CN111378507A - Process method for producing hydrogen by coal gasification - Google Patents
Process method for producing hydrogen by coal gasification Download PDFInfo
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- CN111378507A CN111378507A CN201811624799.6A CN201811624799A CN111378507A CN 111378507 A CN111378507 A CN 111378507A CN 201811624799 A CN201811624799 A CN 201811624799A CN 111378507 A CN111378507 A CN 111378507A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/10—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with metals
- C01B3/105—Cyclic methods
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
A process method for producing hydrogen by coal gasification comprises the following steps of (1) coal gasification, (2) gasification gas and oxygen carrier reaction: the temperature is 450-600 ℃, the pressure is 3-5 MPa, and CO is obtained2And H2O, also includes a small amount of CH4、SO2And H2(ii) a (3) Hydrogen production: in the step (2), the oxygen carrier is reduced, and is separated and then reacts with water vapor to prepare hydrogen; (4) and (3) oxygen carrier oxidation process: in the step (2), the oxygen carrier is partially oxidized and is completely oxidized after being separated and reacted with air. The process method of the invention uses the oxygen carrier to carry out the coal hydrogen production process, can replace the traditional conversion, acid gas removal and gas purification processes of coal hydrogen production, reduces the device investment, improves the economy, improves the coal hydrogen production efficiency, improves the hydrogen recovery rate, and prepares high-purity hydrogen; zero energy consumption enriches carbon dioxide, has avoided the problem of a large amount of carbon dioxide emissions in the coal chemical industry process.
Description
Technical Field
The invention relates to a process method for producing hydrogen by coal gasification, belonging to the technology in the field of coal gasification.
Background
The coal resources in China are rich, the petroleum and natural gas resources are relatively poor, and the reasonable, economic, efficient and clean utilization of coal is an important national policy for national energy construction in China currently and for decades in the future, and is an important foundation for meeting the national conditions of China and ensuring the stable and reliable supply of energy and the sustainable development of economy in China. The production of synthesis gas by coal gasification, and the production of downstream products such as synthetic ammonia, methanol, dimethyl ether, hydrogen production, olefin, synthetic oil, IGCC power generation and the like by the synthesis gas is a main technical route for energy substitution in China in the twenty-first century.
Under the influence of both policy and economy, most residual oil hydrogen and natural gas hydrogen production devices are shut down at present, and most hydrogen sources of newly-built refineries and fertilizer plants are coal hydrogen production. The typical coal-fired hydrogen production process (shown in figure 1) comprises the following steps: after raw materials such as petroleum coke, raw material coal, limestone and the like are prepared into qualified pulverized coal or coal water slurry by a pulverized coal or coal water slurry preparation unit, the qualified pulverized coal or coal water slurry and oxygen provided by an air separation device enter a gasification furnace of a gasification unit together to perform partial oxidation reaction, and crude synthesis gas generated by the reaction mainly comprises hydrogen, carbon monoxide and carbon dioxide. The crude synthesis gas is quenched and washed, then enters a carbon monoxide conversion unit for conversion reaction, most of carbon monoxide and steam are reacted and converted into carbon dioxide and hydrogen through reaction, the carbon dioxide and the hydrogen enter a low-temperature methanol washing unit after waste heat recovery and cooling washing, the conversion gas enters a methanation or PSA system for refining after sulfur (mainly existing in the form of hydrogen sulfide) and carbon dioxide contained in the low-temperature methanol washing unit are removed, and qualified industrial hydrogen products are prepared and then sent out.
The traditional coal gas making process mainly has the following problems: firstly, the synthesis gas needs to enter a conversion device for conversion and heat recovery, then is cooled and enters a low-temperature methanol washing device, and then is heated and enters a methanation device, which is a large loss in energy utilization; secondly, due to the characteristics of the conversion, acid removal, PSA and methanation devices, the utilization rate of the effective gas in the device can only reach about 88 percent when producing high-purity hydrogen; thirdly, the investment of the conversion, acid removal and refining units is high.
