CN102424361B - Deep removal method for CO in hydrogen-rich gas, and apparatus thereof - Google Patents

Deep removal method for CO in hydrogen-rich gas, and apparatus thereof Download PDF

Info

Publication number
CN102424361B
CN102424361B CN 201110255927 CN201110255927A CN102424361B CN 102424361 B CN102424361 B CN 102424361B CN 201110255927 CN201110255927 CN 201110255927 CN 201110255927 A CN201110255927 A CN 201110255927A CN 102424361 B CN102424361 B CN 102424361B
Authority
CN
China
Prior art keywords
bed reactor
fixed
catalyzer
hydrogen
air
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 201110255927
Other languages
Chinese (zh)
Other versions
CN102424361A (en
Inventor
解东来
王子良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN 201110255927 priority Critical patent/CN102424361B/en
Publication of CN102424361A publication Critical patent/CN102424361A/en
Application granted granted Critical
Publication of CN102424361B publication Critical patent/CN102424361B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The present invention discloses a deep removal method for CO in hydrogen-rich gas, and an apparatus thereof. A fixed bed reactor of the apparatus comprises a reactor cylinder, an upper flange and a lower flange. The reactor cylinder is respectively connected with the upper flange and the lower flange by bolts. The upper flange is provided with a raw gas inlet pipe. The lower flange is provided with a product gas extracting pipe. A Pt/gamma-Al2O3 catalyst and gamma-Al2O3 particles are sequentially loaded in the reactor cylinder in a layering manner. The fixed bed reactor is provided with an air distributor. The opening of the air distributor is arranged in the Pt/gamma-Al2O3 catalyst bed layer. The temperature measurement point of a multi-point thermocouple is arranged in the Pt/gamma-Al2O3 catalyst. The reactor cylinder is surrounded by a water vapor jacket. With the present invention, the direct docking of the apparatus of the present invention and the hydrogen-rich synthesis gas produced by fossil fuel reforming and hydrogen production can be achieved; the start speed is rapid; the installation and the disassembly are easy to perform; the apparatus has a small volume, and the occupied area is small.

