CN117945346A - Method for purifying hydrogen for fuel cell - Google Patents
Method for purifying hydrogen for fuel cell Download PDFInfo
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- CN117945346A CN117945346A CN202211289333.1A CN202211289333A CN117945346A CN 117945346 A CN117945346 A CN 117945346A CN 202211289333 A CN202211289333 A CN 202211289333A CN 117945346 A CN117945346 A CN 117945346A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 105
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 105
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000446 fuel Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 100
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 7
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract 3
- 239000000945 filler Substances 0.000 claims description 32
- 238000005470 impregnation Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 26
- 238000001179 sorption measurement Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 17
- 239000003463 adsorbent Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 239000012763 reinforcing filler Substances 0.000 description 6
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
Abstract
The invention provides a method for purifying hydrogen for a fuel cell, which comprises the following steps: reducing the catalyst with hydrogen to obtain a reduction catalyst; treating carbon oxide impurities in hydrogen for fuel cells with a reduction catalyst; the catalyst comprises an alumina carrier, a nickel compound and an auxiliary metal compound, wherein the nickel compound and the auxiliary metal compound are supported on the alumina carrier, the nickel content is 5-50wt% based on the weight of the catalyst, and the auxiliary metal content is 0.01-10wt% based on the element; in the reduction catalyst, the dispersity of nickel is 0.5-5%; the particle size of nickel is 10-100 nm. The catalyst is obtained by centrifugally spraying and dipping the dipping liquid on a rotary alumina carrier, and then drying and roasting. The catalyst of the invention has smaller nickel particle size and nickel dispersity, and can show more excellent low-temperature catalytic activity in purifying carbon oxides in hydrogen for fuel cells.
Description
Technical Field
The invention belongs to the field of hydrogen energy, and particularly relates to a method for purifying hydrogen for a fuel cell.
Background
The hydrogen energy has the advantages of wide source, high heat value, cleanness, no pollution, wide application range and the like, and is one of the indispensable energy carriers for improving the energy structure and promoting the energy revolution in the future. The development of the hydrogen energy industry has been focused on the traffic field, mainly focusing on the development of hydrogen fuel cell vehicles, the construction of hydrogen stations and the like, and the application of hydrogen energy in rail transit in the future is another important point.
Currently, china is the first big world for producing hydrogen, and the annual hydrogen production of China is about 2200 ten thousand tons, which accounts for 1/3 of the world hydrogen production. The large-scale hydrogen production is a mature technology in the world and China, but it is worth noting that the China hydrogen is mainly from coal hydrogen production or industrial byproduct hydrogen at present, including propane, ethane dehydrogenation, chlor-alkali industrial byproduct hydrogen, coal methanol purge gas and the like. The industrial hydrogen is purified by Pressure Swing Adsorption (PSA) technology by enterprises to obtain the general industrial hydrogen. The following table shows the results of analysis of hydrogen for a particular business industry.
From the analysis results of the above table, it is known that the Pressure Swing Adsorption (PSA) outlet industrial hydrogen has the highest content of carbon monoxide (CO) in impurities, followed by nitrogen (calculated as N 2 + Ar); the carbon dioxide (CO 2) content is extremely low. In contrast to the national standard GB/T37244 for hydrogen for fuel cells, it is necessary to further reduce the carbon monoxide (CO) content of hydrogen to achieve the standard for hydrogen for fuel cells.
