CN112812930B - System and process for producing oxygen-containing organic matters from carbon dioxide and coal - Google Patents

System and process for producing oxygen-containing organic matters from carbon dioxide and coal Download PDF

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CN112812930B
CN112812930B CN202110162048.2A CN202110162048A CN112812930B CN 112812930 B CN112812930 B CN 112812930B CN 202110162048 A CN202110162048 A CN 202110162048A CN 112812930 B CN112812930 B CN 112812930B
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fermentation
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carbon dioxide
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CN112812930A (en
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王铁峰
蓝晓程
王宇
金涌
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Tsinghua University
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Abstract

A system and process for producing oxygenated organics from carbon dioxide and coal is provided. The system comprises: a coal gasification unit (1), a biological fermentation unit (2), a fermentation liquor separation unit (3) and a carbon dioxide unit (7); wherein a gas phase outlet of the carbon dioxide unit (7) is connected with a gas phase inlet of the coal gasification unit (1), a gas phase outlet of the coal gasification unit (1) is connected with a gas phase inlet of the fermentation raw material gas purification unit (4), a gas phase outlet of the fermentation raw material gas purification unit (4) is connected with a gas phase inlet of the biological fermentation unit (2), and a liquid phase outlet of the biological fermentation unit (2) is connected with a liquid phase inlet of the fermentation liquid separation unit (3); the coal gasification unit (1) is used for generating a coal gasification process, a gasification agent of the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is provided by the carbon dioxide unit (7).

Description

System and process for producing oxygen-containing organic matters from carbon dioxide and coal
Technical Field
The invention relates to a system and a process for producing oxygen-containing organic matters from carbon dioxide and coal.
Background
The energy is an important support for the development of national economy, the energy of China has the characteristics of rich coal, poor oil and less gas, the oil and natural gas have high external dependence, and the international trade situation is complex and changeable and has more unstable factors. Therefore, the development of a high-efficiency clean utilization technology of coal has important practical significance. The prior novel coal chemical industry technology generally refers to oil preparation from coal, methanol preparation from coal, dimethyl ether preparation from coal, olefin preparation from coal, ethylene glycol preparation from coal and the like, and the common points of the processes are that coal is gasified into synthesis gas, and the synthesis gas is further converted into other chemicals. The process route of the coal chemical industry is relatively long, the process production cost is relatively high, the carbon dioxide emission is large, and the overall economic benefit is poor.
The existing novel coal chemical industry technology requires that hydrogen in synthesis gas reaches a certain proportion, production requirements are difficult to achieve only through the hydrogen content of coal, water is generally used as a gasifying agent, and the hydrogen content in the synthesis gas is improved by utilizing water gas shift reaction. The technical characteristics increase the demand of water resources on one hand, reduce the utilization rate of carbon resources in coal on the other hand, and increase the discharge amount of carbon dioxide.
In recent years, china vigorously promotes the green development of the whole society, and carbon neutralization becomes a novel environment-friendly form. However, the coal consumption of the coal chemical industry in China is large and continuously increased year by year, the corresponding emission amount of greenhouse gas carbon dioxide is also continuously increased, and the coal chemical industry becomes a major household of the carbon dioxide emission industry in China and is bound to become an important emission reduction point.
The method has important significance for developing a novel coal chemical technology and reducing carbon dioxide emission in order to realize strategic tasks of low carbon, environmental protection, energy conservation and emission reduction.
Disclosure of Invention
In view of the background, the invention provides a system and a process for producing oxygen-containing organic matters by using carbon dioxide and coal, the system and the process improve the utilization rate of carbon resources in the coal, reduce the emission of the carbon dioxide, further convert inorganic carbon such as CO and the like into the high-added-value oxygen-containing organic matters such as ethanol and the like by using a biological fermentation technology, and have good economic benefit and environmental protection benefit.
In one aspect, to achieve the above objects, the present invention provides a system for producing oxygen-containing organic matters from carbon dioxide and coal, comprising: a coal gasification unit 1, a biological fermentation unit 2, a fermentation liquor separation unit 3 and a carbon dioxide unit 7; wherein, the gas phase outlet of the carbon dioxide unit 7 is connected with the gas phase inlet of the coal gasification unit 1, the gas phase outlet of the coal gasification unit 1 is connected with the gas phase inlet of the fermentation raw material gas purification unit 4, the gas phase outlet of the fermentation raw material gas purification unit 4 is connected with the gas phase inlet of the biological fermentation unit 2, and the liquid phase outlet of the biological fermentation unit 2 is connected with the liquid phase inlet of the fermentation liquid separation unit 3; in the coal gasification unit 1, a coal gasification process is performed, a gasification agent in the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7.