Disclosure of Invention
In order to solve the problems of low energy efficiency, poor economical efficiency and environmental pollution of coal gasification hydrogen production in the prior art, the invention aims to provide a novel coal gasification hydrogen production process method, wherein an oxygen carrier is combined into the coal hydrogen production technology, and the processes of transformation, acid gas removal and gas purification are simplified, so that the coal hydrogen production energy efficiency is improved, the device investment is reduced, the hydrogen recovery rate is improved, and high-purity hydrogen is prepared.
The technical purpose of the invention is realized by the following technical scheme:
a process method for producing hydrogen by coal gasification comprises the following steps:
(1) coal gasification: gasifying coal to obtain gasified gas containing CO and H2O、H2、CO2、CH4And H2S；
(2) The gasified gas reacts with the oxygen carrier: reacting the gas obtained by gasification with an oxygen carrier at the temperature of 450-600 ℃ and the pressure of 3-5 MPa to obtain CO2And H2O, also includes a small amount of CH4、SO2And H2；
(3) Hydrogen production: the oxygen carrier is reduced in the step (2), and the oxygen carrier is separated and then reacts with steam to prepare hydrogen, wherein the reaction temperature is 400-600 ℃, and the pressure is 3-5 MPa;
(4) and (3) oxygen carrier oxidation process: and (3) oxidizing the oxygen carrier part in the step (2), reacting with air after separation, and completely oxidizing, wherein the reaction temperature is 500-600 ℃, the pressure is 3-5 MPa, and returning to react with gasified gas after the reaction is finished for recycling.
In the above process, further, the reaction temperature in the step (2) is preferably 450 to 550 ℃.
In the above process, further, the oxygen carrier is Fe2O3MgO or Mn2O3-CeZrO3. The oxygen carrier Fe2O3MgO with Fe2O3The active component is 20-50% by mass, and the MgO is a carrier and 50-80% by mass. The oxygen carrier Mn2O3-CeZrO3With Mn2O3Is an active component with the mass fraction of 20-50 percent and CeZrO3Is used as a carrier, and the mass fraction is 50-80%.
In the above process, further, the oxygen carrier is prepared by a conventional method in the art, such as impregnation or coprecipitation. This is well known to those skilled in the art and will not be described further.
In the above process, further, the coal gasification is to obtain gasified gas by coal water slurry gasification, coal powder chilling gasification and waste coal boiler gasification. The main components of the gasified gas are CO and H2O、H2And CO2And also includes a small amount of CH4And H2S。
In the process of the invention, H in the gasification gas2O has certain influence on the main reaction in the step (2) and reacts with CO to generate CO2And H2So that CO can not fully utilize oxygen in the oxygen carrier, the reduction rate of the oxygen carrier is reduced, and the subsequent hydrogen production reaction is influenced. According to the invention, a specific oxygen carrier is selected, and the oxygen carrier can react with gasified gas at a lower temperature (450-600 ℃, more preferably 450-550 ℃), so that the influence of side reaction is reduced as much as possible on the basis of ensuring higher utilization rate of the oxygen carrier.
Compared with the prior art, the invention has the following advantages:
(1) the process method of the invention uses the oxygen carrier to carry out the coal hydrogen production process, and can replace the traditional conversion, acid gas removal and gas purification processes of coal hydrogen production, thereby reducing the device investment and improving the economy.
(2) The process method can improve the coal hydrogen production efficiency, improve the hydrogen recovery rate and prepare high-purity hydrogen.
(3) The method can enrich carbon dioxide with zero energy consumption in the coal gasification process, and avoids the problem of large emission of carbon dioxide in the coal chemical industry process.
(4) The reaction system related to the process method has the advantages of simple structure, high integration level and easy realization of industrialization.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a schematic flow diagram of a typical coal gasification hydrogen production process.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
(1) Coal gasification: lignite is fed into a gasification furnace at a rate of 100g/min, the reaction temperature is 800 ℃, and the composition of gasification gas at an outlet is 42.1 percent of CO and 38 percent of H2O、14.9%H2、3.8%CO2、1%CH4And 0.2% H2S；
(2) Introducing gasified gas into a fixed bed reactor through a grid plate, wherein the gas flow is 500mL/min, and 200g of oxygen carrier Fe is filled in the fixed bed reactor2O3MgO, oxygen carrier is prepared by dipping method, and the oxygen carrier contains Fe2O320 percent of MgO and 80 percent of MgO; controlling the reaction temperature at 500 ℃ and 3MPa, reacting the gasified gas with an oxygen carrier, wherein the product mainly comprises carbon dioxide, water vapor, a small amount of methane, carbon monoxide, sulfur dioxide and the like.
