CN107601430B - Based on CaFe2O4/Ca2Fe2O5Method and device for catalytic circulation hydrogen production and carbon dioxide co-capture - Google Patents
Based on CaFe2O4/Ca2Fe2O5Method and device for catalytic circulation hydrogen production and carbon dioxide co-capture Download PDFInfo
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- CN107601430B CN107601430B CN201710871723.2A CN201710871723A CN107601430B CN 107601430 B CN107601430 B CN 107601430B CN 201710871723 A CN201710871723 A CN 201710871723A CN 107601430 B CN107601430 B CN 107601430B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
Abstract
The invention discloses a method based on CaFe2O4/Ca2Fe2O5The method adopts CaFe to prepare hydrogen and capture carbon dioxide cooperatively by catalytic cycle hydrogen production and a device thereof2O4And Ca2Fe2O5The composite calcium-iron powder is reacted in one step to prepare high-purity hydrogen and capture carbon dioxide, and the reaction is carried out circularly. The device is a stacked circulating fluidized bed or a nested fluidized bed. The invention has the following advantages: the invention is based on CaFe2O4/Ca2Fe2O5The method for preparing hydrogen by catalyzing and circulating hydrogen and capturing carbon dioxide is used for preparing hydrogen by one-step reaction, and can capture carbon dioxide and high-purity hydrogen simultaneously; CaFe used in the method of the invention2O4And Ca2Fe2O5Compared with the iron-based and calcium-based oxygen carriers which are used independently, the oxygen carrier has better strength, is beneficial to being used in a fluidized bed, has shorter reaction time, is not easy to inactivate, and has high purity of the prepared hydrogen; the stacked circulating fluidized bed and the nested circulating fluidized bed device have simple structures and can effectively capture carbon dioxide and high-purity hydrogen.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide capture, relates to a chemical-looping hydrogen production technology, and particularly relates to a CaFe-based hydrogen production technology2O4/Ca2Fe2O5The method and the device for the catalytic cycle hydrogen production and the carbon dioxide capture.
Background
The basic principle of chemical looping hydrogen production is that the conventional combustion of direct contact reaction of fuel and air is decomposed into 2 gas-solid reactions by the action of an Oxygen carrier (Oxygen carrier), the fuel and the air do not need to be in contact, and the Oxygen in the air is transferred into the fuel by the Oxygen carrier.
In the prior chemical looping hydrogen production process, the hydrogen production is divided into gas fuel and solid fuel, wherein the gas fuel hydrogen production process mainly uses an iron-based oxygen carrier, and the solid fuel hydrogen production process mainly uses an iron-based or calcium-based oxygen carrier. The chemical looping combustion and hydrogen production technology is also a key technology in the national important research subjects of clean coal technology, solid waste treatment and the like.
The iron-based oxygen carrier has low fuel conversion efficiency and carbon dioxide removal efficiency, long reaction time, three-step chemical reaction, and relatively complex reaction device structure. The calcium-based oxygen carrier has weak structural strength and easy surface sintering, which easily leads to the inactivation of the calcium-based catalyst after multiple times of circulating catalysis.
Disclosure of Invention
The technical problem to be solved is as follows: in order to overcome the defects of the prior art and obtain a method capable of preparing high-purity hydrogen through one-step reaction and simultaneously capturing carbon dioxide, the invention provides a method based on CaFe2O4/Ca2Fe2O5The method and the device for the catalytic cycle hydrogen production and the carbon dioxide capture.
The technical scheme is as follows: based on CaFe2O4/Ca2Fe2O5The method adopts CaFe2O4And Ca2Fe2O5The composite calcium-iron powder is reacted in one step to prepare high-purity hydrogen and capture carbon dioxide, and the reaction is carried out circularly.
Preferably, the reaction requires addition of a gas or solid fuel, which is one of carbon monoxide, methane or coal.
