CN102674247B - A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation and device - Google Patents
A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation and device Download PDFInfo
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Abstract
The invention discloses a kind of decarburization and the method for the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation, including: composite catalyst is added in fixing bed palladium film reactor by (1), passes into the mixing gas of hydrogen and nitrogen, reduction composite catalyst; (2) methane, water vapour pass in fixing bed palladium film reactor after preheating, carry out reformation hydrogen production reaction under composite catalyst effect, and the hydrogen of generation passes through palladium film, obtains the purity high-purity hydrogen more than 99.0%; (3) when composite catalyst needs desorption and regeneration, stop passing into methane, water vapour, carry out catalyzer temperature-elevating desorption and regeneration; (4), after composite catalyst regeneration, pass into methane and water vapour carries out hydrogen production reaction; Circulation carries out (2)��(3) step. The invention also discloses a kind of fixing bed palladium film reactor adopting said method to carry out methane steam reforming hydrogen manufacturing. The hydrogen purity that the present invention prepares is high, and energy consumption is low, also improves the service life of palladium film simultaneously.
Description
Technical field
The invention belongs to petrochemical industry, chemical industry and Hydrogen Technology field, be specifically related to method and the device of a kind of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation.
Background technology
Hydrogen, as a kind of clean energy resource, is acknowledged as the desirable alternative fuel of oil and coal, becomes world energy sources study hotspot. Hydrogen, as the energy, mainly utilizes combustion of hydrogen produce the heat energy of high heating value and supply two aspects of generating of fuel cell as hydrogen source. Wherein, the proton membrane fuel battery (PEMFC) of employing platinum electrode catalysis material is low because of its operation temperature, and energy transformation ratio is high, advantages of environment protection, becomes development one important direction of hydrogen fuel cell. But PEMFC hydrogen makes fuel, in hydrogen, the concentration of impurity CO is more low more good, because the CO of trace is just enough to make Pt catalyst poisoning lose efficacy in hydrogen-rich system, thus the stability of extreme influence fuel cell and usability. Although the hydrogen without CO can be obtained with water electrolysis hydrogen production, but hydrogen manufacturing cost high and by using restriction. Therefore, the hydrogen source problem solving low cost purity is the wide variety of important topic of Proton Exchange Membrane Fuel Cells technology.
Methane has the highest hydrogen-carbon ratio, and can carry out reforming reaction with water, and the hydrogen in water vapour is become hydrogen, is the hydrogen production process that the most ripe, cost is minimum in the world at present. Methane resource does not only have fossil energy sources (such as natural gas, combustible ice, coal bed gas etc.), industrial by-product gas (such as coke-stove gas etc.), Renewable resource (such as biogas etc.) can also be derived from, so methane steam reforming hydrogen manufacturing also has absolute cost advantage on raw material sources. Methane steam reformation reaction mainly includes reforming reaction and water-gas shift two-step reaction:
��H298=206.2kJ/mol (1)��H298=-41.1kJ/mol (2)
Due to the restriction balanced by reforming reaction, the H of hydrogen manufacturing gained2Volumetric concentration is about 75%, and this reaction is strong endothermic reaction, it is necessary to methane just can be made to convert thoroughly higher than 900 DEG C. In product gas, CO volumetric concentration reaches 5%-10%, through reaction elimination CO such as methanations, to make device for producing hydrogen complicate before use, and running cost improves.
For preparation low cost for the PEMFC hydrogen used, having a kind of modified method is be coupling on a reactor by the step of methane reforming hydrogen manufacturing and separating hydrogen gas, not only dehydrogenation forced mathane steam reforming reaction in course of reaction, and the hydrogen of generation can be directly separating purification and obtain High Purity Hydrogen (JianhuaTong, YasuyukiMatsumura.Purehydrogenproductionbymethanesteamre formingwithhydrogen-permeablemembranereactor.CatalysisTo day, 2006,111 (3): 147-152.). The method separating hydrogen is to use palladium film, comes into one's own with the research of hydrogen after palladium membrance separation methane reforming. Due to few 2 electronics of the 4d break of palladium atom, surface has stronger hydrogen-absorbing ability, palladium and alloy film thereof have very high hydrogen permselective property, palladium film is combined with methane reforming hydrogen-manufacturing reactor and can improve methane conversion while purifying hydrogen of hydrogen, reduce reaction temperature, reduce reactor volume. Palladium membrance separation can produce suitable in fuel cell, containing only the high-purity hydrogen of PPM rank impurity.
