CN101973523B - Method for preparing hydrogen gas by taking marsh gas as raw material - Google Patents
Method for preparing hydrogen gas by taking marsh gas as raw material Download PDFInfo
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- CN101973523B CN101973523B CN2010105218635A CN201010521863A CN101973523B CN 101973523 B CN101973523 B CN 101973523B CN 2010105218635 A CN2010105218635 A CN 2010105218635A CN 201010521863 A CN201010521863 A CN 201010521863A CN 101973523 B CN101973523 B CN 101973523B
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Abstract
The invention discloses a method for preparing hydrogen gas by taking marsh gas as a raw material. The method comprises the following steps of: preheating the marsh gas serving as the raw material, desulfurizing, heating, performing a reforming reaction, and the like. The method has a simple process, increases the heat utilization ratio of a device and lowers production cost.
Description
Technical field
The present invention relates to a kind of is the method for raw material for preparing hydrogen with biogas, and what particularly a kind of catalyticcombustion technology provided heat is the method for raw material for preparing hydrogen with biogas.
Background technology
Biogas be organism under anaerobic, a kind of inflammable gas that generates through the fermentative action of mikrobe.Biogas is the mixture of multiple gases, generally contains methane 50～70%, and all the other are carbonic acid gas and a spot of nitrogen, hydrogen and hydrogen sulfide etc.The staple methane of biogas is a kind of ideal geseous fuel, and its colorless and odorless and is an incendivity after an amount of air mixed, and the thermal value of every cubic metre of pure methane is 34000 kilojoules.The thermal value of every cubic metre of biogas is about 20800～23600 kilojoules, promptly after 1 cubic metre of biogas perfect combustion, can produce and is equivalent to the heat that 0.7 kilogram of hard coal provides.Compare with other inflammable gas, the explosion-proof better performances of biogas is a kind of good clean fuel.Biogas also can be made the fuel of oil engine and produce industrial chemicals such as methyl alcohol, Superlysoform, tetracol phenixin except that direct burning is used for cooking, oven dry agricultural byproducts, heating, illumination and gas welding etc.The feed liquid and the sediment of after the firedamp gas equipment fermentation, discharging contain more rich nutritive substance.Can be used as fertilizer and feed.
China is the abundant relatively country of a biogas resource, and it is main utilizing at present more than the biogas with methane-generating pit in China, is the zymotechnique of master's continuously feeding with straw or excrement of animals promptly, and formation is that master's biogas directly burns with CH4 and CO2.The CO that the biogas that directly burns obtains
2And H
2O directly is thrown into atmosphere, CO
2As the products of combustion of oxygenatedchemicals, its quantity discharged is with annual 40% speed increase.Along with Global warming, how to control CO
2The isothermal chamber gaseous emission has become the huge challenge that countries in the world government faces.
At present, the hydrogen preparation method that adopts in the industry comprises methane vapor reforming reaction (SMR) and methane carbon dioxide reformation reaction (CRM).The reaction formula of methane vapor reforming reaction is: CH
4+ H
2O → CO+H
2, this method prepares hydrogen must isolate CO, and technology is loaded down with trivial details; Simultaneously, H in this method
2/ CO>=3 should not be directly as carrying out oxo process and the Fischer-Tropsch synthetic raw material that the degree of depth transforms.The reaction formula of methane carbon dioxide reformation reaction is: CH
4+ CO
2→ 2CO+2H
2, H in this method
2/ CO is about 1, and directly oxo process and the Fischer-Tropsch synthetic desirable feedstock that the degree of depth transforms carried out in conduct, but this reaction is a kind of strong endothermic reaction, needs device that a large amount of heat energy is provided, and has increased production cost.
Summary of the invention
The objective of the invention is to overcome hydrogen preparation method complex process in the prior art, the deficiency that production cost is high, providing a kind of is the method for raw material for preparing hydrogen with biogas.This method technology is simple, has improved the heat energy utilization rate of device, has reduced production cost.
For realizing above-mentioned purpose, the technical solution adopted for the present invention to solve the technical problems is:
A kind of is the method for raw material for preparing hydrogen with biogas, may further comprise the steps:
A, raw material biogas get into desulphurization reactor and carry out desulfurization after first interchanger is heated to 340～360 ℃, and the total sulfur in the gas is controlled at 20mg/m
3Below;
Gas after B, the desulfurization gets into the tube side of shell and tube-type reactor after second interchanger is heated to 580～600 ℃, under the effect of catalyzer, carry out reforming reaction;
C, the gas that obtains among the step B is sent into the CO umformer and overheated steam reacts after the second interchanger heat exchange, the gas that reaction obtains is sent into membrane separation apparatus and is separated, and separates obtaining product hydrogen and device exhaust;
D, the device exhaust that obtains among the step C is sent into the shell side of shell and tube-type reactor, under the effect of catalyzer with air generation catalyst combustion reaction;
E, the high-temperature flue gas of the catalyst combustion reaction that obtains among the step D sent into the first interchanger heat exchange after, send into vapour generator heating de-salted water, the overheated steam that obtains is sent into the CO umformer as reactant gases.