Description

CO deep removal method and device in a kind of hydrogen-rich gas
Technical field
The present invention relates to method and the device of the CO preferential oxidation of CO in a kind of deep removal hydrogen-rich gas, be used to Proton Exchange Membrane Fuel Cells that the hydrogen-rich synthetic gas of CO content below 10ppm is provided.
Background technology
Fuel cell is the high efficient energy sources transfer equipment that a kind of chemical energy with fuel is converted into electric energy.At present, the Proton Exchange Membrane Fuel Cells of technical development comparative maturity has strict requirement to CO content in fuel in application process, and general requirement is less than 10ppm.Therefore, need the CO in hydrogen rich gas is carried out deep removal (＜10ppm) just can the act as a fuel fuel of battery.The CO preferential oxidation is one of most effectual way of removing at present CO in hydrogen-rich gas, and prior oxidation of co in hydrogen-riched gas is one of gordian technique of fuel cell unstripped gas preparation.
Adopt the preferential oxidation technology, the CO in reformed gas is removed to below 10ppm, reduce the air intake, improve hydrogen yield, the design of preferential oxidation reactor is gordian technique wherein.At present, preferential oxidation reactor mainly contains following several: multistage Oxygenation device, membrane reactor and micro passage reaction.The structure that multistage advances oxygen reactor is relatively simple, and reactivity worth is better, but still needs to be optimized configuration, oxygen feeding amount and heat transfer structure into the oxygen zone, improves the selectivity of catalysts, improves the performance that multistage advances oxygen reactor.Membrane reactor has the advantage of its uniqueness, namely obtains highly purified target product, but the power resources of reaction gas by film be gas in the pressure difference of film both sides, need unstripped gas that higher pressure is arranged.Micro passage reaction can enhanced reactor heat transfer, mass-transfer performance, with respect to traditional fixed-bed reactor, be applied to the reaction of CO preferential oxidation and have some superiority.
The principle of work of CO preferential oxidation is to pass into O in reformed gas 2, O 2With respect to hydrogen preferential oxidation CO, so both removed CO, avoided simultaneously the consumption of hydrogen.CO preferential oxidation process can be down to the concentration of CO below 10ppm by the reactor design of optimization and the catalyzer of highly selective, in oxidation CO, reduces as far as possible the oxidation of H2, guarantees the efficient of whole fuel cell system.Its main reaction process is:
Figure BDA0000088143230000011
ΔH (298)＝-283kJ/mol (1)
Issuable side reaction is:
Figure BDA0000088143230000012
ΔH (298)＝-242kJ/mol (2)
Figure BDA0000088143230000021
ΔH (298)＝-41.1kJ/mol (3)
Summary of the invention
The object of the invention is to overcome the shortcoming of existing fixed-bed reactor, CO deep removal method and device in a kind of hydrogen-rich gas are provided, it is efficient, quick and safe that the present invention has advantages of, the hydrogen-rich synthetic gas that this device adopts the fossil oil reformation to obtain is unstripped gas, compact construction, handled easily, volume is little, is easy to install.
Purpose of the present invention is achieved through the following technical solutions:
A kind of deep removing device for CO in hydrogen-rich gas comprises fixed-bed reactor, Pt/ γ-Al 2O 3Catalyzer, γ-Al 2O 3Particle, air-distributor, multipoint thermocouple, water vapor chuck and thermal insulation layer; Fixed-bed reactor comprise reactor shell, upper flange and lower flange, and reactor shell is bolted with upper flange and lower flange respectively, and upper flange is equipped with the unstripped gas inlet pipe; Lower flange is equipped with the gas product fairlead; Pt/ γ-Al 2O 3Catalyzer and γ-Al 2O 3Particle layering successively fills in reactor shell; Air-distributor is installed on fixed-bed reactor, and the air-distributor opening is arranged at Pt/ γ-Al 2O 3In beds, be used for providing air to reaction; Multipoint thermocouple is installed on fixed-bed reactor, and the point for measuring temperature of multipoint thermocouple is positioned at Pt/ γ-Al 2O 3In catalyzer, be used for the monitoring temperature of reaction; Reactor shell is surrounded by the water vapor chuck, and water vapor chuck bottom is connected with the water vapor inlet tube, and water vapor chuck top is connected with the water vapor fairlead, and the water vapor inlet tube is provided with valve; On water vapor chuck and fixed-bed reactor, lower flange covers with thermal insulation layer.
Further, described Pt/ γ-Al 2O 3Catalyzer is for being carried on γ-Al 2O 3Pt catalyzer on particle, the mass loading amount of Pt is 0.5%～2.0%; γ-Al 2O 3The particle diameter of carrier is 2～5mm, and the micropore size in particle is 5～10nm, and micropore specific area is greater than 270m 2/ g, Pt/ γ-Al 2O 3The CO air speed of catalyzer is 20～100h -1The CO air speed refer to the ratio of volume of CO flow in treatable unstripped gas and catalyzer;
Described Pt/ γ-Al 2O 3Loaded catalyst
Figure BDA0000088143230000022
Wherein: F is the volumetric flow rate (m of CO in unstripped gas 3/ h), v is the CO air speed (h of catalyzer -1).
Described γ-Al 2O 3Particle is selected γ-Al with Pt/ 2O 3The particle that support of the catalyst is same; γ-Al 2O 3Particle packing amount V 2=0.5V 1～V 1
Described fixed-bed reactor are drum, fixed-bed reactor cavity volume V=V 1+ V 2
Fixed-bed reactor cylinder internal diameter D 1=(15～30) d; Wherein d is γ-Al 2O 3The particle diameter of carrier;
The fixed-bed reactor height
Figure BDA0000088143230000023
V is the fixed-bed reactor cavity volume.
Pt/ γ-Al in described fixed-bed reactor 2O 3Catalyzer and γ-Al 2O 3The type of feed of particle is: press successively from top to bottom 0.25V 1Pt/ γ-Al 2O 3Catalyzer, 0.5V 2γ-Al 2O 3Particle, 0.5V 1Pt/ γ-Al 2O 3Catalyzer, 0.5V 2γ-Al 2O 3Particle, 0.25V 1Pt/ γ-Al 2O 3Catalyzer loads.
Described air-distributor is the stainless steel tube of diameter a 3～6mm, and the air that is drilled with 3 diameter 0.4mm～1.0mm on tube wall is introduced the hole, and the position in three holes lays respectively at three Pt/ γ-Al 2O 3The top of beds; Air-distributor is by the air-distributor access tube access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.
Described multipoint thermocouple is the thermopair that contains 3 points for measuring temperature, is K type, Type B, E or S type thermopair; The position of 3 points for measuring temperature lays respectively at three Pt/ γ-Al 2O 3The middle part of beds; Multipoint thermocouple is by the thermopair access tube access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.
The material of described thermal insulation layer is the ceramic fiber of heatproof more than 150 ℃.
In a kind of hydrogen-rich gas, CO deep removal method, comprise the steps:
The first step, the preheating fixed-bed reactor, superheated vapour is incorporated in the water vapor chuck in the future, the Pt/ γ-Al of heating fixed-bed reactor 2O 3Catalyzer and γ-Al 2O 3Particle, until the temperature-averaging value to 115 that three points for measuring temperature of multipoint thermocouple record～125 ℃;
Second step is passed into by the unstripped gas inlet pipe on upper flange the hydrogen-rich gas that needs the degree of depth to remove CO in fixed-bed reactor, and air is incorporated in fixed-bed reactor by air-distributor; The ratio of the molar flow of the aerial oxygen of flow control of air and the molar flow of the CO in hydrogen containing synthesis gas is 1.5～2.8: 1;