Publication number is CN101648105A, publication number is CN101372314A and Chinese patent that publication number is 101406791A has been respectively adopted palladium film and has purified production high-purity hydrogen from hydrogen containing synthesis gas or coke-stove gas, but not all being directly used in reforming reaction, palladium film is intended only as follow-up hydrogen purification and segregation apparatus uses.
US Patent No. 5,525,322 discloses a kind of isotopic method reclaiming hydrogen and hydrogen from hydrocarbon and water. Utilize the hydrogen in palladium film separation reaction mixing gas, enhance reforming reaction and water gas shift reation, and extra process step need not can obtain high-purity hydrogen. US Patent No. 5,938,800 discloses a kind of close-coupled reforming reactor, utilizes membrane separation technique to purify the hydrogen in hydrocarbon reformation gaseous product in reactor, and the high-purity hydrogen of preparation is used directly for fuel cell. The Chinese patent that publication number is CN1931708A discloses a kind of liquid hydrocarbon method of hydrogen making in palladium film reactor, adopt composition metal palladium film, the hydrogen that liquefied hydrocarbon steam reformation produces is separated in time, then obtains high-purity hydrogen through palladium film side.
An important problem is had: reform the CO, the CO that produce at methane reforming and with in palladium membrance separation pure hydrogen research process2Palladium film surface can be adsorbed on etc. foreign gas, cause the poisoning of palladium film and reduce hydrogen permeability energy. Shi Lei et al. (CH4, CO2, CO on palladium-based composite membrane hydrogen permeability can impact. petrochemical industry, 2007,36 (7): 690-693) have studied the CH of different content4��CO2, CO on the hydrogen permeability of palladium-based composite membrane can impact, result shows CH4Almost without impact, CO2Affecting less, CO has the greatest impact. Temperature is more low or CO content is more high, and CO is more serious in palladium-based composite membrane surface adsorption. At 450 DEG C, when the volume fraction of CO is 2%, the hydrogen volume decline through palladium film is about 7%.
In order to reduce COxImpact on hydrogen product concentration, US Patent No. 5,861,137 proposes to load methanation catalyst and steam reforming catalyst in membrane tube, and mixing gas methanation reaction of reforming reduces the CO of palladium membrane permeation sidexConcentration, but owing to methanation reaction is exothermic reaction, it is desirable to reaction temperature is relatively low, if for, in methane steam reformation reactor, there are two unmatched problems of reaction temperature. Therefore, directly with methane steam reforming hydrogen manufacturing because CO concentration is high, performance and life-span to the separating hydrogen gas of palladium film have a significant impact, and are difficult to the advantage of palladium membrance separation hydrogen forced mathane hydrogen manufacturing.
The another kind of method improved is referred to as reaction adsorption forced methane steam reforming (ReSER) hydrogen producing technology. What applicant proposed first adds nanometer CaO by reforming catalyst, by nanoscale CaO and CO2The CO that reaction elimination reforming reaction produces2Reach the purpose of powerforming reaction, and to use containing NiO be reformation catalytic reaction active component with nanometer CaO as CO2The composite catalyst of reaction absorbed component. Methane ReSER hydrogen production reaction formula is shown in (3) (4):
��H298=164.9kJ/mol (3)
��H298=-178.8kJ/mol (4)
Composite catalyst containing NiO and CaO, by the CO that calcium oxide produces with methane reforming2Reaction adsorbing separation, reforming reaction balance is made to move to generating hydrogen direction, a reactor realizes reform and conversion two-step reaction, reduce nearly 200 DEG C of reaction temperature, not only efficient hardening reforming reaction, and directly obtain the hydrogen of more than 90% content of low CO concentration (about 500ppm). Additionally, make full use of the reaction heat of (3) (4) heat absorption and heat release, reach powerforming reaction and energy-conservation purpose. Inventor (InternationalJournalOfHydrogenEnergy, 2010,35 (13): 6518-6524) research shows reaction temperature 600 DEG C, when the reaction adsorption forced methane steam reforming hydrogen manufacturing of reaction pressure 0.1MPa and steam/hydrocarbons ratio 4, and ZrO2Modified Ni based composite catalyst can directly prepare the H of concentration 97.3%2, methane conversion is 93.7%, and has good stability.