As optimal way, in the said steps A, the pressure of raw material biogas is 1.2MPa.
Among the said step B; Shell and tube-type reactor comprises reactor drum shell side, upper sealing plate and following shrouding; The reactor drum shell side is fixedly connected with following shrouding with upper sealing plate respectively, and the top of said reactor drum shell side is connected with exhanst gas outlet, and the middle part is connected with the secondary air import; Bottom one side is connected with the primary air import, and opposite side is connected with the tail gas inlet mouth; Be connected with conversion tube in the said reactor drum shell side; The two ends of this conversion tube are respectively arranged with convertor flange and reforming gas outlet; The top of conversion tube is connected with the virgin gas inlet mouth, and the set inside of conversion tube has adiabatic plug and conversion catalyst pallet, and said convertor flange is connected with blind flange; Be disposed with first gas distribution grid, second gas distribution grid and the 3rd gas distribution grid in the said reactor drum shell side.
Among the said step C, membrane separation apparatus comprises cavity, inlet end and tail gas outlet side, is provided with palladium membrane component in the said cavity; Said cavity is provided with the hydrogen escape pipe, and the two ends of cavity are respectively arranged with first flange and second flange, and said inlet end is connected with the inlet end end socket; This inlet end end socket is connected with the 3rd flange, and said first flange is fixedly connected with the 3rd flange, also is provided with the inlet end tube sheet between first flange and the 3rd flange; Said tail gas outlet side is connected with the outlet side end socket; This outlet side end socket is connected with the 4th flange, and said second flange is fixedly connected with the 4th flange, also is provided with the outlet side tube sheet between second flange and the 4th flange.
As optimal way, among the said step B, the catalyzer of reforming reaction is that noble metal catalyst or loading type Ni are catalyst based.
Catalyst combustion reaction is meant by catalyzer, realizes at a lower temperature organic complete oxidation.Catalyst combustion reaction is a kind of thermopositive reaction, has less energy consumption, the high advantage of purification efficiency simple to operate, safe.(contain volume percent approximately is 20% CO, 21.6% H to device exhaust in the shell side of shell and tube-type reactor of the present invention
2With 7.5% CH
4) carrying out catalyst combustion reaction with air, the heat that reaction produces passes to the reactor drum tube side through the annular gap that shell and tube-type reactor tube side and shell side constitute, and is the CH in the reactor drum tube side
4-CO
2Reforming reaction provides reaction required heat.Catalyst combustion reaction is reused the tail gas in the process for making hydrogen, has realized making full use of of exhaust heat-energy, and the heat energy utilization rate of whole device has improved about 10%, has reduced energy consumption and production cost.Simultaneously, catalyst combustion reaction has reduced the H in the tail gas
2Concentration realizes trouble-free service, also can reduce the floor space of whole device.
High-temperature flue gas among the present invention (about 800 ℃) is except being that first interchanger provides heat, and outside the preheating material biogas, the another one vital role heats de-salted water exactly, has produced superheated vapour (about 280 ℃), and this superheated vapour is one of virgin gas of CO umformer.Make full use of the heat energy of high-temperature flue gas in the technical process, reduced energy consumption and cost.
It is raw material that the present invention adopts biogas, has reduced by 7～8% CO
2Discharging, have environment protection significance, be specially adapted to be rich in CO
2Natural-gas field, reduced separation of C O
2The expense of bringing, with traditional methane steam reformation reacting phase ratio, cost reduces 4～5%, has environmental protection and economic double meaning.
Beneficial effect of the present invention is: technology of the present invention is simple, has improved the heat energy utilization rate of device, has reduced production cost.
Description of drawings
The present invention will explain through example and with reference to the mode of accompanying drawing, wherein:
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Disclosed all characteristics in this specification sheets, or the step in disclosed all methods or the process except mutually exclusive characteristic and/or the step, all can make up by any way.