The 3rd step, pass into the normal pressure saturated vapor in the water vapor chuck, the temperature-averaging value that three points for measuring temperature of the flow control multipoint thermocouple by adjusting water vapor record is between 115～125 ℃, CO is oxidation removal in fixed-bed reactor, and the gas that removes CO is derived by the gas product fairlead on lower flange.
The present invention compared with prior art has the following advantages:
1) Pt/ γ-Al in fixed-bed reactor 2O 3Catalyzer adopts the segmentation filling, has overcome the reaction local superheating, has reduced the generation in channel and dead band;
2) use air-distributor, alleviated reaction local superheating and Pt/ γ-Al 2O 3The problems such as reaction bed temperature skewness;
3) use the water vapour chuck to be conducive to heat and get rid of timely, be conducive to fixed-bed reactor and maintain a metastable temperature;
4) reaction operates under normal pressure, and is safe and reliable to operation;
5) fixed-bed reactor is simple in structure, mounts and dismounts convenient and easyly, and device volume is little, and floor space is few.
Description of drawings
Fig. 1 is a kind of structural representation of deep removing device for CO in hydrogen-rich gas.
Embodiment
The invention will be further described below in conjunction with drawings and Examples; following embodiment is only schematic rather than determinate; other staff are under enlightenment of the present invention; under aim of the present invention and claim; can make and representing like multiple types, within such conversion all falls into protection scope of the present invention.
A kind of deep removing device for CO in hydrogen-rich gas comprises fixed-bed reactor 22, Pt/ γ-Al 2O 3Catalyzer 14, γ-Al 2O 3 Particle 15, air-distributor 3, multipoint thermocouple 5, water vapor chuck 11 and thermal insulation layer 12 etc.Fixed-bed reactor 22 comprise reactor shell 10, upper flange 17 and lower flange 18, and reactor shell is fixedly connected with by bolt 19 nuts 20 with lower flange with upper flange respectively.Upper flange 17 is equipped with unstripped gas inlet pipe 1; Lower flange 18 is equipped with gas product fairlead 2, air-distributor access tube 4 and thermopair access tube 6; Be lined with Graphite pad 21 between upper flange 17, lower flange 18 and fixed-bed reactor cylindrical shell 10, adopt bolt 19, nut 20 to be fixedly connected with.Pt/ γ-Al 2O 3Catalyzer 14 and γ-Al 2O 3 Particle 15 layerings fill in fixed-bed reactor 22 cylindrical shells.Air-distributor 3 is installed on fixed-bed reactor, and the opening 16 of air-distributor 3 is positioned at Pt/ γ-Al 2O 3In catalyzer 14 beds, be used for providing air to reaction.Multipoint thermocouple 5 is installed on fixed-bed reactor, and the point for measuring temperature 13 of multipoint thermocouple 5 is positioned at Pt/ γ-Al 2O 3In beds 14, be used for the monitoring temperature of reaction.Reactor shell 10 is surrounded by water vapor chuck 11, is used for utilizing the superheated vapour preheating when fixed-bed reactor 22 start, and carries out the middle saturated vapor that utilizes in reaction and remove the heat that reaction produces.Water vapor chuck 11 and fixed-bed reactor 22 upper flange 17, lower flange 18 use thermal insulation layers 12 coat, to reduce reaction to the heat lost by radiation of surrounding environment; The material of thermal insulation layer is the ceramic fiber of heatproof more than 150 ℃.Air-distributor 3 is the stainless steel tube of diameter a 3～6mm, and the air that is drilled with 3 diameter 0.4mm～1.0mm on tube wall is introduced the hole, and the position in three holes lays respectively at three Pt/ γ-Al 2O 3The top of beds; Air-distributor 3 is by the air-distributor access tube 4 access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.Pt/ γ-Al in fixed-bed reactor 2O 3Catalyzer and γ-Al 2O 3The type of feed of particle is: press successively from top to bottom 0.25V 1Pt/ γ-Al 2O 3Catalyzer, γ-Al of 0.5V2 2O 3Particle, 0.5V 1Pt/ γ-Al 2O 3Catalyzer, 0.5V 2γ-Al 2O 3Particle, 0.25V 1Pt/ γ-Al 2O 3Catalyzer loads.