Further, the carbon dioxide unit 7 comprises a carbon dioxide separation subunit and a carbon dioxide compressor, and a gas phase outlet of the carbon dioxide separation subunit is connected with an inlet of the carbon dioxide compressor.
Further, the coal gasification unit 1 includes a coal gasification furnace, and the coal gasification furnace is one of a fixed bed gasification furnace, a moving bed gasification furnace, a fluidized bed gasification furnace, and a fluidized bed gasification furnace.
Further, fermentation raw material gas purification unit 4 contains gas-solid separation subunit, gas washing subunit and gas absorption aconite root unit, gas-solid separation subunit contains cyclone separation dust remover, gas washing subunit contains the gas scrubbing tower.
Further, the biological fermentation unit 2 comprises a biological fermentation reactor, and the biological fermentation reactor is one of a bubbling bed reactor, an airlift loop reactor and a stirred tank reactor or a combination thereof.
Further, the fermentation liquid separation unit 3 comprises a rectification column, and the rectification column is one of a packed column, a sieve plate column and a composite column or a combination thereof.
Further, a solid waste outlet in the coal gasification unit 1 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8; a solid waste outlet in the fermentation raw material gas purification unit 4 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8; a wastewater outlet in the fermentation raw material gas purification unit 4 is connected with a wastewater inlet in the solid waste/wastewater treatment unit 8; the outlet of the bacteria-containing raffinate in the fermentation liquor separation unit 3 is connected to the inlet of the bacteria-containing raffinate treatment unit (5, 5').
Further, the system for producing the oxygen-containing organic matter by using the carbon dioxide and the coal comprises a fermentation tail gas treatment unit (10, 10 '), wherein a gas phase inlet of the fermentation tail gas treatment unit (10, 10') is connected with a gas phase outlet of the biological fermentation unit 2; the fermentation tail gas treatment unit 10' comprises a hydrogen purification subunit, and is used for purifying the fermentation tail gas to obtain hydrogen.
Further, the bacteria-containing raffinate treatment unit (5, 5 ') comprises a concentration subunit and a drying subunit, and/or the bacteria-containing raffinate treatment unit (5, 5') comprises an anaerobic fermentation subunit.
On the other hand, the invention provides a process for producing oxygen-containing organic matters by using carbon dioxide and coal, which comprises the following steps:
(1) The coal is pretreated by the raw material coal pretreatment unit 6 and then is sent to the coal gasification unit 1, and the carbon dioxide unit 7 sends carbon dioxide to the coal gasification unit 1;
(2) The coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate a fermentation raw material gas;
(3) The fermentation raw gas generated in the step 2 enters a fermentation raw gas purification unit 4, and impurities in the fermentation raw gas are removed, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds;
(4) The fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a bioreactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic products;
(5) The fermentation liquor generated in the step 4 enters a fermentation liquor separation unit 3, and an oxygen-containing organic product and a bacterium-containing residual liquid are obtained through separation;
(6) The bacterium-containing residual liquid generated in the step 5 enters a bacterium-containing residual liquid treatment unit (5, 5') to carry out a bacterium-containing residual liquid treatment process.
Further, a gasifying agent in the coal gasification process in the step 2 comprises carbon dioxide, and also comprises one or a combination of oxygen and water; the fermentation feed gas comprises carbon monoxide and also comprises one or a combination of carbon dioxide and hydrogen.
Further, the gasification temperature in the coal gasification furnace is 800-2000 ℃, preferably 900-1300 ℃.
Further, the pressure in the coal gasification furnace is 0.5 to 8MPa, preferably 3 to 6MPa.
Further, the oxygen-containing organic matter comprises one or a combination of ethanol, acetic acid, butanol and butanediol.
Further, a coal gasification catalyst comprising one or a combination of an alkali metal compound, an alkaline earth metal compound, and a transition metal compound may be added to the gasifier for increasing the coal gasification rate. Preferably, it is one or a combination of an alkali metal oxide, an alkaline earth metal oxide and a transition metal oxide.
Further, the bioreactor comprises microorganisms of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium ljungdahlii (Clostridium ljungdahlii) and Clostridium magnum (Clostridium magnum).