Inventor's a kind of method for preparing composite catalyst for carbon dioxide adsorption forced methane steam reforming hydrogen manufacturing disclosed in the Chinese patent that publication number is CN1903431A; A kind of adsorption forced methane steam reforming hydrogen manufacturing process adopting fixed bed reactors and device disclosed in the Chinese patent that publication number is CN1974375A. In the Chinese patent that publication number is CN1935634A, disclose a kind of adsorption forced methane steam reforming hydrogen manufacturing process adopting recirculating fluidized bed, composite catalyst is through pretreatment, after reduction under fluidized state composite catalyst and methane, water vapour carries out reformation hydrogen production reaction, transfers to regenerator regeneration, recycle after using, realize stability and the seriality of fluidized bed process, there is mass transfer, advantage that heat transfer efficiency is high.
The CO concentration generated due to ReSER hydrogen manufacturing is low, can effectively reduce the impact on palladium film properties, therefore has the potential advantage with palladium film in conjunction with hydrogen manufacturing, for adopting CO absorption simultaneously2Composite catalyst separation carbon dioxide (decarburization) and palladium membrance separation H2(dehydrogenation) dual enhancement on hydrogen production method from methane steam reformation there is no report at present.
Summary of the invention
The present invention provides a kind of with calcium oxide and CO2Reaction adsorbing separation CO2With palladium membrance separation H2The method of dual forced methane steam reforming hydrogen manufacturing, reduces temperature and the energy consumption of hydrogen manufacturing, can directly prepare the purity high-purity hydrogen more than 99%.
A kind of method of decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation, including:
(1) composite catalyst is added in fixing bed palladium film reactor, passes into the mixing gas of hydrogen and nitrogen, reduction composite catalyst;
(2) methane, water vapour pass in fixing bed palladium film reactor after preheating, carry out reformation hydrogen production reaction under composite catalyst effect, and the hydrogen of generation passes through palladium film, obtains the purity high-purity hydrogen more than 99.0%;
(3) when composite catalyst needs desorption and regeneration, stop passing into methane, water vapour, carry out catalyzer temperature-elevating desorption and regeneration;
(4), after composite catalyst regeneration, circulation carries out (2)��(3) step.
Described composite catalyst mainly by the CaO being presoma with micron order and/or nano level calcium carbonate and/or calcium hydroxide powder and with nickelous carbonate, nickel oxide or nickel nitrate be presoma active nickel composition and alumina support be composited, each component molar ratio is: CaO: NiO: Al2O3=1: (0.1��2.0)��(0.1��3.0), prepared by the preparation method of composite catalyst disclosed in the Chinese patent that described composite catalyst can adopt publication number to be CN1903431A, the particle diameter of described composite catalyst is 0.1��5mm, for methane H-H reaction after thermal decomposition regeneration.
In described mixing gas (hydrogen and nitrogen), hydrogen volume concentration is 5%��100%, and the temperature of described reduction is 30��650 DEG C, and the pressure of reduction is 0.1��1MPa.