Pt/ γ-Al 2O 3Catalyzer is for being carried on γ-Al 2O 3Pt catalyzer on particle, the mass loading amount of Pt is 0.5%～2.0%; γ-Al 2O 3The particle diameter of carrier is 2～5mm, and the micropore size in particle is 5～10nm, and micropore specific area is greater than 270m 2/ g, Pt/ γ-Al 2O 3The CO air speed of catalyzer is 20～100h -1The CO air speed refer to the ratio of volume of CO flow in treatable unstripped gas and catalyzer; Pt/ γ-Al 2O 3Loaded catalyst
Figure BDA0000088143230000041
Wherein: F is the volumetric flow rate (m of CO in unstripped gas 3/ h), v is the CO air speed (h of catalyzer -1).
γ-Al 2O 3Particle is selected γ-Al with Pt/ 2O 3The particle that support of the catalyst is same; γ-Al 2O 3Particle packing amount V 2=0.5V 1～V 1
Preferably, fixed-bed reactor 22 are drum, fixed-bed reactor cavity volume V=V 1+ V 2
Fixed-bed reactor cylinder internal diameter D 1=(15～30) d; Wherein d is γ-Al 2O 3The particle diameter of carrier;
The fixed-bed reactor height
Figure BDA0000088143230000051
V is the fixed-bed reactor cavity volume.
Multipoint thermocouple 5 is K type, Type B, E or S type thermopair for containing the thermopair of 3 points for measuring temperature; The position of 3 points for measuring temperature lays respectively at three Pt/ γ-Al 2O 3The middle part of beds; Multipoint thermocouple is by the thermopair access tube 6 access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.
Embodiment
In deep removing device for CO in hydrogen-rich gas, Pt/ γ-Al 2O 3Catalyzer 14 is for being carried on γ-Al 2O 3Pt catalyzer on carrier, the mass loading amount of Pt is 1.0%.γ-Al 2O 3Carrier is from the buying of Tianjin chemical research institute, and particle diameter d is 2.6mm, and the micro-pore diameter in particle is 7nm, and micropore specific area is 280m 2/ g, (application number: 201010191716.6), the suitable CO air speed of the prepared catalyzer ratio of volume of CO flow in treatable unstripped gas and catalyzer () is 30h to the preparation method of catalyzer with reference to China invention -1Pt/ γ-Al that fixed-bed reactor 22 are equipped with 2O 3Catalyzer 14 volumes are 500ml.
γ-Al 2O 3Particle 15 is from the buying of Tianjin chemical research institute, and particle diameter d is 2.6mm, and the aperture in particle is 7nm, and micropore specific area is 280m 2/ g, loadings is 300ml.
Fixed-bed reactor 22 adopt drum, comprise that reactor shell 10, upper flange 17, lower flange 18 3 parts form, and design temperature is 150 ℃; Design pressure is normal pressure.Reactor shell 10 adopts the processing of SS316 stainless steel, volume 800ml, high 200mm, internal diameter 70mm, wall thickness 3mm.
Air-distributor 3 is the stainless steel tube of a diameter 3mm, the air that is drilled with 3 diameter 0.8mm on tube wall is introduced hole 16, the interval that three air are introduced adjacent two of hole is respectively 70mm and 115mm, makes three air introduce hole 16 during installation and lays respectively at three Pt/ γ-Al 2O 3The top of catalyzer 14 beds.Air-distributor is by the air-distributor access tube 4 access fixed-bed reactor 22 of lower flange, and the employing cutting ferrule connects and sealing.
