol), gasoline, diesel oil or other fuel be applicable to.
Usually, the carbon monoxide of carbon dioxide, about 1%-5% and the methane of less than 2% of hydrogen, the about 15%-25% of about 65%-75% is comprised through reaction I and the reacting gas of reaction IV; The reacting gas passing through reaction II and reaction IV comprises the nitrogen (oxygen is taken from air usually needed for reaction II, therefore contains nitrogen) of the carbon monoxide of carbon dioxide, about 1%-5% of hydrogen, the about 10%-20% of about 40%-60%, the methane of less than 2% and 10%-30%; And, the reacting gas passing through reaction III and reaction IV comprises the nitrogen (oxygen is taken from air usually needed for reaction III, therefore contains nitrogen) of the carbon monoxide of carbon dioxide, about 1%-5% of hydrogen, the about 10%-15% of about 15%-30%, the methane of less than 2% and 20%-30%.
Can find out, in the reacting gas of above-mentioned three kinds of fuel reforming reactions, all comprise the carbon monoxide of about 1%-5%.Should be understood that before reacting gas is transported to fuel cell system, the content of carbon monoxide should be reduced to 10/1000000ths (10ppm) below, even lower.
Temperature control type monomer reaction device of the present invention can be used for the content reducing carbon monoxide.
In a preferred embodiment of the invention, the thickness of the aluminium alloy vane of each lamination shape is about 0.1mm to 2mm, and has square, triangle or the corrugated cross sectional shape of semicircle.
In a preferred embodiment of the invention, the aluminium alloy vane of described multiple lamination shape can be in alignment with each other ground horizontal arrangement, ground interlaced with each other horizontal arrangement or at angle be in tilted layout each other, preferably each other in 120 ° to 175 °, with the thermal conduction characteristic of enhance fluid, not excessively increase the import and export pressure drop of cooling system simultaneously.
Particularly point out at this, adopt above-mentioned configured and disposed lamination shape aluminium alloy vane to have extraordinary radiating effect, contribute to the control to reaction temperature of temperature control type monomer reaction device of the present invention.
In a preferred embodiment of the invention, described catalyst is filled in described main line in granular form, in fixed bed state.
In a preferred embodiment of the invention, described catalyst-coated on the inwall of described main line, and preferably has the thickness of about 0.5mm to 2.0mm.
In a preferred embodiment scheme, catalyst is ruthenium catalyst, is loaded catalyst or coating type catalyst, and the former preferably uses with fixed bed form, is benchmark by vehicle weight, calculates for 5-20%Ru(presses metal)/Al
2o
3or 5-20%Ru(presses metal calculating)/SiO
2; The latter is used for reactor wall with coating form, and based on total coating weight, the content of ruthenium is that 5-20%Ru(calculates by metal), coating is silicon sol solution or the Alumina gel solution of ruthenium soluble-salt, coated, is attached to the inwall of reactor.
In a preferred embodiment of the invention, at least one external refrigeration system described is fan, air blast, air pump, pressure-air steel cylinder or other cooling systems be applicable to, and contributes to temperature control type monomer reaction device of the present invention to the control of reaction temperature.
In a preferred embodiment of the invention, described fuel reforming reaction is carburretion reforming reaction, fuel autothermal reforming reaction or fuel meat oxyreforming reaction.
In a preferred embodiment of the invention, described fuel cell system is low-temperature protonic exchange film fuel battery system, also can be the fuel cell system that other are applicable to.