Currently, the process of further purifying industrial hydrogen to produce hydrogen for fuel cells is still based on Pressure Swing Adsorption (PSA) technology. Pressure Swing Adsorption (PSA) is a gas separation technique that relies on pressure changes to adsorb and regenerate different components of a gas using an adsorbent. The Pressure Swing Adsorption (PSA) technology consists of a plurality of adsorption tanks, each adsorption tank is filled with adsorbents with the same filling sequence, and impurities in gas passing through a bed layer are adsorbed by utilizing the characteristic that the adsorbents have weak adsorption capability on hydrogen components in mixed gas and strong adsorption capability on other components, so that high-purity hydrogen is obtained. During the regeneration of the adsorbent, impurities adsorbed on the adsorbent are desorbed and discharged into a desorption gas system through a reverse desorption process and the like. In a typical Pressure Swing Adsorption (PSA) hydrogen purification process, the gas in the feedstock enters the adsorption tank from bottom to top, sequentially passes through adsorbents with different functions, is adsorbed by impurities, has higher and higher purity, and finally reaches the top to become high-purity hydrogen. In general, the first layer of the adsorption tank from bottom to top is an activated alumina adsorbent for removing water; the second layer of adsorbent is special silica gel for removing water and carbon dioxide (CO 2); the third layer of adsorbent is special activated carbon for strongly removing carbon dioxide (CO 2); the fourth layer is a metal complexing adsorbent of an active carbon carrier and is used for removing carbon monoxide (CO); the fifth layer is a 5A molecular sieve, which is used for carrying out fine removal on methane (CH 4), nitrogen (N 2) and carbon monoxide (CO) in hydrogen to ensure the final purity of the product.
Although the Pressure Swing Adsorption (PSA) process is mature, the operation is complicated and complicated, and the adsorbent needs to be frequently desorbed and regenerated. In addition, the purity of hydrogen in the desorption gas generated at the time of the adsorbent regeneration is still high. In fuel cell hydrogen production, the amount of desorbed gas typically accounts for over 20% of the Pressure Swing Adsorption (PSA) industrial hydrogen feed. Because the Pressure Swing Adsorption (PSA) desorption gas pressure is normal, hydrogen is extremely low in pressure and difficult to use despite high purity, and can only be discharged to a flare system as low-pressure release gas, and the problems of high value, low use, serious waste and the like are caused. Because fuel cell hydrogen has a severe requirement on impurity content, in order to ensure that impurity removal reaches the standard, the hydrogen yield of the fuel cell hydrogen produced by a Pressure Swing Adsorption (PSA) technology is generally low, and is generally 80% or even lower.
CN 113929056A discloses an integrated adsorption separation device for purifying hydrogen. The device is filled with a large amount of adsorbents with different types, frequent adsorption-desorption operations are needed in the operation process, and the operation is complex.
CN 111377404B system discloses a device and an operation method for preparing high purity hydrogen by PSA. The PSA10-2-4 flow scheme was used with a loading of 41 tons of adsorbent and during operation the product gas and the analysis gas were 49000Nm 3/h and 25035Nm 3/h, respectively. The hydrogen yield is only 66%, which causes a great deal of hydrogen resource waste.
CN 1512615A discloses a technology for preparing hydrogen for fuel cell by converting carbon monoxide (CO) in hydrogen into carbon dioxide (CO 2) using a catalyst and further removing carbon dioxide (CO 2). Specifically, a water gas shift method of carbon monoxide (CO) is used, and hydrogen (H 2) and carbon dioxide (CO 2) are obtained by a reaction of carbon monoxide (CO) with water (H 2 O). Although carbon monoxide (CO) is removed, carbon dioxide (CO 2) and H 2 O are additionally added, and a subsequent separation step is still required.
In summary, a hydrogen purification method for fuel cells is developed, which has high hydrogen utilization rate and simple operation, reduces the content of carbon monoxide (CO) which is a main impurity in industrial hydrogen to be less than 0.2ppm, meets the requirements of the national standard GB/T37244-2018 of fuel cell hydrogen, and has important application value.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for purifying hydrogen for a fuel cell, the catalyst used in the method is prepared by using a rotary reinforced impregnating device, and the prepared catalyst removes trace carbon oxides in the hydrogen through hydrogenation reaction under the gas-solid two-phase condition, so that the carbon oxides in the hydrogen can be removed to be below 0.2ppm, and the hydrogen for the fuel cell meeting the requirements of the national standard GB/T37244-2018 of hydrogen for the fuel cell is obtained.