The condition of described hydrogen production reaction is: reaction temperature is 500��650 DEG C, and reaction pressure is 0.1��1MPa, steam/hydrocarbons ratio 3��6, and palladium film thickness is 5 ��m��50 ��m, carbon space velocity 150��1500h-1��
The condition of described catalyzer temperature-elevating desorption and regeneration is: temperature is 750��950 DEG C, and pressure is normal pressure, and regeneration atmosphere is N2Atmosphere or tail gas, described tail gas be device for producing hydrogen produce tail gas or regenerating unit produce tail gas, described tail gas be with arbitrary proportion mixing H2��CH4��CO��CO2With H2The mixing gas of O.
Present invention also offers a kind of fixing bed palladium film reactor adopting said method to carry out methane steam reforming hydrogen manufacturing, including reaction tube and palladium membrane tube, described reaction tube is from bottom to top, it is followed successively by packing layer and catalyst layer, described reaction tube top is provided with mixed material gas feed, bottom is provided with offgas outlet, and described palladium membrane tube is embedded in catalyst layer, and the top of described palladium membrane tube is connected to the conveying pipe of the high-purity hydrogen that conveying obtains through palladium film.
Described palladium membrane tube is made up of with the palladium film being plated in outside matrix matrix, and described matrix is porous ceramic pipe or porous stainless steel.
It is provided with heater outside described reaction tube, with the temperature in reasonable adjusting reaction tube, is beneficial to the carrying out of hydrogen production reaction and the regeneration of catalyst.
Compared with prior art, the invention have the advantages that
(1) the inventive method adopts the adsorption forced separation carbon dioxide of reaction and the dual forced methane steam reforming technique of palladium membrance separation hydrogen simultaneously, improve methane conversion, reduce reaction temperature, prepare the purity high-purity hydrogen more than 99.0%, can be directly used for the hydrogen source of fuel cell.
(2) present invention adopts composite catalyst and fixing bed palladium film reactor, meets decarburization and the carrying out of the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation from aspects such as catalyst and equipment.
(3) owing to reacting adsorption forced effect, prepared the hydrogen of CO containing low content (about 500ppm), greatly reduced the CO poisoning harm to palladium film, improve the life-span of palladium film and reduce use cost.
(4) the inventive method greatly reduces tradition methane steam reformation reaction condition, reduces energy consumption, it is provided that the hydrogen production process of energy-saving and emission-reduction, is suitable for the methane reforming device for producing hydrogen of different scales.
Accompanying drawing explanation
Fig. 1 is the FB(flow block) of the inventive method.
Fig. 2 is the structural representation of the fixing bed palladium film reactor of the present invention.
Fig. 3 is the dual forced methane steam reforming hydrogen manufacturing process flow chart of the present invention.
Fig. 4 is the graph of relation of methane conversion and hydrogen production reaction temperature in application examples 4 of the present invention, application examples 5.
Fig. 5 is under different temperatures, applies composite catalyst of the present invention and reforming catalyst without CaO and carries out during hydrogen production reaction the graph of relation of CO concentration and reaction temperature in tail gas. (reaction condition: pressure 0.5MPa, steam/hydrocarbons ratio is 4, and the amount of the catalyst of filling is 10g, thickness 5 ��m).
Wherein, in accompanying drawing 2,3: 1-methane steel cylinder, 2-hydrogen gas cylinder, 3-nitrogen cylinder, 4-mass flow controller, 5-precision liquid phase pump, 6-fixes bed palladium film reactor, 7-mass-flow gas meter, 8-gas chromatograph, 9-methane and water vapour, 10-high-purity hydrogen, 11-tail gas (H2��CH4��CO��CO2��H2O), 61-reaction tube, 62-palladium membrane tube, 611-packing layer, 612-catalyst layer.
Detailed description of the invention
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
The preparation of embodiment 1 palladium membrane tube
With porous ceramic pipe for matrix, first clean matrix with dilute hydrochloric acid and distilled water, after removing surface blot, be placed in baking oven in 40 DEG C of dry 5h.
By porous ceramic pipe respectively at SnCl2��PdCl2Solution carries out sensitization activation.