Preferably, the reaction is of the formula:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2(1)
CaFe2O4+3CO→CaO+2Fe+3CO2(2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2(3)
CaO+2Fe+3H2O→CaFe2O4+3H2(4)
as shown in FIG. 1, a catalyst based on CaFe2O4/Ca2Fe2O5The device for the catalytic circulation hydrogen production and the carbon dioxide capture is a stacked circulating fluidized bed and comprises a riser, a fuel reactor and a steam reactor, wherein the riser is positioned above the fuel reactor, and the lower part of the fuel reactor is communicated with the lower part of the steam reactor through a U-shaped material returning valve B; the upper part of the steam reactor is communicated with the lower part of the riser and the upper part of the fuel reactor through a cyclone separator B, a vertical pipe and a U-shaped material returning valve C; the upper part of the lifting pipe is communicated with a cyclone separator A, and the cyclone separator A is communicated with the fuel reactor through a return pipe and a U-shaped return valve A; and an air distribution plate is arranged below the fuel reactor.
As shown in FIG. 2, a CaFe-based alloy2O4/Ca2Fe2O5The device for the catalytic circulation hydrogen production and the carbon dioxide capture is a nested fluidized bed and comprises a vertical pipe, a fuel reactor, a steam reactor and a fuel reactor injection device, wherein the fuel reactor consists of at least one pipeline penetrating through the steam reactor; the fuel reactor injection device is positioned below a pipeline of the fuel reactor, and the upper part of the fuel reactor is communicated with the lower part of the water vapor reactor through a cyclone separator A, a vertical pipe and a U-shaped return valve A in sequence; a steam reactor chamber is arranged below the steam reactor, and an air distribution plate is arranged between the steam reactor chamber and the steam reactor chamber; the upper part of the water vapor reactor is communicated with the fuel reactor injection device through a cyclone separator B, a return pipe and a U-shaped return valve B.
Has the advantages that: (1) the invention is based on CaFe2O4/Ca2Fe2O5The method for preparing hydrogen by catalyzing and circulating hydrogen and capturing carbon dioxide is used for preparing hydrogen by one-step reaction, and can capture carbon dioxide and high-purity hydrogen simultaneously; (2) CaFe used in the method of the invention2O4And Ca2Fe2O5Compared with the iron-based and calcium-based oxygen carriers which are used independently, the oxygen carrier has better strength, is beneficial to being used in a fluidized bed, has shorter reaction time, is not easy to inactivate, and has high purity of the prepared hydrogen; (3) the stacked circulating fluidized bed and the nested circulating fluidized bed device have simple structures and can effectively capture carbon dioxide and high-purity hydrogen.
Drawings
FIG. 1 is a schematic structural view of a stacked circulating fluidized bed;
the system comprises a cyclone separator 1, a vertical pipe 10, a cyclone separator B11, a riser pipe 12, a return pipe 13, a U-shaped return valve A14, an air distribution plate 15, a U-shaped return valve B16, a fuel reactor 17, a steam reactor 18 and a U-shaped return valve C19, wherein the cyclone separator A is arranged on the top of the vertical pipe, the air distribution plate B is arranged on the bottom of the vertical pipe, the fuel reactor B is arranged on the bottom of;
FIG. 2 is a schematic structural view of a nested circulating fluidized bed;
the system comprises a cyclone separator A2, a cyclone separator B20, a fuel reactor 21, a vertical pipe 22, a U-shaped return valve A23, a steam reactor 24, an air distribution plate 25, a steam reactor chamber 26, a fuel reactor injection device 27, a U-shaped return valve B28 and a return pipe 29, wherein the cyclone separator A is a cyclone separator A, the cyclone separator B20 is a fuel reactor B, the air distribution plate 25 is a steam reactor chamber 26;
FIG. 3 is a reaction scheme; a is a schematic diagram of carbon dioxide capture by calcium circulation hydrogen production, and b is a schematic diagram of carbon dioxide capture by calcium-iron composite powder circulation hydrogen production.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
Based on CaFe2O4/Ca2Fe2O5The method adopts CaFe2O4And Ca2Fe2O5The composite calcium-iron powder is reacted in one step to prepare high-purity hydrogen and capture carbon dioxide, and the reaction is carried out circularly.