Further, gasification ash in the coal gasification unit 1 and wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
Further, fermentation tail gas of the biological fermentation unit 2 enters a fermentation tail gas treatment unit (10, 10 '), and the fermentation tail gas is purified in the fermentation tail gas treatment unit 10' to obtain hydrogen.
Further, the bacteria-containing raffinate is concentrated and dried in a bacteria-containing raffinate treatment unit (5, 5 ') to produce a solid protein, and/or the bacteria-containing raffinate is anaerobically fermented in an anaerobic fermentation subunit of the bacteria-containing raffinate treatment unit (5, 5') to produce biogas.
The invention has the beneficial effects that:
1) The system and the process for preparing the oxygen-containing organic matters such as ethanol and the like by using the carbon dioxide and the coal provided by the invention firstly produce the fermentation raw material gas containing the carbon monoxide by using the coal and the gasifying agent containing the carbon dioxide, further combine the biological fermentation technology to produce the oxygen-containing organic matters such as the ethanol and the like, and simultaneously ferment thalli to further produce the solid protein or the methane. The invention improves the utilization rate of carbon resources in coal, reduces the emission of carbon dioxide, can obtain oxygen-containing organic matters with high added values such as ethanol and the like, and has good economic benefit and environmental protection benefit;
2) The existing novel coal chemical industry technology requires that hydrogen in the synthesis gas obtained by coal gasification reaches a certain proportion, and the biological fermentation technology in the invention has low requirement on the hydrogen content, so that the emission of carbon dioxide caused by water gas shift reaction in the existing novel coal chemical industry is reduced, and the invention has the advantages of simple process and less three-waste emission, and realizes the effect of high-efficiency clean utilization of coal; and
3) The coal gasification process of the invention can directly utilize the original coal gasification equipment, reduces the waste of original fixed assets under the condition of low economic benefit of the existing coal chemical technology, and provides a new technical path for the development of the coal chemical industry.
Drawings
FIG. 1 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal in accordance with an embodiment of the present invention.
FIG. 2 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal according to another embodiment of the present invention.
FIG. 3 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal according to another embodiment of the present invention.
FIG. 4 is a schematic diagram of a system for producing oxygenated organics from coal according to another embodiment of the present invention.
Detailed Description
Embodiments of various preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example 1
FIG. 1 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal. The system of the embodiment comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a carbon dioxide unit 7, a solid waste/wastewater treatment unit 8 and a bacteria-containing raffinate treatment unit 5.
As shown in fig. 1, a gas phase outlet of the carbon dioxide unit 7 is connected to a gas phase inlet of the coal gasification unit 1, a gas phase outlet of the coal gasification unit 1 is connected to a gas phase inlet of the fermentation raw material gas purification unit 4, a gas phase outlet of the fermentation raw material gas purification unit 4 is connected to a gas phase inlet of the biological fermentation unit 2, and a liquid phase outlet of the biological fermentation unit 2 is connected to a liquid phase inlet of the fermentation liquid separation unit 3.
As shown in fig. 1, a solid waste outlet in the coal gasification unit 1 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected to a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected to an inlet of the bacteria-containing residual liquid treatment unit 5.
In this reaction system, a coal gasification process is performed in the coal gasification unit 1, a gasification agent in the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7
In the reaction system, a fermentation tail gas treatment unit 10 is included, and a gas phase inlet of the fermentation tail gas treatment unit 10 is connected with a gas phase outlet of the biological fermentation unit 2.
In the reaction system, the coal gasification unit 1 includes a coal gasification furnace, which is one of a fixed bed gasification furnace, a moving bed gasification furnace, a fluidized bed gasification furnace, and a fluidized bed gasification furnace; the fermentation raw material gas purification unit 4 comprises a gas-solid separation subunit, a gas washing subunit and a gas absorption subunit, wherein the gas-solid separation subunit comprises a cyclone separation dust collector, and the gas washing subunit comprises a gas washing tower; the biological fermentation unit 2 comprises a biological fermentation reactor, wherein the biological fermentation reactor is one or the combination of a bubbling bed reactor, an airlift loop reactor and a stirred tank reactor; the fermentation liquor separation unit 3 comprises a rectifying tower which is one or a combination of a packed tower, a sieve plate tower and a composite tower.
Example 2
The system of the embodiment comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a carbon dioxide unit 7, a solid waste/wastewater treatment unit 8 and a bacteria-containing residual liquid treatment unit 5.