According to constituent content each in 1L chemical plating fluid it is: PdCl22g/L, mass fraction 28% NH3��H2O150ml/L��NH4Cl20g/L��Na2H2PO2��H2O14g/L prepares chemical plating fluid, puts in this chemical plating fluid by the porous matrix after activation, controls pH value between 9��11, and operation temperature is 50 DEG C. When, after bubble collapse in solution, changing chemical plating fluid.
After 4 hours chemical platings, forming dense palladium film at porous ceramic pipe matrix surface, after cleaning with distilled water, at 40 DEG C, dry 12h obtains palladium membrane tube.
The thickness of the palladium film of the palladium membrane tube that the present embodiment prepares is 5 ��m, and saturating hydrogen speed can reach 0.122mol/ (m2��s)��
The preparation of embodiment 2 palladium membrane tube
With porous ceramic pipe for matrix, first clean matrix with dilute hydrochloric acid and distilled water, remove surface blot, then be placed in baking oven in 40 DEG C of dry 5h with distilled water flushing.
By porous ceramic pipe respectively at SnCl2��PdCl2Solution carries out sensitization activation.
According to constituent content each in 1L chemical plating fluid it is: PdCl22g/L, mass fraction 28% NH3��H2O150ml/L��NH4Cl20g/L��Na2H2PO2��H2O14g/L prepares chemical plating fluid, puts in this chemical plating fluid by the porous matrix after activation, controls pH value between 9��11, and operation temperature is 50 DEG C. When, after bubble collapse in solution, changing chemical plating fluid.
After 8 hours chemical platings, form dense palladium film at porous palladium membrane tube matrix surface. After cleaning with distilled water, at 40 DEG C, dry 12h obtains palladium membrane tube.
The thickness of the palladium film of the palladium membrane tube that the present embodiment prepares is 50 ��m, and saturating hydrogen speed can reach 0.015mol/ (m2��s)��
The fixing palladium film reactor of application examples 1
As shown in Figure 2, a kind of fixing bed palladium film reactor 6, including reaction tube 61 and palladium membrane tube 62, reaction tube 61 from bottom to top, is followed successively by packing layer 611 and catalyst layer 612, reaction tube 61 top is provided with mixed material gas feed, bottom is provided with offgas outlet, is provided with heater outside reaction tube 61, and palladium membrane tube 62 is embedded in catalyst layer 612, palladium membrane tube 62 is made up of with the palladium film being plated in outside porous ceramic pipe porous ceramic pipe, and the top of palladium membrane tube 62 is connected to the conveying pipe of conveying high-purity hydrogen.
The fresh composite catalyst (preparation method refers to the Chinese patent that publication number is CN1903431A) of mean diameter 1 millimeter is seated in fixing bed palladium film reactor 6, passes into the mixing gas reducing catalyst of hydrogen and nitrogen. After reduction, the mixing gas of raw material methane and water vapour enters in fixing bed palladium film reactor 6, carries out methane steam reforming hydrogen manufacturing reaction.
The technique of the dual forced methane steam reforming hydrogen manufacturing reaction of application examples 2
As shown in Figure 3, adopt the technique that fixing bed palladium film reactor as shown in Figure 2 carries out dual forced methane steam reforming hydrogen manufacturing reaction, the flow of methane, hydrogen, nitrogen is controlled respectively by three mass flowmenters 4, water vapour is by accurate liquid phase pump 5 water filling, gas enters fixing bed palladium film reactor 6 and reacts, hydrogen can pass through palladium film, and exit gas is detected flow by mass-flow gas meter 7 respectively, is then analyzed each constituent content of gas by gas chromatograph 8 respectively again.
Should use-case select palladium membrane tube be embodiment 1 preparation palladium membrane tube, palladium film thickness is 5 ��m, and hydrogen production reaction condition is: reaction temperature 500 DEG C, reaction pressure 1MPa, steam/hydrocarbons ratio is 4, methane flow 15ml/min, the amount of the composite catalyst of filling is 10g, result: methane conversion is 76.5%; High-purity hydrogen concentration: 99.01%, each material molar concentration (butt) of tail gas: CH4It is 17.8%, CO2Being 0.6%, CO is 0.05%, H2It is 81.5%.