In the reaction, gas or solid fuel is required to be added, and carbon monoxide is selected in the embodiment.
The reaction is represented by the following formula:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2(1)
CaFe2O4+3CO→CaO+2Fe+3CO2(2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2(3)
CaO+2Fe+3H2O→CaFe2O4+3H2(4)
the above reaction was carried out using a stacked circulating fluidized bed as shown in FIG. 1, the apparatus being:
based on CaFe2O4/Ca2Fe2O5The device for the catalytic circulation hydrogen production and the carbon dioxide capture is a stacked circulating fluidized bed and comprises a riser 12, a fuel reactor 17 and a steam reactor 18, wherein the riser 12 is positioned above the fuel reactor 17, and the lower part of the fuel reactor 17 is communicated with the lower part of the steam reactor 18 through a U-shaped material returning valve B16; the upper part of the steam reactor 18 is communicated with the lower part of the riser 12 and the upper part of the fuel reactor 17 through a cyclone separator B11, a riser 10 and a U-shaped material returning valve C19; the upper part of the riser 12 is communicated with a cyclone separator A1, and the cyclone separator A1 is communicated with a fuel reactor 17 through a return pipe 13 and a U-shaped return valve A14; an air distribution plate 15 is arranged below the fuel reactor 17.
The reaction process is as follows: CaFe2O4And Ca2Fe2O5Reacting with carbon monoxide in a fuel reactor 17, and generating calcium oxide, iron simple substance and carbon dioxide as shown in the formula (1) and (2), wherein the calcium oxide and the iron simple substance enter a steam reactor 18 through a U-shaped material returning valve B16 to react with steam to generate Ca2Fe2O5、CaFe2O4And hydrogen, the reaction formula is shown as formula (3) and formula (4). Ca produced2Fe2O5、CaFe2O4And hydrogen is separated by cyclone B11, Ca2Fe2O5、CaFe2O4Enters the riser 10 and enters the riser 12 through a U-shaped return valve C19, and hydrogen and steam enter the condenser to obtain high-purity hydrogen. Ca discharged by carbon dioxide entering the lifting pipe 12 with the U-shaped material returning valve C192Fe2O5And CaFe2O4Enters a cyclone A1 together for gas-solid separation, wherein Ca2Fe2O5And CaFe2O4The carbon dioxide is separated in the cyclone a1 and captured after passing through the condenser, again entering the fuel reactor 17 through the return pipe 13 and the U-shaped return valve a 14.
Example 2
Based on CaFe2O4/Ca2Fe2O5The method adopts CaFe2O4And Ca2Fe2O5The composite calcium-iron powder is reacted in one step to prepare high-purity hydrogen and capture carbon dioxide, and the reaction is carried out circularly.
In the reaction, gas or solid fuel is required to be added, and carbon monoxide is selected in the embodiment.
The reaction is represented by the following formula:
Ca2Fe2O5+3CO→2CaO+2Fe+3CO2(1)
CaFe2O4+3CO→CaO+2Fe+3CO2(2)
2CaO+2Fe+3H2O→Ca2Fe2O5+3H2(3)
CaO+2Fe+3H2O→CaFe2O4+3H2(4)
the above reaction was carried out using a nested circulating fluidized bed as shown in FIG. 2, the apparatus being:
based on CaFe2O4/Ca2Fe2O5The device for the catalytic cycle hydrogen production and the carbon dioxide capture is a nested fluidized bed and comprises a vertical pipe 22, a fuel reactor 21, a steam reactor 24 and a fuel reactor injection device 27, wherein the fuel reactor 21 consists of at least one pipeline penetrating through the steam reactor 24; the fuel reactor ejector 27 is positioned below a pipeline of the fuel reactor 21, and the upper part of the fuel reactor 21 is communicated with the lower part of the water vapor reactor 24 through a cyclone separator A2, a vertical pipe 22 and a U-shaped return valve A23 in sequence; a steam reactor chamber 26 is arranged below the steam reactor 24, and an air distribution plate 25 is arranged between the steam reactor chamber and the steam reactor chamber; the upper part of the water vapor reactor 24 is communicated with the fuel reactor injection device 27 through a cyclone separator B20, a return pipe 29 and a U-shaped return valve B28.