Multipoint thermocouple 5 for containing the thermopair of 3 points for measuring temperature 13, is the K type, and the position of adjacent 2 of 3 points for measuring temperature is interval 90mm and 90mm respectively, makes three points for measuring temperature lay respectively at three Pt/ γ-Al during installation 2O 3The middle part of catalyzer 14 beds.Multipoint thermocouple is by the thermocouple access tube 6 access fixed-bed reactor 22 of lower flange, and the employing cutting ferrule connects and sealing.
Water vapor chuck 11 is peripheral for being surrounded on fixed-bed reactor 22 cylindrical shells, the inner diameter D of described water vapor chuck 2With the D outer diameter than reactor shell 1Large 2mm～5mm.The ring-like gas communication passage that the SS316 stainless steel tube that is 80mm by wall and the another one internal diameter of fixed-bed reactor 22 cylindrical shells forms; 150 ℃ of design temperatures; Design pressure is normal pressure.The water vapor inlet tube 7 of diameter 8mm is established in the bottom of stainless steel tube, and the water vapor fairlead 8 of diameter 8mm is established on top, establishes the valve 9 of a nominal diameter 8mm on the water vapor inlet tube, is used for discharging water vapor chuck 11 issuable water of condensation.
The material of thermal insulation layer 12 is resistant to elevated temperatures ceramic fiber, is coated on the upper flange 17, lower flange 18 of water vapor chuck 11 outer walls and fixed-bed reactor 22, and the thickness of thermal insulation layer is 40mm.
The device setting up procedure is as follows:
The first step, preheating fixed-bed reactor 22, the superheated vapour (150 ℃, normal pressure) that will come from other technological processs is incorporated in water vapor chuck 11, the Pt/ γ-Al of heating fixed-bed reactor 22 2O 3Beds and γ-Al 2O 3Particle is until the temperature-averaging value that three points for measuring temperature of multipoint thermocouple record is between 115～125 ℃;
Second step is passed into the hydrogeneous unstripped gas 60L/min that needs the degree of depth to remove CO in fixed-bed reactor 22, and unstripped gas consists of (percent by volume): 0.45%CO, 0.34%CH 4, 16.55%CO 2, 50.25%H 2, N 2Balance is incorporated into air in fixed-bed reactor 22 by air-distributor 3.The ratio of the molar flow of the aerial oxygen of flow control of air and the molar flow of the CO in hydrogen containing synthesis gas is 2.5, and flow is 0.675L/min.
The 3rd step passed into the normal pressure saturated vapor in water vapor chuck 11, the temperature-averaging value that three points for measuring temperature of the flow control multipoint thermocouple by adjusting water vapor record is between 115～125 ℃.CO is oxidation removal in fixed-bed reactor, and the gas that removes CO is derived by the gas product fairlead on lower flange.
Before the reaction beginning, first beds being preheating to medial temperature is 120 ℃, and this moment, the beds upper temp was more even, and there is the temperature difference of 10 ℃ of left and right in the middle part, and fixed-bed reactor 22 temperature of lower are 130 ℃ of left and right.Reaction is carried out 20min rear catalyst bed upper temp and is on average risen 20 ℃, and beds radially maximum temperature difference only has 4 ℃, and radially heat transfer property is fine.The beds middle portion temperature difference further dwindles, and average the rising only has 15 ℃, and radial temperature difference is less than 10 ℃, and the temperature in the middle part of bed still will be lower than fixed-bed reactor 22 tops.After testing, the CO transformation efficiency is that 99.9%, CO concentration is 6ppm.
When reaction finishes, first stop supplies air, then stop supplies hydrogen containing synthesis gas stops the saturated vapor supply at last.After fixed-bed reactor 22 temperature are reduced to room temperature, discharge the water coolant of the water vapor that in the water vapor chuck, the Yin Wendu reduction produces by the valve on water vapor fairlead 8.