Application examples 3
The technique adopting dual forced methane steam reforming hydrogen manufacturing carries out hydrogen production reaction, and wherein, the palladium membrane tube of employing is the palladium membrane tube of embodiment 2 preparation, and palladium film thickness is 50 ��m. Hydrogen production reaction condition: reaction temperature 500 DEG C, reaction pressure 0.5MPa, steam/hydrocarbons ratio is 4, methane flow 15ml/min, and the amount of the composite catalyst of filling is 10g. Result: methane conversion is 73.4%; High-purity hydrogen concentration: 99.9%, each material molar concentration (butt) of tail gas: CH4It is 13.1%, CO2Being 0.4%, CO is 0.05%, H2It is 86.5%.
Application examples 4
The technique adopting dual forced methane steam reforming hydrogen manufacturing carries out hydrogen production reaction, and wherein, the palladium membrane tube of employing is the palladium membrane tube of embodiment 1 preparation, and palladium film thickness is 5 ��m. Hydrogen production reaction condition: reaction temperature 550 DEG C, reaction pressure 0.5MPa, steam/hydrocarbons ratio is 4, methane flow 15ml/min, and the amount of the composite catalyst of filling is 10g. Result: methane conversion is 94.5%; High-purity hydrogen concentration: 99.1%, each material molar concentration (butt) of tail gas: CH4It is 3.1%, CO2Being 0.3%, CO is 0.06%, H2It is 96.6%.
Application examples 5
The technique adopting dual forced methane steam reforming hydrogen manufacturing carries out hydrogen production reaction, and wherein, the palladium membrane tube of employing is the palladium membrane tube of embodiment 1 preparation, and palladium film thickness is 50 ��m. Hydrogen production reaction condition: reaction temperature 650 DEG C, reaction pressure 1MPa, steam/hydrocarbons ratio is 6, methane flow 15ml/min, and the amount of the composite catalyst of filling is 5g. Result: methane conversion is 98.9%; High-purity hydrogen concentration: 99.9%, each material molar concentration (butt) of tail gas: CH4It is 1.0%, CO2Being 0.9%, CO is 0.28%, H2It is 97.7%.
Comparative example 1
Such as Fig. 2 and fixing bed palladium film reactor as shown in Figure 3 is adopted not to react adsorption forced methane steam reforming hydrogen manufacturing.
Wherein, the catalyst of employing is the catalyst granules (without CaO adsorbent) containing NiO, and the palladium membrane tube of employing is the palladium membrane tube of embodiment 1 preparation, and palladium film thickness is 50 ��m. Hydrogen production reaction condition: reaction temperature 650 DEG C, reaction pressure 0.5MPa, steam/hydrocarbons ratio is 3, methane flow 15ml/min, and the amount of the catalyst of filling is 5g. Result: methane conversion is 66.6%; The each material molar concentration (butt) of tail gas: CH4It is 11.3%, CO2Being 14.8%, CO is 7.8%, H2It is 66.1%.
Comparative example 2
Adopt as Fig. 2 and fixing bed palladium film reactor as shown in Figure 3 with do not react adsorption forced methane steam reforming hydrogen manufacturing.
Wherein, the catalyst of employing is the catalyst granules (without CaO adsorbent) containing NiO, and the palladium membrane tube of selection is the palladium membrane tube of embodiment 1 preparation, and thickness is 5 ��m. Hydrogen production reaction condition: reaction temperature 650 DEG C, reaction pressure 1MPa, steam/hydrocarbons ratio is 6, methane flow 15ml/min, and the amount of the catalyst of filling is 10g. Result: methane conversion is 79.4%; The each material molar concentration (butt) of tail gas: CH4It is 6.9%, CO2Being 21.5%, CO is 5.31%, H2It is 66.2%.