Now by reference to the accompanying drawings, further exemplary illustration is done to invention.Totally with reference to Fig. 1 and 2, Fig. 1-2, schematic perspective view according to the temperature control type monomer reaction device 1 of one embodiment of the invention and front view are shown respectively.Described temperature control type monomer reaction device 1 is preferably made up of aluminium alloy, but also can be made up of copper, stainless steel or other materials be applicable to, its for be supplied to fuel cell system, by fuel reforming reaction (such as, can for carburretion reforming reaction, fuel autothermal reforming reaction or fuel meat oxyreforming reaction) the carbon monoxide preferential methanation reaction of reacting gas (generally including the carbon monoxide of about 1-5%) that obtains, this reactor comprises: a housing 2; An entrance 3, is arranged on described housing 2, to introduce described reacting gas; An outlet 4, is arranged on described housing 2, to discharge described reacting gas; The main line 6 of multiple hollow, for placing catalyst, described multiple main line 6 to be encapsulated in described housing 2 and to be communicated with described outlet 4 with described entrance 3; A temperature control device (unmarked), comprise: multiple radiating component 7, stacked with described multiple main line about 6, wherein radiating component 7 and main line 6 alternately stacking, be arranged in described housing 2 in the mode of a side on the other, each radiating component 7 is formed by the aluminium alloy vane of one or more lamination shape substantially; A pair Cooling Holes 5,5 ' (according to actual needs, also can be multipair Cooling Holes), be arranged on described housing 2 relative to one another, be communicated with radiating component 7 respectively, and for (not shown with the cooling system of at least one outside, according to actual needs, also can be multiple cooling system, such as, can be fan, air blast, air pump, pressure-air steel cylinder or other cooling devices be applicable to) connection; Wherein, the reaction temperature in described main line 6 controls at about 180 DEG C-230 DEG C by described temperature control device, preferably controls at about 190 DEG C-210 DEG C, thus can by the conversion rate control of described carbon dioxide reduction reaction at about 1%-4%.
See Fig. 3 and 4, show main line 6 and radiating component about 7 is stacked, the alternately stereogram of stacked arrangement (on the other side) and sectional view.As shown in Figure 5, show the flow direction of reacting gas, reacting gas passes into the inside of temperature control type monomer reaction device 1, carry out carbon monoxide preferential methanation reaction, there is the reaction A removing CO, and because reaction temperature is controlled in about 180 DEG C-230 DEG C, preferably at about 190 DEG C-210 DEG C, restrained effectively the generation of reaction B, that is, the conversion ratio reacting B is controlled in about 1%-4%, far below the control (usually at about 5%-40%) of conventional reactor system to reaction B conversion ratio, ensure that hydrogen can not be consumed in a large number, ensure that hydrogen production efficiency.
In a preferred embodiment of the invention, the thickness of the aluminium alloy vane of each lamination shape is about 0.1mm to 2mm, and there is square, triangle or the corrugated cross sectional shape of semicircle or other shapes be applicable to, see the basic blade construction of the radiating component shown in Fig. 6.
In a preferred embodiment of the invention, see Fig. 7 A and Fig. 7 B, aluminium alloy vane 8 ' the ground interlaced with each other horizontal arrangement of four lamination shapes, the radiating component in forming reactions device; Or, see Fig. 8 A and Fig. 8 B, aluminium alloy vane 8 " be in tilted layout each other, in the radiating component 7 in forming reactions device, preferably each other in 120 ° to 175 °, to strengthen thermal conduction characteristic at angle.
In a preferred embodiment of the invention, described catalyst is filled in described main line in granular form, becomes fixed bed state; Or described catalyst-coated on the inwall of described main line, and has the thickness of about 0.5mm to 2.0mm.
See Fig. 9 and 10, the schematic perspective view according to the temperature control type monomer reaction device of a further embodiment of the invention and front view are shown respectively.What be different from the temperature control type monomer reaction device shown in Fig. 1 and 2 is, this temperature control type monomer reaction device 10 comprises two pairs of Cooling Holes 50,50 ' and 51,51 ', be connected with two cooling systems respectively, such cooling effect can be better, more contributes to the control of reactor to temperature.
In a preferred embodiment of the invention, described fuel cell system is low-temperature protonic exchange film fuel battery system.
The present invention utilize above-mentioned temperature control type monomer reaction device carry out to be supplied to fuel cell system, the method for the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, comprise and the reaction temperature of carbon monoxide preferential methanation reaction is controlled, at about 180 DEG C-230 DEG C, preferably to control at about 190 DEG C-210 DEG C.Thus, by the conversion rate control of carbon dioxide reduction reaction at about 1%-4%.
In a preferred embodiment of the inventive method, react and carry out under ruthenium catalyst exists.Ruthenium catalyst is loaded catalyst or coating type catalyst, and the former preferably uses with fixed bed form, is benchmark by vehicle weight, calculates for 5-20%Ru(presses metal)/Al
2o
3or 5-20%Ru(presses metal calculating)/SiO
2; The latter is used for reactor wall with coating form, and based on total coating weight, the content of ruthenium is that 5-20%Ru(calculates by metal), coating is silicon sol solution or the Alumina gel solution of ruthenium soluble-salt, coated, is attached to the inwall of reactor.
Hereafter will provide non-limiting example of the present invention and adopt the comparative example of pre-existing reactors system, more clearly to explain advantage of the present invention.Should be understood that embodiment does not hereafter limit the scope of the invention.