In the reaction system, a gas phase outlet of the carbon dioxide unit 7 is connected with a gas phase inlet of the coal gasification unit 1, a gas phase outlet of the coal gasification unit 1 is connected with a gas phase inlet of the fermentation raw material gas purification unit 4, a gas phase outlet of the fermentation raw material gas purification unit 4 is connected with a gas phase inlet of the biological fermentation unit 2, and a liquid phase outlet of the biological fermentation unit 2 is connected with a liquid phase inlet of the fermentation liquid separation unit 3.
In the reaction system, a solid waste outlet in the coal gasification unit 1 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected with a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected with an inlet of the bacteria-containing residual liquid treatment unit 5.
In this reaction system, a coal gasification process is performed in the coal gasification unit 1, a gasification agent of the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7.
In this reaction system, the coal gasification unit 1, the fermentation raw material gas purification unit 4, the biological fermentation unit 2, and the fermentation liquid separation unit 3 are the same as those of example 1.
In the reaction system, the bacteria-containing raffinate treatment unit 5 comprises a concentration centrifuge subunit and a drying subunit, and is used for preparing solid protein after concentrating and drying the bacteria-containing raffinate.
Example 3
The system of the embodiment comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a carbon dioxide unit 7, a solid waste/wastewater treatment unit 8 and a bacteria-containing raffinate treatment unit 5.
In the reaction system, a gas phase outlet of the carbon dioxide unit 7 is connected with a gas phase inlet of the coal gasification unit 1, a gas phase outlet of the coal gasification unit 1 is connected with a gas phase inlet of the fermentation raw material gas purification unit 4, a gas phase outlet of the fermentation raw material gas purification unit 4 is connected with a gas phase inlet of the biological fermentation unit 2, and a liquid phase outlet of the biological fermentation unit 2 is connected with a liquid phase inlet of the fermentation liquid separation unit 3.
In the reaction system, a solid waste outlet in the coal gasification unit 1 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected with a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected with a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected with an inlet of the bacteria-containing residual liquid treatment unit 5.
In this reaction system, a coal gasification process is performed in the coal gasification unit 1, a gasification agent of the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7.
In this reaction system, the coal gasification unit 1, the fermentation raw material gas purification unit 4, the biological fermentation unit 2, and the fermentation liquid separation unit 3 are the same as those of example 1.
In the reaction system, the bacteria-containing residual liquid treatment unit 5 comprises a centrifugal concentration subunit and an anaerobic fermentation subunit, and is used for producing methane after fermenting the bacteria-containing residual liquid.
Example 4
Fig. 2 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal. The system of the embodiment comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a carbon dioxide unit 7, a solid waste/wastewater treatment unit 8 and a bacteria-containing raffinate treatment unit 5.
As shown in fig. 2, a gas phase outlet of the carbon dioxide unit 7 is connected to a gas phase inlet of the coal gasification unit 1, a gas phase outlet of the coal gasification unit 1 is connected to a gas phase inlet of the fermentation raw material gas purification unit 4, a gas phase outlet of the fermentation raw material gas purification unit 4 is connected to a gas phase inlet of the biological fermentation unit 2, and a liquid phase outlet of the biological fermentation unit 2 is connected to a liquid phase inlet of the fermentation liquid separation unit 3.
As shown in fig. 2, a solid waste outlet in the coal gasification unit 1 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected to a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected to an inlet of the bacteria-containing residual liquid treatment unit 5.
In this reaction system, a coal gasification process is performed in the coal gasification unit 1, a gasification agent of the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7
As shown in fig. 2, the reaction system comprises a fermentation tail gas treatment unit 10', wherein a gas phase inlet of the fermentation tail gas treatment unit 10' is connected with a gas phase outlet of the biological fermentation unit 2; the fermentation tail gas treatment unit 10' comprises a hydrogen purification subunit, and is used for purifying fermentation tail gas to obtain hydrogen.
In the reaction system, a coal gasification unit 1, a fermentation raw material gas purification unit 4, a biological fermentation unit 2, a fermentation liquid separation unit 3, and a bacteria-containing residual liquid treatment unit 5 are the same as in example 1.
Example 5
Fig. 3 is a schematic diagram of a system for producing oxygenated organics from carbon dioxide and coal. In the system of the embodiment, the system comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a carbon dioxide unit 7, a solid waste/wastewater treatment unit 8 and a bacteria-containing raffinate treatment unit 5'.