In order to achieve the above object, the present invention provides a method for purifying hydrogen for a fuel cell, comprising the steps of:
(1) Hydrogen reduction: placing the catalyst in a hydrogen atmosphere for reduction to obtain a reduction catalyst;
(2) Purifying hydrogen: treating carbon oxide impurities in hydrogen for fuel cells with the reduction catalyst;
The catalyst comprises an alumina carrier, a nickel compound and an auxiliary metal compound, wherein the nickel content is 5-50wt%, preferably 10-45wt%, and the auxiliary metal content is 0.01-10wt%, preferably 0.1-1.5wt%, based on the weight of the catalyst;
in the reduction catalyst, the dispersity of nickel is 0.5-5%, preferably 1.0-2.5%; the particle size of nickel is 10 to 100nm, preferably 20 to 65nm.
The invention has the following effects:
(1) The catalyst for purifying the hydrogen for the fuel cell has high dispersivity of nickel components and small average particle size, and shows more excellent low-temperature catalytic activity when purifying the carbon oxide in the hydrogen for the fuel cell.
(2) The invention relates to a preparation method of a catalyst for purifying hydrogen for a fuel cell, which uses a rotary impregnation technology, takes a rotary reinforced impregnation device as catalyst preparation equipment, and the impregnation liquid positioned at the inner side of a rotary filler forms liquid mist and liquid drops under the action of centrifugal force and is sprayed and immersed on an alumina carrier in a carrier ring rotating at the outer side at an extremely high speed. The highly dispersed fine liquid drops, extremely high initial speed and continuously updated phase interface can effectively improve the diffusion permeation rate of the impregnating solution in the pores of the alumina carrier, promote the uniform adsorption of active components on the surface of the alumina carrier, and greatly shorten the impregnating time.
(3) The purification method of the hydrogen for the fuel cell is simple and convenient to operate, carbon oxide impurities in the hydrogen can be purified only through one-step catalytic reaction, the hydrogen yield is high, and the prepared hydrogen meets the hydrogen standard for the fuel cell.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular descriptions of exemplary embodiments of the invention as illustrated in the accompanying drawings wherein like reference numbers generally represent like parts throughout the exemplary embodiments of the invention.
Fig. 1 is a schematic structural view of a catalyst preparation apparatus used in a method for purifying hydrogen for a fuel cell according to the present invention.
Reference numerals illustrate:
101-a first motor; 102-a second motor; 103-rotating the reinforced packed bed; 104-a liquid storage tank; 105-liquid pump; 106-a liquid distributor; 107-rotating packing; 108-a carrier ring; 109-carrier particles; 110-an immersion liquid inlet; 111-impregnation fluid outlet.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
In this disclosure, unless otherwise indicated, terms of orientation such as "upper and lower" are used to generally refer to the upper and lower of the device in normal use, e.g., with reference to the orientation of the drawing of fig. 1, and "inner and outer" are used with respect to the outline of the device. Furthermore, the terms "first, second, third and the like" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first, second, third" may explicitly or implicitly include one or more such feature. In the description of the present disclosure, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The invention provides a method for purifying hydrogen for a fuel cell, which comprises the following steps:
(1) Hydrogen reduction: placing the catalyst in a hydrogen atmosphere for reduction to obtain a reduction catalyst;
(2) Purifying hydrogen: treating carbon oxide impurities in hydrogen for fuel cells with a reduction catalyst;
The catalyst comprises an alumina carrier, a nickel compound and an auxiliary metal compound, wherein the nickel content is 5-50wt%, preferably 10-45wt%, and the auxiliary metal content is 0.01-10wt%, preferably 0.1-1.5wt%, based on the weight of the catalyst;
in the reduction catalyst, the dispersity of nickel is 0.5-5%, preferably 1.0-2.5%; the particle size of nickel is 10 to 100nm, preferably 20 to 65nm.
According to the invention, the nickel compound is nickel oxide; the compound of the auxiliary metal is at least one of oxides of magnesium, calcium, lanthanum, barium and cerium.
According to the invention, the specific surface area of the alumina support is from 100 to 300m 2/g, preferably from 140 to 250m 2/g. The pore volume is 0.5-1.5 m 3/g, preferably 0.7-1.2 m 3/g.