Claims (1)
1. the method for a decarburization and the dual forced methane steam reforming hydrogen manufacturing of dehydrogenation, it is characterised in that
A kind of fixing bed palladium film reactor, including reaction tube and palladium membrane tube, reaction tube is from bottom to top, being followed successively by packing layer and catalyst layer, reaction tube top is provided with mixed material gas feed, and bottom is provided with offgas outlet, heater it is provided with outside reaction tube, palladium membrane tube is embedded in catalyst layer, and palladium membrane tube is made up of with the palladium film being plated in outside porous ceramic pipe porous ceramic pipe, and the top of palladium membrane tube is connected to the conveying pipe of conveying high-purity hydrogen;
The fresh composite catalyst of mean diameter 1 millimeter is seated in fixing bed palladium film reactor, passes into the mixing gas reducing catalyst of hydrogen and nitrogen; After reduction, the mixing gas of raw material methane and water vapour enters in fixing bed palladium film reactor, carries out methane steam reforming hydrogen manufacturing reaction;
The technique adopting dual forced methane steam reforming hydrogen manufacturing carries out hydrogen production reaction, and wherein, the preparation process of palladium membrane tube is as follows:
With porous ceramic pipe for matrix, first clean matrix with dilute hydrochloric acid and distilled water, after removing surface blot, be placed in baking oven in 40 DEG C of dry 5h;
By porous ceramic pipe respectively at SnCl2��PdCl2Solution carries out sensitization activation;
According to constituent content each in 1L chemical plating fluid it is: PdCl22g/L, mass fraction 28% NH3��H2O150ml/L��NH4Cl20g/L��Na2H2PO2��H2O14g/L prepares chemical plating fluid, puts in this chemical plating fluid by the porous matrix after activation, controls pH value between 9��11, and operation temperature is 50 DEG C; When, after bubble collapse in solution, changing chemical plating fluid;
After 4 hours chemical platings, forming dense palladium film at porous ceramic pipe matrix surface, after cleaning with distilled water, at 40 DEG C, dry 12h obtains palladium membrane tube;
The thickness of the palladium film of described palladium membrane tube is 5 ��m, and saturating hydrogen speed can reach 0.122mol/ (m2S);
Hydrogen production reaction condition: reaction temperature 650 DEG C, reaction pressure 1MPa, steam/hydrocarbons ratio is 6, methane flow 15ml/min, and the amount of the composite catalyst of filling is 5g;
Result: methane conversion is 98.9%; High-purity hydrogen concentration: 99.9%, each material molar concentration (butt) of tail gas: CH4It is 1.0%, CO2Being 0.9%, CO is 0.28%, H2It is 97.7%.
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| CN104176706A (en) * | 2013-05-23 | 2014-12-03 | 中国科学院大连化学物理研究所 | Method for extracting high purity hydrogen from coke oven gas reformed gas |
| CN108686522A (en) * | 2017-04-06 | 2018-10-23 | 中国科学院大连化学物理研究所 | A kind of application of high temperature resistant palladium alloy composite membrane in vapor reforming hydrogen production reaction |
| CN109181800B (en) * | 2018-10-22 | 2024-02-20 | 广东索特能源科技有限公司 | Coupling device for decarbonizing and reforming methane and decarbonizing and reforming system for methane |
| CN110902652A (en) * | 2019-11-20 | 2020-03-24 | 中国科学院广州能源研究所 | On-line separation reforming hydrogen production method capable of enhancing reaction efficiency and device for implementing method |
| CN110975851B (en) * | 2019-12-26 | 2022-06-03 | 江苏南大环保科技有限公司 | Resin desorption regeneration method for adsorbing organic matters |
| CN111960381A (en) * | 2020-08-19 | 2020-11-20 | 大连理工大学 | Hydrocarbon reforming hydrogen production reaction device and method for preventing CO poisoning |
| CN114408866B (en) * | 2022-01-05 | 2023-03-14 | 大连理工大学 | Methane steam reforming reaction device based on high-purity gas product full recovery and use method thereof |
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