As shown in fig. 3, a gas phase outlet of the carbon dioxide unit 7 is connected to a gas phase inlet of the coal gasification unit 1, a gas phase outlet of the coal gasification unit 1 is connected to a gas phase inlet of the fermentation raw material gas purification unit 4, a gas phase outlet of the fermentation raw material gas purification unit 4 is connected to a gas phase inlet of the biological fermentation unit 2, and a liquid phase outlet of the biological fermentation unit 2 is connected to a liquid phase inlet of the fermentation liquid separation unit 3.
As shown in fig. 3, a solid waste outlet in the coal gasification unit 1 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected to a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected to an inlet of the bacteria-containing residual liquid treatment unit 5'.
In this reaction system, a coal gasification process is performed in the coal gasification unit 1, a gasification agent of the coal gasification process contains carbon dioxide, and the carbon dioxide contained in the gasification agent is supplied from the carbon dioxide unit 7
As shown in FIG. 3, a fermentation tail gas treatment unit 10 is included in the reaction system, and a gas phase inlet of the fermentation tail gas treatment unit 10 is connected with a gas phase outlet of the biological fermentation unit 2.
In this reaction system, the coal gasification unit 1, the fermentation raw material gas purification unit 4, the biological fermentation unit 2, and the fermentation liquid separation unit 3 are the same as those of example 1.
In the implementation reaction system, the bacteria-containing raffinate treatment unit 5' comprises a centrifugal concentration subunit and an anaerobic fermentation subunit, and is used for producing methane after the bacteria-containing raffinate is fermented; the gas phase outlet of the bacteria-containing residual liquid treatment unit 5 'is connected with the gas phase inlet of the coal gasification unit 1 and is used for conveying the methane generated in the bacteria-containing residual liquid treatment unit 5' back to the coal gasification unit 1 to participate in coal gasification reaction.
Example 6
The system of the embodiment comprises a coal gasification unit 1, a biological fermentation unit 2, a fermentation raw material gas purification unit 4, a fermentation liquor separation unit 3, a solid waste/wastewater treatment unit 8 and a bacteria-containing raffinate treatment unit 5.
As shown in fig. 4, the gas phase outlet of the coal gasification unit 1 is connected to the gas phase inlet of the fermentation raw material gas purification unit 4, the gas phase outlet of the fermentation raw material gas purification unit 4 is connected to the gas phase inlet of the biological fermentation unit 2, and the liquid phase outlet of the biological fermentation unit 2 is connected to the liquid phase inlet of the fermentation liquid separation unit 3.
As shown in fig. 4, a solid waste outlet in the coal gasification unit 1 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a solid waste outlet in the fermentation raw material gas purification unit 4 is connected to a solid waste inlet in the solid waste/wastewater treatment unit 8, a wastewater outlet in the fermentation raw material gas purification unit 4 is connected to a wastewater inlet in the solid waste/wastewater treatment unit 8, and a bacteria-containing residual liquid outlet in the fermentation liquid separation unit 3 is connected to an inlet of the bacteria-containing residual liquid treatment unit 5.
As shown in fig. 4, the reaction system comprises a fermentation tail gas treatment unit 10', wherein a gas phase inlet of the fermentation tail gas treatment unit 10' is connected with a gas phase outlet of the biological fermentation unit 2; the fermentation tail gas treatment unit 10' comprises a hydrogen purification subunit, and is used for purifying the fermentation tail gas to obtain hydrogen.
In this reaction system, the coal gasification unit 1, the fermentation raw material gas purification unit 4, the biological fermentation unit 2, and the fermentation liquid separation unit 3 are the same as those of example 1.
Example 7
A process for producing oxygenated organics from carbon dioxide and coal using the system described in examples 1-3.
In the process of the embodiment, coal is pretreated by the raw material coal pretreatment unit 6 and then is fed into the coal gasification unit 1, and the carbon dioxide unit 7 feeds carbon dioxide into the coal gasification unit 1; coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate fermentation raw material gas; the fermentation raw gas enters a fermentation raw gas purification unit 4 to remove impurities in the fermentation raw gas, wherein the impurities include but are not limited to fly ash, sulfur-containing compounds and chlorine-containing compounds; the fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a biological fermentation reactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic matter products; the fermentation liquor enters a fermentation liquor separation unit 3, and an oxygen-containing organic product and a bacterium-containing residual liquid are obtained through separation; the bacteria-containing residual liquid enters a bacteria-containing residual liquid treatment unit 5 for a bacteria-containing residual liquid treatment process; and the gasification ash in the coal gasification unit 1 and the wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
In the process of this example, the gasifying agent in the coal gasification process comprises carbon dioxide, oxygen and water; the ratio of the molar weight of carbon dioxide added to the coal gasification unit 1 to the molar weight of carbon in the coal is 0.1 to 1.2, preferably 0.5 to 1; the gasification temperature in the coal gasification furnace is 800-2000 ℃, and preferably 900-1300 ℃; the pressure in the coal gasification furnace is 0.5-8 MPa, preferably 3-6 MPa; the generated fermentation raw material gas comprises carbon monoxide, hydrogen and carbon dioxide, wherein the content of the carbon monoxide is 30-95%, and preferably 50-80%.