The alumina carrier used in the invention can be a commercial molded alumina carrier, or can be obtained by treating commercial alumina, so long as the obtained alumina carrier meets the requirements of the specific surface area and the pore volume, and the molded alumina carrier produced by Beijing chemical industry research institute is the best according to the preferred embodiment of the invention.
According to the invention, the above catalyst is prepared by a process comprising the steps of:
Taking a salt solution containing nickel and additive metal as impregnating solution, placing an alumina carrier in a carrier ring 108, centrifugally spraying the impregnating solution on the rotating alumina carrier through a rotary filler 107, and drying and roasting the impregnated alumina carrier to obtain the catalyst.
Preferably, the above catalyst is prepared by a process comprising the steps of:
Step one, taking a mixed salt solution containing metal nickel salt and auxiliary metal salt as an impregnating solution;
Step two, loading an alumina carrier into a carrier ring 108, pumping the impregnating solution into a liquid distributor 106 in the center of the rotary filler 107, and uniformly spraying the impregnating solution into the inner side of the rotary filler 107 through the liquid distributor 106;
step three, the impregnating solution on the inner side of the rotary filler 107 is centrifugally sprayed on the alumina carrier in the carrier ring 108 on the outer side by the rotation of the rotary filler 107, and then the impregnated alumina carrier is dried and roasted;
And step four, optionally repeating the operations from the step two to the step three at least once to obtain the catalyst.
According to the present invention, the metal nickel salt is at least one selected from the group consisting of nickel nitrate, nickel sulfate and basic nickel carbonate.
The auxiliary metal salt is selected from at least one of metal salts of magnesium, calcium, lanthanum, barium and cerium, preferably at least one of nitrate, sulfate or carbonate of magnesium, calcium, lanthanum, barium and cerium.
According to the invention, the mass percentage concentration of the metallic nickel in the mixed salt solution is 1-15%, preferably 5-15%. In the mixed salt solution, the mass percentage concentration of the auxiliary metal is 0.01-5%, preferably 0.1-1%.
The specific surface area of the alumina carrier is 100-300 m 2/g, preferably 140-250 m 2/g; the pore volume is 0.5-1.5 m 3/g, preferably 0.7-1.2 m 3/g.
Preferably, the carrier ring 108 is a wire mesh carrier ring in accordance with the present invention.
Preferably, according to the present invention, the rotating packing 107 is a wire mesh or cylindrical packing.
According to the present invention, the rotational speed of the rotary filler 107 is preferably 1000 to 2000rpm.
Preferably, according to the invention, the carrier ring 108 rotates at a speed of 10 to 20rpm.
According to the present invention, it is preferable that the time for the intensified spray is 10 to 30 minutes.
According to the present invention, it is preferable that the drying temperature is 100 to 120℃and the time is 2 to 10 hours.
According to the present invention, it is preferable that the baking temperature is 400 to 600℃for 2 to 10 hours.
In the present invention, the rotary packing 107 may be a stainless steel wire mesh packing or a stainless steel column packing.
According to the invention, the preparation of the catalyst is carried out in a rotary intensified impregnation device, which comprises: a rotating reinforced packed bed 103, a liquid storage tank 104, a liquid pump 105, a first motor 101 and a second motor 102;
the rotary reinforced packed bed 103 is of a cylindrical structure, a liquid distributor 106 is arranged in the center, and an impregnating liquid outlet 111 is arranged at the lower end and used for discharging the impregnating liquid which is not impregnated and returning the impregnating liquid to the liquid storage tank 104;
The outer side of the liquid distributor 106 is sequentially provided with a rotary filler 107 and a carrier ring 108, and carrier particles 109 are filled in the carrier ring 108;
the liquid distributor 106, the rotary packing 107 and the carrier ring 108 are all cylindrical structures;
The first motor 101 is used for driving the carrier ring 108 to rotate and controlling the rotating speed, and the second motor 102 is used for driving the rotary filler 107 to rotate and controlling the rotating speed;
one end of the liquid distributor 106 is closed, the other end is provided with an impregnating liquid inlet 110, and a plurality of spraying holes are uniformly distributed on the cylinder wall and are used for spraying the impregnating liquid into the inner side of the rotary filler 107;
An inlet of the liquid pump 105 is connected to the liquid reservoir 104, and an outlet is connected to the dip inlet 110 for pumping dip in the liquid reservoir 104 into the liquid distributor 106.