Claims (9)

1. a deep removing device for CO in hydrogen-rich gas, is characterized in that, comprises fixed-bed reactor, Pt/ γ-Al 2O 3Catalyzer, γ-Al 2O 3Particle, air-distributor, multipoint thermocouple, water vapor chuck and thermal insulation layer; Fixed-bed reactor comprise reactor shell, upper flange and lower flange, and reactor shell is bolted with upper flange and lower flange respectively, and upper flange is equipped with the unstripped gas inlet pipe; Lower flange is equipped with the gas product fairlead; Pt/ γ-Al 2O 3Catalyzer and γ-Al 2O 3Particle layering successively fills in reactor shell; Air-distributor is installed on fixed-bed reactor, and the air-distributor opening is arranged at Pt/ γ-Al 2O 3In beds, be used for providing air to reaction; Multipoint thermocouple is installed on fixed-bed reactor, and the point for measuring temperature of multipoint thermocouple is positioned at Pt/ γ-Al 2O 3In catalyzer, be used for the monitoring temperature of reaction; Reactor shell is surrounded by the water vapor chuck, and water vapor chuck bottom is connected with the water vapor inlet tube, and water vapor chuck top is connected with the water vapor fairlead, and the water vapor inlet tube is provided with valve; On water vapor chuck and fixed-bed reactor, lower flange covers with thermal insulation layer.
2. deep removing device for CO in hydrogen-rich gas according to claim 1, is characterized in that: described Pt/ γ-Al 2O 3Catalyzer is for being carried on γ-Al 2O 3Pt catalyzer on particle, the mass loading amount of Pt is 0.5% ~ 2.0%; γ-Al 2O 3The particle diameter of carrier is 2 ~ 5mm, and the micropore size in particle is 5 ~ 10 nm, and micropore specific area is greater than 270m 2/ g, Pt/ γ-Al 2O 3The CO air speed of catalyzer is 20 ~ 100 h -1The CO air speed refer to the ratio of volume of CO flow in treatable unstripped gas and catalyzer;
Described Pt/ γ-Al 2O 3Loaded catalyst
Figure 2011102559276100001DEST_PATH_IMAGE001
Wherein: FBe the volumetric flow rate of CO in unstripped gas, ν is the CO air speed of catalyzer.
3. deep removing device for CO in hydrogen-rich gas according to claim 2, is characterized in that: described γ-Al 2O 3Particle is selected γ-Al with Pt/ 2O 3The particle that support of the catalyst is same; γ-Al 2O 3The particle packing amount
Figure 543453DEST_PATH_IMAGE002
4. deep removing device for CO in hydrogen-rich gas according to claim 3, it is characterized in that: described fixed-bed reactor are drum, the fixed-bed reactor cavity volume
Figure DEST_PATH_IMAGE003
The fixed-bed reactor cylinder internal diameter
Figure 585228DEST_PATH_IMAGE004
Wherein dBe γ-Al 2O 3The particle diameter of carrier;
The fixed-bed reactor height
Figure DEST_PATH_IMAGE005
VBe the fixed-bed reactor cavity volume.
5. deep removing device for CO in hydrogen-rich gas according to claim 4, is characterized in that: Pt/ γ-Al in described fixed-bed reactor 2O 3Catalyzer and γ-Al 2O 3The type of feed of particle is: from top to bottom successively by 0.25 V 1Pt/ γ-Al 2O 3Catalyzer, 0.5 V 2γ-Al 2O 3Particle, 0.5 V 1Pt/ γ-Al 2O 3Catalyzer, 0.5 V 2γ-Al 2O 3Particle, 0.25 V 1Pt/ γ-Al 2O 3Catalyzer loads.
6. deep removing device for CO in hydrogen-rich gas according to claim 1, it is characterized in that: described air-distributor is the stainless steel tube of diameter a 3 ~ 6mm, the air that is drilled with 3 diameter 0.4 mm ~ 1.0 mm on tube wall is introduced the hole, and the position in three holes lays respectively at three Pt/ γ-Al 2O 3The top of beds; Air-distributor is by the air-distributor access tube access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.
7. deep removing device for CO in hydrogen-rich gas according to claim 1, it is characterized in that: described multipoint thermocouple is the thermopair that contains 3 points for measuring temperature, is K type, Type B, E or S type thermopair; The position of 3 points for measuring temperature lays respectively at three Pt/ γ-Al 2O 3The middle part of beds; Multipoint thermocouple is by the thermopair access tube access fixed-bed reactor of lower flange, and the employing cutting ferrule connects and sealing.
8. deep removing device for CO in hydrogen-rich gas according to claim 1, it is characterized in that: the material of described thermal insulation layer is the ceramic fiber of heatproof more than 150 ℃.
9. CO deep removal method in the hydrogen-rich gas of the described device of application rights requirement 1-8 any one, is characterized in that, comprises the steps:
The first step, the preheating fixed-bed reactor are incorporated into superheated vapour in the water vapor chuck, the Pt/ γ-Al of heating fixed-bed reactor 2O 3Catalyzer and γ-Al 2O 3Particle, until the temperature-averaging value to 115 that three points for measuring temperature of multipoint thermocouple record ~ 125 ℃;
Second step is passed into by the unstripped gas inlet pipe on upper flange the hydrogen-rich gas that needs the degree of depth to remove CO in fixed-bed reactor, and air is incorporated in fixed-bed reactor by air-distributor; The ratio of the molar flow of the aerial oxygen of flow control of air and the molar flow of the CO in hydrogen containing synthesis gas is 1.5 ~ 2.8:1;
The 3rd step, pass into the normal pressure saturated vapor in the water vapor chuck, the temperature-averaging value that three points for measuring temperature of the flow control multipoint thermocouple by adjusting water vapor record is between 115 ~ 125 ℃, CO is oxidation removal in fixed-bed reactor, and the gas that removes CO is derived by the gas product fairlead on lower flange.
CN 201110255927 2011-08-31 2011-08-31 Deep removal method for CO in hydrogen-rich gas, and apparatus thereof Expired - Fee Related CN102424361B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110255927 CN102424361B (en) 2011-08-31 2011-08-31 Deep removal method for CO in hydrogen-rich gas, and apparatus thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110255927 CN102424361B (en) 2011-08-31 2011-08-31 Deep removal method for CO in hydrogen-rich gas, and apparatus thereof