In the process of this example, microorganisms of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium (Clostridium ljungdahlii) and Clostridium macrocephalum (Clostridium magnum) are contained in the bioreactor.
In the process of the embodiment, the CO conversion rate in the biological fermentation unit 2 is 60-99%, preferably 75-90%, and the mass concentration of the oxygen-containing organic product in the fermentation liquid is 3-15%; preferably, the mass concentration of the oxygen-containing organic product is 4-10%; more preferably, the mass concentration of the oxygen-containing organic product is 5 to 8%.
In the process of this embodiment, the oxygenate product comprises one or a combination of ethanol, acetic acid, butanol, and butanediol.
In the method of this example, the bacteria-containing raffinate is concentrated and dried in the bacteria-containing raffinate treating unit 5 to produce a solid protein; and/or the bacteria-containing residual liquid is subjected to anaerobic fermentation in an anaerobic fermentation subunit of the bacteria-containing residual liquid treatment unit 5 to generate the biogas.
Example 9
A process for producing oxygenated organics from carbon dioxide and coal using the system described in examples 1-3.
In the process of the embodiment, coal is pretreated by the raw material coal pretreatment unit 6 and then is fed into the coal gasification unit 1, and the carbon dioxide unit 7 feeds carbon dioxide into the coal gasification unit 1; coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate fermentation raw material gas; the fermentation raw gas enters a fermentation raw gas purification unit 4 to remove impurities in the fermentation raw gas, wherein the impurities include but are not limited to fly ash, sulfur-containing compounds and chlorine-containing compounds; the fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a biological fermentation reactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic matter products; the fermentation liquor enters a fermentation liquor separation unit 3, and oxygen-containing organic products and bacteria-containing residual liquor are obtained through separation; the bacteria-containing residual liquid enters a bacteria-containing residual liquid treatment unit 5 for a bacteria-containing residual liquid treatment process; and the gasification ash in the coal gasification unit 1 and the wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
In the process of this embodiment, the gasifying agent in the coal gasification process is carbon dioxide; the ratio of the molar weight of the carbon dioxide added into the coal gasification unit 1 to the molar weight of the carbon in the coal is 0.1-1.5, preferably 0.8-1; the gasification temperature in the coal gasification furnace is 800-2000 ℃, and preferably 900-1300 ℃; the pressure in the coal gasification furnace is 0.5-8 MPa, preferably 3-6 MPa; the produced fermentation raw material gas comprises carbon monoxide, hydrogen and carbon dioxide, wherein the content of the carbon monoxide is 30-95%, and preferably 60-85%.
In the process of this embodiment, the bioreactor comprises a microorganism of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium (Clostridium ljungdahlii) and Clostridium magnum (Clostridium magnum).
In the process of this embodiment, the CO conversion rate in the biological fermentation unit 2 is 60 to 99%, preferably 75 to 90%, and the mass concentration of the oxygen-containing organic product in the fermentation liquid is 3 to 15%; preferably, the mass concentration of the oxygen-containing organic product is 4-10%; more preferably, the mass concentration of the oxygen-containing organic product is 5 to 8%; the oxygen-containing organic product is ethanol.
In the process of this example, the bacteria-containing residual liquid is concentrated and dried in the bacteria-containing residual liquid treatment unit 5 to produce solid protein; and/or the bacteria-containing raffinate is subjected to anaerobic fermentation in an anaerobic fermentation subunit of the bacteria-containing raffinate treatment unit 5 to generate the biogas.
Example 10
A process for producing oxygenated organics from carbon dioxide and coal using the system described in example 4.