In the invention, under the action of high-speed centrifugal force, the impregnating solution is sheared into tiny liquid microelements by the rotary filler 107, and is contacted with carrier particles 109 in the carrier ring 108 at an extremely high tangential initial speed; the carrier ring 108 rotates at a low speed to ensure that the carrier particles 109 are in sufficient contact with the impregnating liquid microelements; the immersed liquid returns to the liquid storage tank 104 for liquid circulation.
According to the present invention, it is preferable that the temperature of hydrogen reduction is 400 to 500 ℃ and the time of reduction is 2 to 8 hours.
According to the present invention, a method for treating carbon oxide impurities in hydrogen for a fuel cell with a reduction catalyst may be: the catalyst is contacted with hydrogen for the fuel cell, for example, the catalyst is charged into a fixed bed reactor, and then the hydrogen for the fuel cell is passed through the fixed bed reactor.
According to the present invention, the temperature of the hydrogen purge is preferably 100 to 200 ℃. The pressure of hydrogen purification is 0.1-10 MPa.
Preferably, the hydrogen space velocity for the hydrogen purged fuel cell is less than 5000h -1 according to the present invention.
According to the present invention, it is preferable that the concentration of carbon oxides in the hydrogen gas for the hydrogen-purged fuel cell is less than 50ppm.
In the method, the purification of hydrogen for fuel cells is carried out in a fixed bed reactor, hydrogen is introduced into the catalyst to reduce partial nickel oxide into active nickel in the methanation catalyst before the catalyst reacts with the hydrogen containing carbon oxides, and then a trace amount of hydrogen-rich gas containing carbon oxides is contacted with the catalyst to remove the carbon oxides.
The present invention will be described in more detail with reference to examples.
The test instruments and test conditions used in the examples are as follows:
The specific surface area parameter (BET) and the pore volume parameter are both measured by the (N 2) adsorption and desorption method.
The dispersity of the nickel component and the average nickel particle size were measured by hydrogen chemisorption.
The sources of the raw materials used in the examples are as follows:
The molded alumina carrier is produced by Beijing chemical industry institute;
other reagents were all commercially available and analytically pure.
The rotary intensified impregnation apparatus used for the preparation of the catalyst is shown in fig. 1, and comprises: a rotating reinforced packed bed 103, a liquid storage tank 104, a liquid pump 105, a first motor 101 and a second motor 102;
the rotary reinforced packed bed 103 is of a cylindrical structure, a liquid distributor 106 is arranged in the center, and an impregnating liquid outlet 111 is arranged at the lower end and used for discharging the impregnating liquid which is not impregnated and returning the impregnating liquid to the liquid storage tank 104;
The outer side of the liquid distributor 106 is sequentially provided with a rotary filler 107 and a carrier ring 108, and carrier particles 109 are filled in the carrier ring 108;
the liquid distributor 106, the rotary packing 107 and the carrier ring 108 are all cylindrical structures;
The first motor 101 is used for driving the carrier ring 108 to rotate and controlling the rotating speed, and the second motor 102 is used for driving the rotary filler 107 to rotate and controlling the rotating speed;
one end of the liquid distributor 106 is closed, the other end is provided with an impregnating liquid inlet 110, and a plurality of spraying holes are uniformly distributed on the cylinder wall and are used for spraying the impregnating liquid into the inner side of the rotary filler 107;
An inlet of the liquid pump 105 is connected to the liquid reservoir 104, and an outlet is connected to the dip inlet 110 for pumping dip in the liquid reservoir 104 into the liquid distributor 106.