Publications (2)

Publication Number Publication Date
CN102424361A CN102424361A (en) 2012-04-25
CN102424361B true CN102424361B (en) 2013-05-08

Family

ID=45958405

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110255927 Expired - Fee Related CN102424361B (en) 2011-08-31 2011-08-31 Deep removal method for CO in hydrogen-rich gas, and apparatus thereof

Country Status (1)

Country Link
CN (1) CN102424361B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129732B (en) * 2015-09-18 2017-10-20 华南理工大学 A kind of use fluid bed carries out deep removal CO preferential oxidation method and device
CN108083228B (en) * 2017-12-04 2019-09-13 大连大学 A kind of method of micro CO in removing hydrogen-rich gas

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1243096A (en) * 1998-07-29 2000-02-02 松下电器产业株式会社 Hydrogen refining apparatus
CN202246046U (en) * 2011-08-31 2012-05-30 华南理工大学 Deep removing device for CO in hydrogen-rich gas

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100669393B1 (en) * 2005-07-22 2007-01-16 삼성에스디아이 주식회사 Catalyst for reformer used in fuel cell system, reformer, and fuel cell system comprising same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1243096A (en) * 1998-07-29 2000-02-02 松下电器产业株式会社 Hydrogen refining apparatus
CN202246046U (en) * 2011-08-31 2012-05-30 华南理工大学 Deep removing device for CO in hydrogen-rich gas

Also Published As

Publication number Publication date
CN102424361A (en) 2012-04-25

Similar Documents

Publication Publication Date Title
CN101208264B (en) Compact reforming reactor
EP1899046B1 (en) Compact reforming reactor
CN101837955B (en) Method for producing hydrogen through coupled catalytic reforming and membrane separation reaction, and device thereof
CN101177240B (en) Integrated device for preparing hydrogen by the recapitalization of dimethyl ether aqueous vapor and method
CN106132529A (en) Pseudo-isothermal reactor
CN110171804B (en) Hydrogen production and purification integrated device and use method
CN103086325A (en) Natural gas hydrogen production reactor and hydrogen production process thereof
CN102424361B (en) Deep removal method for CO in hydrogen-rich gas, and apparatus thereof
CN203525669U (en) Non-equidistant cold plate radial baffle reactor
CN202246046U (en) Deep removing device for CO in hydrogen-rich gas
CN102826507A (en) Method and device of hydrogen production by natural gas and steam reforming for micro fuel cells
CN204643838U (en) Based on the residual air heat exchange combustion-supporting system of methanol-water hydrogen production system employing reforming technology
JP5312355B2 (en) Reactor and reaction product manufacturing method using the same
CN103980091B (en) A kind of preparing methanol from coke oven gas system
CN102133512B (en) Reactor applied to gas-phase exothermic reaction
CN204981129U (en) Adopt fluidized bed to carry out degree of depth desorption CO's preferential oxidation unit
CN105129732B (en) A kind of use fluid bed carries out deep removal CO preferential oxidation method and device
CN101966472B (en) Device for reducing catalyst for catalytic synthesis of dimethyl ether by one-step method
CN201245575Y (en) Water cooled low-voltage methyl alcohol converter synthesizing tower
CN202715401U (en) Fixed bed catalytic reaction device capable of adjusting temperature of material at inlet
CN102452641A (en) Method for recovering Fischer-Tropsch synthesis technology purge gas
CN201603549U (en) Reactor suitable for gas phase heat generating reaction
CN102744018B (en) Fixed bed catalytic reaction device with adjustable inlet material temperature
CN202730075U (en) Temperature control type methanol-to-gasoline synthesis reactor
CN202191894U (en) Dimethyl ether synthesis reactor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130508

Termination date: 20150831

EXPY Termination of patent right or utility model