In the process of the embodiment, coal is pretreated by the raw material coal pretreatment unit 6 and then is fed into the coal gasification unit 1, and the carbon dioxide unit 7 feeds carbon dioxide into the coal gasification unit 1; coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate fermentation raw material gas; the fermentation raw gas enters a fermentation raw gas purification unit 4 to remove impurities in the fermentation raw gas, wherein the impurities include but are not limited to fly ash, sulfur-containing compounds and chlorine-containing compounds; the fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a biological fermentation reactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic matter products; the fermentation liquor enters a fermentation liquor separation unit 3, and oxygen-containing organic products and bacteria-containing residual liquor are obtained through separation; the bacteria-containing residual liquid enters a bacteria-containing residual liquid treatment unit 5 for a bacteria-containing residual liquid treatment process; and the gasification ash in the coal gasification unit 1 and the wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
In the process of this example, the gasifying agent in the coal gasification process comprises carbon dioxide, oxygen and water; the ratio of the molar weight of carbon dioxide added to the coal gasification unit 1 to the molar weight of carbon in the coal is 0.1 to 1.2, preferably 0.5 to 1; the gasification temperature in the coal gasification furnace is 800-2000 ℃, and preferably 900-1300 ℃; the pressure in the coal gasification furnace is 0.5-8 MPa, preferably 3-6 MPa; the generated fermentation raw material gas comprises carbon monoxide, hydrogen and carbon dioxide, wherein the content of the carbon monoxide is 30-95%, and preferably 50-80%.
In the process of this example, microorganisms of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium (Clostridium ljungdahlii) and Clostridium macrocephalum (Clostridium magnum) are contained in the bioreactor.
In the process of this embodiment, the CO conversion rate in the biological fermentation unit 2 is 60 to 99%, preferably 75 to 90%, and the mass concentration of the oxygen-containing organic product in the fermentation liquid is 3 to 15%; preferably, the mass concentration of the oxygen-containing organic product is 4-10%; more preferably, the mass concentration of the oxygen-containing organic product is 5 to 8%.
In the process of this embodiment, the oxygenate product comprises one or a combination of ethanol, acetic acid, butanol, and butanediol.
In the process of this embodiment, the fermentation tail gas of the biological fermentation unit 2 enters the fermentation tail gas treatment unit 10', and the fermentation tail gas is purified in the fermentation tail gas treatment unit 10' to obtain hydrogen.
In the method of this example, the bacteria-containing raffinate is concentrated and dried in the bacteria-containing raffinate treating unit 5 to produce a solid protein; and/or the bacteria-containing raffinate is subjected to anaerobic fermentation in an anaerobic fermentation subunit of the bacteria-containing raffinate treatment unit 5 to generate the biogas.
Example 11
A process for producing oxygenated organics from carbon dioxide and coal using the system described in example 5.
In the process of the embodiment, coal is pretreated by the raw material coal pretreatment unit 6 and then is fed into the coal gasification unit 1, and the carbon dioxide unit 7 feeds carbon dioxide into the coal gasification unit 1; the coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate a fermentation raw material gas; the fermentation raw gas enters a fermentation raw gas purification unit 4 to remove impurities in the fermentation raw gas, wherein the impurities include but are not limited to fly ash, sulfur-containing compounds and chlorine-containing compounds; the fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a biological fermentation reactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic matter products; the fermentation liquor enters a fermentation liquor separation unit 3, and oxygen-containing organic products and bacteria-containing residual liquor are obtained through separation; the bacteria-containing residual liquid enters a bacteria-containing residual liquid treatment unit 5' to carry out a bacteria-containing residual liquid treatment process; and the gasified ash in the coal gasification unit 1 and the wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
In the process of this example, the gasifying agent in the coal gasification process comprises carbon dioxide, oxygen and water; the ratio of the molar weight of carbon dioxide added to the coal gasification unit 1 to the molar weight of carbon in the coal is 0.1 to 1.2, preferably 0.5 to 1; the gasification temperature in the coal gasification furnace is 800-2000 ℃, and preferably 900-1300 ℃; the pressure in the coal gasifier is 0.5 to 8MPa, preferably 3 to 6MPa; the generated fermentation raw material gas comprises carbon monoxide, hydrogen and carbon dioxide, wherein the content of the carbon monoxide is 30-95%, and preferably 50-80%.
In the process of this example, microorganisms of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium (Clostridium ljungdahlii) and Clostridium macrocephalum (Clostridium magnum) are contained in the bioreactor.
In the process of the embodiment, the CO conversion rate in the biological fermentation unit 2 is 60-99%, preferably 75-90%, and the mass concentration of the oxygen-containing organic product in the fermentation liquid is 3-15%; preferably, the mass concentration of the oxygen-containing organic product is 4-10%; more preferably, the mass concentration of the oxygen-containing organic product is 5 to 8%.