Preparation example 1
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 143m 2/g, pore volume: 0.74m 3/g, manufactured by Beijing chemical research institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and magnesium nitrate (containing 15wt% of nickel and 0.5wt% of magnesium) was placed into a liquid storage tank 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, the catalyst precursor was taken out after reinforcing impregnation for 30 minutes, and then dried at 120℃for 4 hours and calcined at 600℃for 6 hours. Repeating the steps for two times to obtain the catalyst with 39% of nickel and 0.40% of magnesium, which is marked as A1.
Preparation example 2
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 143m 2/g, pore volume: 0.74m 3/g, manufactured by Beijing chemical research institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and calcium nitrate (containing 15wt% of nickel and 0.5wt% of calcium) was placed into a liquid storage tank 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, the catalyst precursor was taken out after reinforcing impregnation for 30 minutes, and then dried at 120℃for 4 hours and calcined at 600℃for 6 hours. Repeating the steps for two times to obtain the catalyst with 39% of nickel and 0.37% of calcium, which is marked as A2.
Preparation example 3
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 143m 2/g, pore volume: 0.74m 3/g, manufactured by Beijing chemical institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and lanthanum nitrate (containing 15wt% of nickel and 0.5wt% of lanthanum) was placed into a liquid storage tank 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, the catalyst precursor was taken out after reinforcing impregnation for 30 minutes, and then dried at 120℃for 4 hours and calcined at 600℃for 6 hours. Repeating the steps for two times to obtain the catalyst with the nickel content of 39% and the lanthanum content of 1.14%, and marking the catalyst as A3.
Preparation example 4
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 143m 2/g, pore volume: 0.74m 3/g, manufactured by Beijing chemical institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and cerium nitrate (containing 15wt% of nickel and 0.5wt% of cerium) was placed into a liquid storage tank 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, the catalyst precursor was taken out after reinforcing impregnation for 30 minutes, and then dried at 120℃for 4 hours and calcined at 600℃for 6 hours. Repeating the steps for two times to obtain the catalyst with 39% of nickel and 1.15% of cerium, which is marked as A4.
Preparation example 5
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 193m 2/g, pore volume: 0.94m 3/g, produced by Beijing chemical institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and lanthanum nitrate (containing 15wt% of nickel and 0.5wt% of lanthanum) was placed into a liquid reservoir 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, and a catalyst precursor was taken out after reinforcing impregnation for 30 minutes. Drying at 120deg.C for 4 hr and calcining at 600deg.C for 6 hr. Repeating the steps for two times to obtain the catalyst with the nickel content of 40% and the lanthanum content of 1.14%, and recording the catalyst as A5.
Preparation example 6
With the catalyst preparation apparatus shown in FIG. 1, 50g of a molded alumina carrier (BET specific surface area: 231m 2/g, pore volume: 1.20m 3/g, produced by Beijing chemical institute) was charged into a wire mesh carrier ring, an impregnation liquid containing nickel nitrate and lanthanum nitrate (containing 15wt% of nickel and 0.5wt% of lanthanum) was placed into a liquid storage tank 104, a rotating reinforcing filler bed 103 was started, the rotational speed of the rotating filler 107 was 2000rpm, the rotational speed of the wire mesh carrier ring was 10rpm, the impregnation liquid was pumped into a liquid distributor 106 by a liquid pump 105, the catalyst precursor was taken out after reinforcing impregnation for 30 minutes, and then dried at 120℃for 4 hours and calcined at 600℃for 6 hours. Repeating the steps for two times to obtain the catalyst with the nickel content of 41% and the lanthanum content of 1.15%, and recording the catalyst as A6.
Comparative example 1
A50 g shaped alumina carrier (BET specific surface area: 143m 2/g, pore volume: 0.74m 3/g, manufactured by Beijing chemical institute) was impregnated with a nickel nitrate/magnesium nitrate impregnation solution containing 15wt% of nickel and 0.5wt% of magnesium by a conventional equivalent impregnation method, and then dried at 100℃for 10 hours and calcined at 400℃for 10 hours. Repeating the steps of soaking, drying and roasting twice to finally obtain the catalyst with the nickel content of 39% and the magnesium content of 0.40%, which is marked as D1.