(3) And taking out the oxygen carrier after reaction, flowing into another reactor through an inclined tube, introducing steam, controlling the flow rate of the steam to be 150mL/min, controlling the reaction temperature to be 600 ℃, reacting with the oxygen carrier to generate hydrogen, and primarily oxidizing the oxygen carrier.
(4) And (3) contacting the preliminarily oxidized oxygen carrier with air to perform a complete oxidation reaction, controlling the reaction temperature to be 600 ℃, the reaction pressure to be 3MPa and the air flow to be 800mL/min, and returning the completely oxidized oxygen carrier to the step (2) for recycling.
Example 2
The procedure of example 1 was repeated except that the reaction temperature in step (2) was changed to 450 ℃.
Example 3
The procedure of example 1 was repeated except that the reaction temperature in step (2) was changed to 550 ℃.
Example 4
The procedure of example 1 was repeated except that the reaction temperature in step (2) was changed to 600 ℃.
Example 5
The same procedure as in example 1 was conducted except that the reaction pressure in step (2) was changed to 4 MPa.
Example 6
The same procedure as in example 1 was conducted except that the reaction pressure in step (2) was changed to 5 MPa.
Example 7
Replacing oxygen carrier, using Fe in oxygen carrier2O3The mass fraction of MgO was 30% and the mass fraction of MgO was 70%, and the other operations were carried out in the same manner as in example 1.
Example 8
Replacing oxygen carrier, using Fe in oxygen carrier2O3The mass fraction of MgO is 50%, and the other operation steps are the same as in example 1.
Example 9
Replacing oxygen carrier, wherein the used oxygen carrier is Mn2O3-CeZrO3The oxygen carrier is prepared by an impregnation method, and Mn in the oxygen carrier2O3Is 20% by mass, CeZrO3The mass fraction of (A) is 80%; the other procedures were the same as in example 1.
Example 10
The procedure of example 8 was followed except that the reaction temperature of the gasification gas and the oxygen carrier in step (2) was changed to 450 ℃.
Example 11
The procedure of example 8 was followed except that the reaction temperature of the gasification gas and the oxygen carrier in step (2) was changed to 550 ℃.
Example 12
The procedure of example 8 was followed except that the reaction temperature of the gasification gas and the oxygen carrier in step (2) was changed to 600 ℃.
Example 13
Replacing oxygen carrier and using oxygen carrier Mn2O3-CeZrO3Middle Mn2O3Is 30% by mass, CeZrO3The mass fraction of (A) is 70%; other operationsThe procedure is as in example 8.
Example 14
Replacing oxygen carrier and using oxygen carrier Mn2O3-CeZrO3Middle Mn2O3Is 50% by mass, CeZrO3The mass fraction of (A) is 50%; the other procedures were the same as in example 8.
Comparative example 1
After the coal is made into qualified coal water slurry by the coal water slurry preparation unit, the qualified coal water slurry and oxygen provided by the air separation device enter a gasification furnace of the gasification unit together to perform partial oxidation reaction, and crude synthesis gas generated by the reaction mainly comprises hydrogen, carbon monoxide and carbon dioxide. The crude synthesis gas is quenched and washed, then enters a carbon monoxide conversion unit for conversion reaction, most of carbon monoxide and steam are reacted and converted into carbon dioxide and hydrogen through reaction, the carbon dioxide and the hydrogen enter a low-temperature methanol washing unit after waste heat recovery and cooling washing, and the converted gas enters a methanation or PSA system for refining after sulfur (mainly existing in the form of hydrogen sulfide) and carbon dioxide contained in the low-temperature methanol washing unit are removed, so that the hydrogen is prepared.
Performing online analysis by adopting Agilent 7820A type gas chromatography, performing 5A molecular sieve column and Porapak Q column, and performing TCD detection. CO and H in examples and comparative examples2Oxygen carrier conversion and H2The purity is shown in table 1.