Embodiment
embodiment 1
There is provided a temperature control type monomer reaction device, it is made up of aluminium alloy, and general structure as shown in Figure 1, has the main line (long-300mm of 40 hollows; Wide-150mm; Height-10mm, wherein the wall thickness of main line is 2mm) and 39 radiating component (long-150mm; Wide-300mm; Height-5mm; Wherein radiating component length is different from main line with the orientation of width), the aluminium alloy vane of lamination shape is not arranged in main line, the arrangement of the lamination shape aluminium alloy vane of main line and formation radiating component as shown in Figure 6, wherein blade height is 5mm, and stack width (intervals between two laminations) is 3mm; That be connected with a pair Cooling Holes of this reactor is a fan (model: W1G250HH6752-BA-ENG, purchased from German EBM PAPST); Catalyst adopts graininess ruthenium catalyst (5 % by weight/Al
2o
3, model: PM0400321, purchased from American An Ge Co., Ltd), particle is the cylinder of 1.5mm diameter X1.5mm height, is filled in main line, in fixed bed state; The initial reacting gas total flow be obtained by reacting by methane gasifying reforming is 67 gram/minute, this reacting gas comprises hydrogen 6.2 gram/minute, carbon dioxide 43.6 gram/minute, carbon monoxide 1 gram/minute, water 16.2 gram/minute, temperature of charge is 200 degrees Celsius; Wherein, the air mass flow that fan is sent into is 577 gram/minute, and temperature is 25 degrees Celsius; Reacted generation gas comprises hydrogen 5.67 gram/minute, carbon dioxide 41.83 gram/minute, methane 1.2 gram/minute, water 18.27 gram/minute, product temperature is (corresponding to reaction temperature, lower same) be about 200 degrees Celsius, Carbon monoxide reduction reaction conversion ratio 100%, carbon dioxide reduction reaction conversion ratio 4%; Wherein, the heat exchange amount of main line and radiating component is 185 watts.
embodiment 2
There is provided a temperature control type monomer reaction device, it is made up of aluminium alloy, and general structure as shown in Figure 9, has 30 main lines (long-500mm; Wide-150mm; Height-10mm; Wherein the wall thickness of main line is 2mm) and 29 radiating component (long-200mm; Wide-500mm; Height-5mm); Be furnished with the aluminium alloy vane of lamination shape in each main line, blade height is 6mm, and stack width is 4mm, and length of blade is 500mm; As shown in Figure 7 A, the height of each blade is 5mm to the layout of the lamination shape aluminium alloy vane that four dislocation forming radiating component are arranged, stack width is 3mm, and length is 50mm; What be connected respectively with two pairs of Cooling Holes of this reactor is two fans (model: PSD17051, purchased from Taiwan quasi-corporations); Catalyst adopts ruthenium catalyst (model: PM0400321, purchased from American An Ge Co., Ltd), and be coated on the inwall of main line, coating layer thickness is 0.5mm, and coating is the Ludox containing ruthenium, based on SiO in coating
2weight, Ru content is 7 % by weight; The initial reacting gas total flow obtained by ethane chlorination reforming reaction is 41.8 gram/minute, this reacting gas comprises hydrogen 3.63 gram/minute, carbon dioxide 26.41 gram/minute, carbon monoxide 2.77 gram/minute, water 9.03 gram/minute, temperature of charge is 220 degrees Celsius; Wherein, the air mass flow of a fan feeding is 1154 gram/minute, and temperature is 25 degrees Celsius, and the air mass flow that another fan is sent into is 577 gram/minute, and temperature is 25 degrees Celsius; Reacted generation gas comprises hydrogen 2.91 gram/minute, carbon dioxide 25.75 gram/minute, methane 1.83 gram/minute, water 11.35 gram/minute, product temperature is about 180 degrees Celsius, Carbon monoxide reduction reaction conversion ratio 100%, carbon dioxide reduction reaction conversion ratio 1.5%; Wherein, the heat exchange amount of main line and radiating component is totally 755 watts.