Test example 1
The catalyst samples of A1-6 and D1 are subjected to chemical pulse adsorption characterization of hydrogen, and the specific method is as follows: the sample was reduced in a hydrogen atmosphere at 450 ℃ for 4 hours, kept at 450 ℃ for 2 hours with argon purge, cooled to 45 ℃, pulse adsorbed with 10% hydrogen-argon mixture at this temperature, and finally the nickel dispersity and nickel particle size of the reduction catalyst were obtained, and the results are shown in table 1.
TABLE 1
Example 1
Taking 10ml of catalyst samples from A1-6 and D1, respectively loading the catalyst samples into a stainless steel fixed bed reactor, introducing high-purity hydrogen with the flow rate of 300ml/min, heating to 450 ℃, and reducing the catalyst samples for 4 hours; switching to high purity nitrogen gas with flow rate of 300ml/min, and introducing raw material gas with CO+CO 2 content of 50ppm when the temperature is reduced to a set value, wherein other conditions are listed in Table 2. The composition of the reacted gas was analyzed using gas chromatography and the detector was FID.
TABLE 2
Compared with the method for removing carbon oxides in hydrogen for fuel cells by the PSA method commonly used in the industry at present, the catalytic method has higher hydrogen yield; and the operation process is simple, the concentration of the carbon oxide can be reduced to below 0.2ppm by only one-step reaction, and repeated desorption and regeneration operations are not needed.
In addition, the catalysts A1 to 6 prepared in the preparation examples 1 to 6 according to the present invention using the preparation apparatus of the catalyst shown in fig. 1 have a higher nickel dispersity and a smaller nickel particle diameter than the catalysts prepared in the conventional equivalent impregnation method of comparative example 1. The alumina carrier is loosely packed in the silk screen carrier ring, and the rotation of the silk screen carrier ring can drive the slow displacement of the carrier, so that the impregnating solution which forms liquid mist and liquid drops under the action of centrifugal force can be uniformly sprayed on the surface of the carrier at extremely high speed.
In addition, in table 2, at the reaction temperatures of 120 and 150 ℃, the concentration of the carbon oxide after the catalytic reaction of A1 is still lower than 0.2ppm, and the catalytic activity of D1 decreases with the decrease of the reaction temperature, thus indicating that although the catalyst prepared by the conventional impregnation and the impregnation method of the present invention can completely remove the carbon oxide in the hydrogen gas for the fuel cell under the high temperature condition, the catalyst prepared by the impregnation method of the present invention has better activity under the low temperature condition because the catalyst of the present invention has smaller nickel particle size and nickel dispersity, and can exhibit more excellent low temperature catalytic activity in the purification of the carbon oxide in the hydrogen gas for the fuel cell.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (10)
1. A method for purifying hydrogen for a fuel cell, said method comprising the steps of:
(1) Hydrogen reduction: placing the catalyst in a hydrogen atmosphere for reduction to obtain a reduction catalyst;
(2) Purifying hydrogen: treating carbon oxide impurities in hydrogen for fuel cells with the reduction catalyst;
The catalyst comprises an alumina carrier, a nickel compound and an auxiliary metal compound, wherein the nickel content is 5-50wt%, preferably 10-45wt%, and the auxiliary metal content is 0.01-10wt%, preferably 0.1-1.5wt%, based on the weight of the catalyst;
in the reduction catalyst, the dispersity of nickel is 0.5-5%, preferably 1.0-2.5%; the particle size of nickel is 10 to 100nm, preferably 20 to 65nm.
2. The purification method of claim 1, wherein the nickel compound is nickel oxide;
the compound of the auxiliary metal is at least one of oxides of magnesium, calcium, lanthanum, barium and cerium.
3. The purification method according to claim 1, characterized in that the specific surface area of the alumina carrier is 100-300 m 2/g, preferably 140-250 m 2/g; the pore volume is 0.5-1.5 m 3/g, preferably 0.7-1.2 m 3/g.