TABLE 1
Data in the table are averages after 100 cycles.
The CO conversion in the gas in step (2) is shown as the conversion of CO to CO2The conversion of (a); h2The conversion rate is H in the gas gasified in the step (2)2Conversion to H2The conversion of O; the conversion rate of the oxygen carrier is the utilization rate of oxygen in the oxygen carrier in the step (2), and is influenced by the activity of the oxygen carrier and the steam in the gasified gas; h2The purity is H prepared in the step (3)2The purity of (2).
Claims (7)
1. A process method for producing hydrogen by coal gasification comprises the following steps:
(1) coal gasification: gasifying coal to obtain gasified gas containing CO and H2O、H2、CO2、CH4And H2S；
(2) The gasified gas reacts with the oxygen carrier: reacting the gas obtained by gasification with an oxygen carrier at the temperature of 450-600 ℃ and the pressure of 3-5 MPa to obtain CO2And H2O, also includes a small amount of CH4、SO2And H2；
(3) Hydrogen production: the oxygen carrier is reduced in the step (2), and the oxygen carrier is separated and then reacts with steam to prepare hydrogen, wherein the reaction temperature is 400-600 ℃, and the pressure is 3-5 MPa;
(4) and (3) oxygen carrier oxidation process: and (3) oxidizing the oxygen carrier part in the step (2), reacting with air after separation, and completely oxidizing, wherein the reaction temperature is 500-600 ℃, the pressure is 3-5 MPa, and returning to react with gasified gas after the reaction is finished for recycling.
2. The process of claim 1, wherein the reaction temperature in step (2) is preferably 450 to 550 ℃.
3. The process of claim 1, wherein the oxygen carrier is Fe2O3MgO or Mn2O3-CeZrO3。
4. Process according to claim 3, characterized in that the oxygen carrier is Fe2O3MgO with Fe2O3The active component is 20-50% by mass, and the MgO is a carrier and 50-80% by mass.
5. Process according to claim 3, characterized in that the oxygen carrier Mn is2O3-CeZrO3With Mn2O3Is an active component20 to 50 percent of CeZrO3Is used as a carrier, and the mass fraction is 50-80%.
6. The process according to claim 3, wherein the oxygen carrier is prepared by impregnation or co-precipitation.
7. The process method of claim 1, wherein the coal gasification is a gasification gas obtained by coal water slurry gasification, pulverized coal quench gasification and pulverized coal waste boiler gasification.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343624A (en) * | 1979-12-10 | 1982-08-10 | Caterpillar Tractor Co. | Rotating fluidized bed hydrogen production system |
| CN101746721A (en) * | 2009-08-12 | 2010-06-23 | 东南大学 | Method and device for producing hydrogen and separating CO2 based on iron or iron oxide |
| CN102515096A (en) * | 2011-11-22 | 2012-06-27 | 中国科学院广州能源研究所 | Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain |
| CN107934914A (en) * | 2017-12-14 | 2018-04-20 | 太原理工大学 | A kind of coal bed gas deoxidation device for producing hydrogen and technique |
| CN109761192A (en) * | 2019-03-07 | 2019-05-17 | 浦江思欣通科技有限公司 | A kind of producing hydrogen by using chemical chain |
-
2018
- 2018-12-28 CN CN201811624799.6A patent/CN111378507A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4343624A (en) * | 1979-12-10 | 1982-08-10 | Caterpillar Tractor Co. | Rotating fluidized bed hydrogen production system |
| CN101746721A (en) * | 2009-08-12 | 2010-06-23 | 东南大学 | Method and device for producing hydrogen and separating CO2 based on iron or iron oxide |
| CN102515096A (en) * | 2011-11-22 | 2012-06-27 | 中国科学院广州能源研究所 | Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain |
| CN107934914A (en) * | 2017-12-14 | 2018-04-20 | 太原理工大学 | A kind of coal bed gas deoxidation device for producing hydrogen and technique |
| CN109761192A (en) * | 2019-03-07 | 2019-05-17 | 浦江思欣通科技有限公司 | A kind of producing hydrogen by using chemical chain |
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Application publication date: 20200707 |