embodiment 3
There is provided a reactor assembly, it is made up of stainless steel, and general structure as shown in Figure 1, has 40 main lines (long-600mm; Wide-150mm; Height-10mm; Wherein the wall thickness of main line is 2mm) and 39 radiating component (long-250mm; Wide-600mm; Height-5mm), be furnished with the aluminium alloy vane of lamination shape in each main line, each blade height is 6mm, and stack width is 4mm, and length of blade is 600mm; Form the layout of five lamination shape aluminium alloy vanes of radiating component as shown in Figure 8 A, the height of each blade is 5mm, and stack width is 3mm, and length is 50mm, becomes 150 ° of layouts each other; What be connected with a pair Cooling Holes of this reactor is a fan (model: PSD17051, purchased from Taiwan quasi-corporation); Catalyst adopts ruthenium catalyst (model: PM0400321, purchased from American An Ge Co., Ltd), and be coated on the inwall of main line, coating layer thickness is 1.0mm, and coating is the Alumina gel containing ruthenium, based on Al in coating
2o
3weight, Ru content is 10 % by weight; The total flow of the initial reacting gas obtained by methyl alcohol vaporizing reforming reaction is 37.79 gram/minute, comprise hydrogen 3.02 gram/minute, carbon dioxide 27.51 gram/minute, carbon monoxide 1.4 gram/minute, water 5.85 gram/minute, temperature of charge is 200 degrees Celsius; Wherein, the air mass flow that fan is sent into is 1100 gram/minute, and temperature is 35 degrees Celsius; Reacted generation gas comprises hydrogen 2.56 gram/minute, carbon dioxide 26.63 gram/minute, methane 1.12 gram/minute, water 7.47 gram/minute, product temperature is about 190 degrees Celsius, Carbon monoxide reduction reaction conversion ratio 100%, carbon dioxide reduction reaction conversion ratio 2.2%; Through calculating wherein, total heat exchange amount of main line and radiating component is 565 watts.
comparative example 1
There is provided the reactor assembly that conventional, it comprises the shell-and-tube exchanger adopting stainless steel to make, and (model is 8H25, purchased from Shanghai City Ou Deke fluid treating plant Co., Ltd; Its mesochite diameter: 120mm, shell is high: 600mm; Pipe diameter 6mm; Pipe quantity: 15) as carbon monoxide preferential methanator; Inside reactor adopts granular ruthenium catalyst (5 % by weight/Al
2o
3, model: PM0400321, purchased from American An Ge Co., Ltd), particle is the cylinder of 1.5mm diameter X1.5mm height, is filled to fixed bed state; That be connected with reactor is a fan (model: W1G250HH6752-BA-ENG, purchased from German EBM PAPST); The total flow of the initial reacting gas be obtained by reacting by methane gasifying reforming is 67 gram/minute, comprises hydrogen 6.2 gram/minute, carbon dioxide 43.6 gram/minute, carbon monoxide 1 gram/minute, water 16.2 gram/minute, and temperature of charge is 200 degrees Celsius; Wherein, the air mass flow that fan is sent into is 577 gram/minute, and temperature is 25 degrees Celsius; Reacted generation gas comprises hydrogen 2.95 gram/minute, carbon dioxide 27.01 gram/minute, methane 6.6 gram/minute, water 30.4 gram/minute, product temperature is 380 degrees Celsius, Carbon monoxide reduction reaction conversion ratio 100%, carbon dioxide reduction reaction conversion ratio 38%; Wherein, the heat exchange amount of reaction channel and heat dissipation channel is 755 watts.
comparative example 2
There is provided the reactor assembly that conventional, it comprises employing two stainless steel shell-and-tube heat exchangers as carbon monoxide preferential methanator; That is, (model is 8H15 to a preposition methanator, purchased from Shanghai City Ou Deke fluid treating plant Co., Ltd; Its mesochite diameter: 120mm, shell is high: 300mm; Pipe diameter 6mm, pipe quantity: (model is 8H15 to 15) and one rearmounted methanator, purchased from Shanghai City Ou Deke fluid treating plant Co., Ltd; Its mesochite diameter: 120mm, shell is high: 200mm; Pipe diameter 6mm, pipe quantity: 15); What be connected with this reactor is two fans (model: PSD17051, purchased from Taiwan quasi-corporations); Inside reactor adopts graininess ruthenium catalyst (7 % by weight/SiO
2, model: PM0400321, purchased from American An Ge Co., Ltd), particle is the cylinder of 1.5mm diameter X1.5mm height, is filled to fixed bed state; The total flow of the initial reacting gas obtained by ethane chlorination reforming reaction is 41.8 gram/minute, comprise hydrogen 3.63 gram/minute, carbon dioxide 26.41 gram/minute, carbon monoxide 2.77 gram/minute, water 9.03 gram/minute, temperature of charge is 220 degrees Celsius; Wherein, the air mass flow of a fan feeding is 1154 gram/minute, and temperature is 25 degrees Celsius, and the air mass flow that another fan is sent into is 577 gram/minute, and temperature is 25 degrees Celsius; Reacted generation gas comprises hydrogen 2.50 gram/minute, carbon dioxide 23.53 gram/minute, methane 2.64 gram/minute, water 13.17 gram/minute, product temperature is 240 degrees Celsius, Carbon monoxide reduction reaction conversion ratio 100%, carbon dioxide reduction reaction conversion ratio 10%; Wherein, the heat exchange amount of reaction channel and heat dissipation channel is totally 544 watts.