4. The purification process of claim 1, wherein the catalyst is prepared by a process comprising the steps of:
Taking a salt solution containing nickel and additive metal as impregnating solution, placing an alumina carrier in a carrier ring, centrifugally spraying the impregnating solution on the rotating alumina carrier through a rotary filler, and drying and roasting the impregnated alumina carrier to obtain the catalyst.
5. The purification process of claim 4, wherein the catalyst is prepared by a process comprising the steps of:
Step one, taking a mixed salt solution containing metal nickel salt and auxiliary metal salt as an impregnating solution;
Step two, loading an alumina carrier into a carrier ring, pumping the impregnating solution into a liquid distributor in the center of the rotary filler, and uniformly spraying the impregnating solution into the inner side of the rotary filler through the liquid distributor;
Step three, the impregnating solution on the inner side of the rotary filler is centrifugally sprayed and immersed on the alumina carrier in the carrier ring with the outer side rotating through the rotation of the rotary filler, and then the immersed alumina carrier is dried and roasted;
And step four, optionally repeating the operations from the step two to the step three at least once to obtain the catalyst.
6. The method according to claim 5, wherein the metal nickel salt is at least one selected from the group consisting of nickel nitrate, nickel sulfate and basic nickel carbonate;
the auxiliary metal salt is selected from at least one of magnesium, calcium, lanthanum, barium and cerium metal salts, preferably at least one of magnesium, calcium, lanthanum, barium and cerium nitrate, sulfate or carbonate.
7. The purification method according to claim 5, wherein the mass percentage concentration of metallic nickel in the mixed salt solution is 1-15%, preferably 5-15%; the mass percentage concentration of the auxiliary metal is 0.01-5%, preferably 0.1-1%.
8. The method of claim 5, wherein the carrier ring is a wire mesh carrier ring;
The rotary filler is silk screen or cylindrical filler;
The rotating speed of the rotary filler is 1000-2000 rpm;
The rotating speed of the carrier ring is 10-20 rpm;
the time of the intensified spray dipping is 10-30 min;
The drying temperature is 100-120 ℃ and the drying time is 2-10 h;
the roasting temperature is 400-600 ℃ and the roasting time is 2-10 h.
9. The purification method according to any one of claims 4 to 8, wherein the preparation of the catalyst is performed in a rotary intensified impregnation apparatus comprising: the device comprises a rotary reinforced packed bed, a liquid storage tank, a liquid pump, a first motor and a second motor;
the rotary reinforced packed bed is of a cylindrical structure, a liquid distributor is arranged in the center of the rotary reinforced packed bed, and an impregnating liquid outlet is arranged at the lower end of the rotary reinforced packed bed and used for discharging the impregnating liquid which is not impregnated and returning the impregnating liquid to the liquid storage tank;
the outer side of the liquid distributor is sequentially provided with a rotary filler and a carrier ring, and carrier particles are filled in the carrier ring;
the liquid distributor, the rotary filler and the carrier ring are all cylindrical structures;
the first motor is used for driving the carrier ring to rotate and controlling the rotating speed, and the second motor is used for driving the rotary filler to rotate and controlling the rotating speed;
One end of the liquid distributor is closed, the other end of the liquid distributor is provided with an impregnating solution inlet, and a plurality of spraying holes are uniformly distributed on the cylinder wall and are used for spraying the impregnating solution into the inner side of the rotary filler;
The inlet of the liquid pump is connected with the liquid storage tank, and the outlet of the liquid pump is connected with the impregnating liquid inlet and is used for pumping the impregnating liquid in the liquid storage tank into the liquid distributor.
10. The purification method according to claim 1, wherein the hydrogen gas is reduced at 400 to 500 ℃ for 2 to 8 hours;
The temperature of the hydrogen purification is 100-200 ℃;
The pressure of the hydrogen purification is 0.1-10 MPa;
the space velocity of the hydrogen for the fuel cell purified by the hydrogen is less than 5000h -1;
the concentration of carbon oxides in the hydrogen for the hydrogen-purified fuel cell is less than 50ppm.
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