The reaction process is as follows: ca2Fe2O5And CaFe2O4The calcium oxide and the iron simple substance enter the water vapor reactor 24 through the cyclone separator A2, the vertical pipe 22 and the U-shaped return valve A23, and the carbon dioxide is separated by the cyclone separator A2 and collected after passing through a condenser. In the steam reactor 24, the steam firstly enters the steam reactor air chamber 26 and uniformly enters the steam reactor 24 through the air distribution plate 5 to react with the steam to generate Ca2Fe2O5、CaFe2O4And hydrogen, the reaction formula is shown as formula (3) and formula (4). Ca produced2Fe2O5、CaFe2O4And the hydrogen and the excessive water vapor are subjected to gas-solid separation by a cyclone separator B20, and the separated hydrogen and water vapor enter a condenser to obtain high-purity hydrogen and Ca2Fe2O5And CaFe2O4It is returned to the fuel reactor eductor assembly 27 through a return line 29 and a U-shaped return valve B28.
Claims (1)
1. Based on CaFe2O4/Ca2Fe2O5The device for the catalytic circulation hydrogen production and the carbon dioxide capture is characterized by being a nested fluidized bed and comprising a vertical pipe (22), a fuel reactor (21), a steam reactor (24) and a fuel reactor injection device (27), wherein the fuel reactor (21) consists of at least one pipeline penetrating through the steam reactor (24); the fuel reactor injection device (27) is positioned below a pipeline of the fuel reactor (21), and the upper part of the fuel reactor (21) is communicated with the lower part of the water vapor reactor (24) through a cyclone separator A (2), a vertical pipe (22) and a U-shaped material returning valve A (23) in sequence; a steam reactor chamber (26) is arranged below the steam reactor (24), and an air distribution plate (25) is arranged between the steam reactor chamber and the steam reactor chamber; the upper part of the water vapor reactor (24) is communicated with an injection device (27) of the fuel reactor through a cyclone separator B (20), a return pipe (29) and a U-shaped return valve B (28).
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| CN110721691B (en) * | 2019-11-12 | 2020-07-24 | 中南大学 | CFAN catalyst, preparation thereof and application thereof in methane hydrogen production |
| CN112892544B (en) * | 2021-01-18 | 2022-07-05 | 山东大学 | High-activity CaO-based bifunctional material, and preparation method and application thereof |
| CN114229910A (en) * | 2021-11-08 | 2022-03-25 | 宁夏大学 | Calcium-iron dual-function composite oxygen carrier and large-scale preparation method thereof |
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| CN104401938B (en) * | 2014-10-31 | 2016-04-20 | 东南大学 | Be rich in methane gas and prepare H 2the apparatus and method of the synthetic gas that/CO ratio is adjustable |
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| CN101049927A (en) * | 2007-04-18 | 2007-10-10 | 清华大学 | Method for producing Nano carbon tubes continuously and equipment |
| EP1982957A1 (en) * | 2007-04-20 | 2008-10-22 | Air Products and Chemicals, Inc. | Preparation of complex metal oxides |
| CN102977927A (en) * | 2012-11-07 | 2013-03-20 | 东南大学 | Apparatus for preparing synthesis gas based on dual fluidized bed biomass gasification and preparation method thereof |
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