Embodiment 1: shown in Fig. 1-3, a kind of is the method for raw material for preparing hydrogen with biogas, may further comprise the steps:
A, normal temperature, pressure be the raw material biogas of 1.2Mpa (G) after first interchanger is heated to 340～360 ℃, get into desulphurization reactor and carry out desulfurization, the total sulfur in the gas is controlled at 20mg/m
3Below;
Gas after B, the desulfurization gets into the tube side of shell and tube-type reactor, at Ni/Al after second interchanger is heated to 580～600 ℃
2O
3Carry out reforming reaction under the effect of catalyzer;
C, the gas that obtains among the step B is sent into the CO umformer and overheated steam reacts after the second interchanger heat exchange, the gas that reaction obtains is sent into membrane separation apparatus and is separated, and separates obtaining product hydrogen and device exhaust;
D, the device exhaust that obtains among the step C is sent into the shell side of shell and tube-type reactor, down and air generation catalyst combustion reaction in, the effect of Mg-Cr-O catalyzer;
E, the high-temperature flue gas of the catalyst combustion reaction that obtains among the step D sent into the first interchanger heat exchange after, send into vapour generator heating de-salted water, the overheated steam that obtains is sent into the CO umformer as reactant gases.
Among the said step B; Shell and tube-type reactor comprises reactor drum shell side, upper sealing plate and following shrouding; The reactor drum shell side is fixedly connected with following shrouding with upper sealing plate respectively, and the top of said reactor drum shell side is connected with exhanst gas outlet, and the middle part is connected with the secondary air import; Bottom one side is connected with the primary air import, and opposite side is connected with the tail gas inlet mouth; Be connected with conversion tube in the said reactor drum shell side; The two ends of this conversion tube are respectively arranged with convertor flange and reforming gas outlet; The top of conversion tube is connected with the virgin gas inlet mouth, and the set inside of conversion tube has adiabatic plug and conversion catalyst pallet, and said convertor flange is connected with blind flange; Be disposed with first gas distribution grid, second gas distribution grid and the 3rd gas distribution grid in the said reactor drum shell side.
Among the said step C, membrane separation apparatus comprises cavity, inlet end and tail gas outlet side, is provided with palladium membrane component in the said cavity; Said cavity is provided with the hydrogen escape pipe, and the two ends of cavity are respectively arranged with first flange and second flange, and said inlet end is connected with the inlet end end socket; This inlet end end socket is connected with the 3rd flange, and said first flange is fixedly connected with the 3rd flange, also is provided with the inlet end tube sheet between first flange and the 3rd flange; Said tail gas outlet side is connected with the outlet side end socket; This outlet side end socket is connected with the 4th flange, and said second flange is fixedly connected with the 4th flange, also is provided with the outlet side tube sheet between second flange and the 4th flange.
Embodiment 2: shown in Fig. 1-3, a kind of is the method for raw material for preparing hydrogen with biogas, may further comprise the steps:
A, normal temperature, pressure be the raw material biogas of 1.2Mpa (G) after first interchanger is heated to 340～360 ℃, get into desulphurization reactor and carry out desulfurization, the total sulfur in the gas is controlled at 20mg/m
3Below;
Gas after B, the desulfurization gets into the tube side of shell and tube-type reactor after second interchanger is heated to 580～600 ℃, under the effect of Ni/SBA-15 catalyzer, carry out reforming reaction;
C, the gas that obtains among the step B is sent into the CO umformer and overheated steam reacts after the second interchanger heat exchange, the gas that reaction obtains is sent into membrane separation apparatus and is separated, and separates obtaining product hydrogen and device exhaust;
D, the device exhaust that obtains among the step C is sent into the shell side of shell and tube-type reactor, under the effect of noble metal catalyst with air generation catalyst combustion reaction;
E, the high-temperature flue gas of the catalyst combustion reaction that obtains among the step D sent into the first interchanger heat exchange after, send into vapour generator heating de-salted water, the overheated steam that obtains is sent into the CO umformer as reactant gases.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
Claims (2)
1. one kind is the method for raw material for preparing hydrogen with biogas, it is characterized in that may further comprise the steps:
A, raw material biogas get into desulphurization reactor and carry out desulfurization after first interchanger is heated to 340～360 ℃, and the total sulfur in the gas is controlled at 20mg/m
3Below;
Gas after B, the desulfurization gets into the tube side of shell and tube-type reactor after second interchanger is heated to 580～600 ℃, under the effect of catalyzer, carry out reforming reaction;
C, the gas that obtains among the step B is sent into the CO umformer and overheated steam reacts after the second interchanger heat exchange, the gas that reaction obtains is sent into membrane separation apparatus and is separated, and separates obtaining product hydrogen and device exhaust;
D, the device exhaust that obtains among the step C is sent into the shell side of shell and tube-type reactor, under the effect of catalyzer with air generation catalyst combustion reaction;
E, the high-temperature flue gas of the catalyst combustion reaction that obtains among the step D sent into the first interchanger heat exchange after, send into vapour generator heating de-salted water, the overheated steam that obtains is sent into the CO umformer as reactant gases;
In the wherein said steps A, the pressure of raw material biogas is 1.2MPa;
Among the said step B; Shell and tube-type reactor comprises reactor drum shell side, upper sealing plate and following shrouding; The reactor drum shell side is fixedly connected with following shrouding with upper sealing plate respectively, and the top of said reactor drum shell side is connected with exhanst gas outlet, and the middle part is connected with the secondary air import; Bottom one side is connected with the primary air import, and opposite side is connected with the tail gas inlet mouth; Be connected with conversion tube in the said reactor drum shell side; The two ends of this conversion tube are respectively arranged with convertor flange and reforming gas outlet; The top of conversion tube is connected with the virgin gas inlet mouth, and the set inside of conversion tube has adiabatic plug and conversion catalyst pallet, and said convertor flange is connected with blind flange; Be disposed with first gas distribution grid, second gas distribution grid and the 3rd gas distribution grid in the said reactor drum shell side;
Among the said step C, membrane separation apparatus comprises cavity, inlet end and tail gas outlet side, is provided with palladium membrane component in the said cavity; Said cavity is provided with the hydrogen escape pipe, and the two ends of cavity are respectively arranged with first flange and second flange, and said inlet end is connected with the inlet end end socket; This inlet end end socket is connected with the 3rd flange, and said first flange is fixedly connected with the 3rd flange, also is provided with the inlet end tube sheet between first flange and the 3rd flange; Said tail gas outlet side is connected with the outlet side end socket; This outlet side end socket is connected with the 4th flange, and said second flange is fixedly connected with the 4th flange, also is provided with the outlet side tube sheet between second flange and the 4th flange.