In order to more clearly explain advantage of the present invention, in following table 1, list the related data of the conversion ratio about hydrogen, carbon monoxide, methane, carbon dioxide, reaction temperature, reaction A and reaction B in above-described embodiment and comparative example:
Table 1 is about the related data of above-described embodiment and comparative example
Note: total flow, H in table 1
2flow, CO flow, CO
2flow and CH
4the unit of flow is g/min.
Can find out, reaction temperature can control between about 180 DEG C-230 DEG C by temperature control type monomer reaction device of the present invention, preferably control between about 190 DEG C-210 DEG C, be while 100% in guarantee reaction percent conversion, restrained effectively the carrying out of reaction B, that is, by reacting the conversion rate control of B at about 1%-4%, prevent from consuming a large amount of hydrogen.
But, although conventional reactor assembly makes the conversion ratio of reaction A be 100%, but due to the restriction of low heat emission efficiency and internal structure, reaction temperature can be caused too high, catalyst activity reduction, thus make the conversion ratio of reaction B greatly improve (such as, conversion ratio is about 10%, even up to about 38%), this makes a large amount of hydrogen be consumed, even and if adopt multiple stainless steel reactor and multiple cooling heat radiation system, can not very effectively control to react the conversion ratio of B, and this layout also add the complexity of system, cost is caused to increase.
Therefore, temperature control type monomer reaction device of the present invention improves hydrogen production efficiency generally.Such as, about embodiment 1 and comparative example 1, in initial reaction gas, each content of material is identical, passed into after carrying out carbon monoxide preferential methanation reaction in temperature control type monomer reaction device of the present invention and conventional reactor system respectively, the conversion ratio reacting B in embodiment 1 is 4%, hydrogen flowing quantity becomes 5.8g/min, improves about 1 times (react the conversion ratio of B in comparative example 1 up to 38%, hydrogen flowing quantity is 2.95g/min) than the hydrogen flowing quantity in comparative example 1; Embodiment 2 is compared with comparative example 2, and hydrogen flowing quantity also improves about 15%.
In addition, the high thermal conductivity coefficient of aluminum alloy materials is made full use of and effective radiator structure controls to realize efficient temperature due to the temperature control type monomer reaction device in present system, eliminate local overheating phenomenon, reaction temperature is controlled between about 180 DEG C-230 DEG C, preferably control between about 190 DEG C-210 DEG C, ensure that the activity of catalyst can not be subject to the impact of excessive temperature, the reaction time is long, enables temperature control type monomer reaction device of the present invention more effectively keep operating efficiency.In addition, temperature control type monomer reaction device structure of the present invention is simple, and manufacturing cost is reduced.
Should be understood that the present invention is not limited to the above embodiment and embodiment.When not departing from connotation of the present invention, any for improvement of the present invention, modification or amendment, within the protection range being all intended to be included in appending claims of the present invention.
Claims (16)
1. a temperature control type monomer reaction device, for be supplied to fuel cell system, the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, it is characterized in that, this temperature control type monomer reaction device comprises:
A housing;
An entrance, is arranged on the housing, to introduce described reacting gas;
An outlet, is arranged on the housing, to discharge described reacting gas;
The main line of multiple hollow, for placing catalyst, described multiple main line to be encapsulated in described housing and with described entrance and described outlet, each main line is furnished with the aluminium alloy vane of one or more lamination shape within it;
A temperature control device, comprising:
Multiple radiating component, stacked up and down with described multiple main line, wherein radiating component
Alternately stacking with main line, with one on the other side mode be arranged in described shell
Body is inner, and each radiating component is formed by the aluminium alloy vane of one or more lamination shape;
At least one pair of Cooling Holes, arranges relative to one another on the housing, is communicated with respectively with radiating component, and for being communicated with the cooling system of at least one outside;
Wherein, the reaction temperature in described main line controls at 180 DEG C-230 DEG C by described temperature control device;
Wherein, the aluminium alloy vane of described multiple lamination shape is in alignment with each other ground horizontal arrangement, alternately horizontal arrangement or be in tilted layout each other at angle.