2. as claimed in claim 1 a kind of be the method for raw material for preparing hydrogen with biogas, it is characterized in that: among the said step B, the catalyzer of reforming reaction is that noble metal catalyst or loading type Ni are catalyst based.
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| CN2010105218635A CN101973523B (en) | 2010-10-28 | 2010-10-28 | Method for preparing hydrogen gas by taking marsh gas as raw material |
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|---|---|---|---|
| CN2010105218635A CN101973523B (en) | 2010-10-28 | 2010-10-28 | Method for preparing hydrogen gas by taking marsh gas as raw material |
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| CN101973523B true CN101973523B (en) | 2012-08-08 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173381B (en) * | 2011-02-28 | 2012-08-08 | 四川亚联高科技股份有限公司 | Method for preparing hydrogen with natural gas as raw material |
| CN104910988B (en) * | 2015-05-15 | 2017-03-08 | 大连理工大学 | A kind of Methane Resources diversification utilization technique of environmental protection |
| CN106299421B (en) * | 2016-08-27 | 2019-03-08 | 温州集智科技有限公司 | A kind of biomass energy and Hydrogen Energy combined power generation device |
| CN107986233B (en) * | 2017-12-12 | 2020-12-01 | 天津大学 | Method for preparing hydrogen by catalyzing biogas slurry |
| CN108249400A (en) * | 2018-02-26 | 2018-07-06 | 刘约翰 | A kind of specific function nonferrous materials equipment |
| CN108342304A (en) * | 2018-02-26 | 2018-07-31 | 孙克雷 | A kind of biomass hydrogen preparation equipment |
| CN108179106B (en) * | 2018-02-26 | 2019-01-08 | 徐州大利精创传动机械有限公司 | A kind of novel specific function nonferrous materials equipment |
| CN108060065B (en) * | 2018-02-26 | 2019-01-25 | 江山华隆能源开发有限公司 | A kind of novel biomass hydrogen producer |
| CN109179320B (en) * | 2018-11-08 | 2020-02-07 | 新地能源工程技术有限公司 | Natural gas on-site hydrogen production device and method |
| CN112142003B (en) * | 2019-06-27 | 2022-05-17 | 中石化南京化工研究院有限公司 | Carbon monoxide conversion process |
| CN113772628A (en) * | 2021-08-13 | 2021-12-10 | 中国石油大学(北京) | Method for preparing hydrogen by utilizing methane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1094030A2 (en) * | 1999-10-20 | 2001-04-25 | Nippon Chemical Plant Consultant Co., Ltd. | Reforming method and apparatus for hydrogen production |
| CN101219919A (en) * | 2008-01-21 | 2008-07-16 | 四川亚联高科技有限责任公司 | Method for purifying and recycling methyl hydride from garbage landfill gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010095424A (en) * | 2008-10-20 | 2010-04-30 | Aienji:Kk | Steam reforming reactor for hydrogen production |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1094030A2 (en) * | 1999-10-20 | 2001-04-25 | Nippon Chemical Plant Consultant Co., Ltd. | Reforming method and apparatus for hydrogen production |
| CN101219919A (en) * | 2008-01-21 | 2008-07-16 | 四川亚联高科技有限责任公司 | Method for purifying and recycling methyl hydride from garbage landfill gas |
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| Title |
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| JP特开2010-95424A 2010.04.30 |
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