2. the temperature control type monomer reaction device of claim 1, is characterized in that, the catalyst placed in main line or arrange is ruthenium catalyst, and this ruthenium catalyst is loaded catalyst or coating type catalyst.
3. the temperature control type monomer reaction device of claim 1, is characterized in that, the thickness of the aluminium alloy vane of each lamination shape is 0.1mm to 2mm, and has square, triangle or the corrugated cross sectional shape of semicircle.
4. the temperature control type monomer reaction device of claim 1 or 2, it is characterized in that, described catalyst is filled in described main line in granular form.
5. the temperature control type monomer reaction device of claim 1 or 2, is characterized in that, described catalyst-coated is on the inwall of described main line.
6. the temperature control type monomer reaction device of claim 5, it is characterized in that, the catalyst be coated on the inwall of described main line has the thickness of 0.5mm to 2.0mm.
7. the temperature control type monomer reaction device of claim 1, is characterized in that, described fuel reforming reaction is carburretion reforming reaction, fuel autothermal reforming reaction or fuel meat oxyreforming reaction.
8. the temperature control type monomer reaction device of claim 1, is characterized in that, described temperature control type monomer reaction device is made up of aluminium alloy, but also can be become by stainless steel or copper.
9. the temperature control type monomer reaction device of claim 1, is characterized in that, described fuel cell system is low-temperature protonic exchange film fuel battery system.
10. the temperature control type monomer reaction device of claim 1, it is characterized in that, the reaction temperature in described main line controls at 190 DEG C-210 DEG C by described temperature control device.
The temperature control type monomer reaction device of 11. claims 2, is characterized in that, described loaded catalyst uses with fixed bed form, is benchmark by vehicle weight, for pressing the 5-20%Ru/Al that metal calculates
2o
3or press the 5-20%Ru/SiO of metal calculating
2; Described coating type catalyst is used for reactor wall with coating form, based on total coating weight, the content of ruthenium is the 5-20%Ru calculated by metal, and coating is silicon sol solution or the Alumina gel solution of ruthenium soluble-salt, coated, be attached to the inwall of reactor main line.
The temperature control type monomer reaction device of 12. claims 1, is characterized in that, the aluminium alloy vane of described multiple lamination shape is in tilted layout each other in 120 ° to 175 ° ground.
13. 1 kinds utilize the temperature control type monomer reaction device any one of claim 1-12 carry out to be supplied to fuel cell system, the method for the carbon monoxide preferential methanation reaction of reacting gas that obtained by fuel reforming reaction, it is characterized in that, the reaction temperature of carbon monoxide preferential methanation reaction is controlled at 180 DEG C-230 DEG C.
The method of 14. claims 13, wherein adopts ruthenium catalyst, and this ruthenium catalyst is loaded catalyst or coating type catalyst.
The method of 15. claims 13, wherein controls the reaction temperature of carbon monoxide preferential methanation reaction at 190 DEG C-210 DEG C.
The method of 16. claims 14, wherein said loaded catalyst uses with fixed bed form, is benchmark by vehicle weight, for pressing the 5-20%Ru/Al that metal calculates
2o
3or press the 5-20%Ru/SiO of metal calculating
2; Described coating type catalyst is used for reactor wall with coating form, based on total coating weight, the content of ruthenium is the 5-20%Ru calculated by metal, and coating is silicon sol solution or the Alumina gel solution of ruthenium soluble-salt, coated, be attached to the inwall of reactor main line.
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| CN101128257A (en) * | 2004-11-12 | 2008-02-20 | 万罗赛斯公司 | Process using microchannel technology for conducting alkylation or acylation reaction |
| CN201251378Y (en) * | 2008-05-22 | 2009-06-03 | 董祥顺 | High-efficiency heat radiator |
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| CN101128257A (en) * | 2004-11-12 | 2008-02-20 | 万罗赛斯公司 | Process using microchannel technology for conducting alkylation or acylation reaction |
| CN201251378Y (en) * | 2008-05-22 | 2009-06-03 | 董祥顺 | High-efficiency heat radiator |
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