In the process of this embodiment, the oxygenate product comprises one or a combination of ethanol, acetic acid, butanol, and butanediol.
In the method of this embodiment, the bacteria-containing raffinate is anaerobically fermented in the anaerobic fermentation subunit of the bacteria-containing raffinate treatment unit 5 'to generate biogas, and the biogas generated in the bacteria-containing raffinate treatment unit 5' is further conveyed back to the coal gasification unit 1 to be involved in coal gasification reaction.
Example 13
A process for producing an oxygenated organic using the system described in example 6.
In the process of the embodiment, coal is pretreated by the raw material coal pretreatment unit 6 and then is fed into the coal gasification unit 1; coal is gasified in a coal gasification furnace of the coal gasification unit 1 to generate fermentation raw material gas; the fermentation raw material gas enters a fermentation raw material gas purification unit 4 to remove impurities in the fermentation raw material gas, wherein the impurities include but are not limited to fly ash, sulfur-containing compounds and chlorine-containing compounds; the fermentation raw material gas purified by the fermentation raw material gas purification unit 4 enters the biological fermentation unit 2, and fermentation process is carried out on the fermentation gas in a biological fermentation reactor of the biological fermentation unit 2 to generate fermentation liquid, wherein the fermentation liquid contains oxygen-containing organic matter products; the fermentation liquor enters a fermentation liquor separation unit 3, and an oxygen-containing organic product and a bacterium-containing residual liquid are obtained through separation; the residual liquid containing the bacteria enters a residual liquid containing the bacteria treatment unit 5 to carry out the treatment process of the residual liquid containing the bacteria; and the gasification ash in the coal gasification unit 1 and the wastewater in the fermentation raw material gas purification unit 4 enter a solid waste/wastewater treatment unit 8 for solid waste and wastewater treatment.
In the process of the embodiment, the gasifying agents in the coal gasification process are water and oxygen; the gasification temperature in the coal gasification furnace is 800-2000 ℃, and preferably 900-1300 ℃; the pressure in the coal gasification furnace is 0.5-8 MPa, preferably 3-6 MPa; the produced fermentation raw material gas comprises carbon monoxide, hydrogen and carbon dioxide, wherein the content of the carbon monoxide is 30-70%, and preferably 40-65%.
In the process of this embodiment, the bioreactor comprises a microorganism of the genus Clostridium comprising one or a combination of Clostridium (Clostridium carboxidigorans), clostridium (Clostridium ljungdahlii) and Clostridium magnum (Clostridium magnum).
In the process of this embodiment, the CO conversion in the biological fermentation unit 2 is 60 to 99%, preferably 75 to 85%, and the mass concentration of the oxygen-containing organic product in the fermentation broth is 3 to 15%; preferably, the mass concentration of the oxygen-containing organic product is 4-10%; more preferably, the mass concentration of the oxygen-containing organic product is 5 to 8%.
In the process of this embodiment, the oxygenate product comprises one or a combination of ethanol, acetic acid, butanol, and butanediol.
In the method of this example, the bacteria-containing raffinate is concentrated and dried in the bacteria-containing raffinate treating unit 5 to produce a solid protein; and/or the bacteria-containing residual liquid is subjected to anaerobic fermentation in an anaerobic fermentation subunit of the bacteria-containing residual liquid treatment unit 5 to generate the biogas.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (15)

1. A process for producing oxygenated organics from carbon dioxide and coal, comprising a system for producing oxygenated organics from carbon dioxide and coal, the system comprising: the system comprises a coal gasification unit (1), a biological fermentation unit (2), a fermentation liquor separation unit (3) and a carbon dioxide unit (7); wherein the content of the first and second substances,
a gas phase outlet of the carbon dioxide unit (7) is connected with a gas phase inlet of the coal gasification unit (1), a gas phase outlet of the coal gasification unit (1) is connected with a gas phase inlet of the fermentation raw material gas purification unit (4), a gas phase outlet of the fermentation raw material gas purification unit (4) is connected with a gas phase inlet of the biological fermentation unit (2), and a liquid phase outlet of the biological fermentation unit (2) is connected with a liquid phase inlet of the fermentation liquid separation unit (3);
a coal gasification process is carried out in the coal gasification unit (1) to generate a fermentation raw material gas, the fermentation raw material gas contains carbon monoxide, the content of the carbon monoxide is 60-95%, a gasification agent in the coal gasification process contains carbon dioxide, the carbon dioxide contained in the gasification agent is provided by the carbon dioxide unit (7),
the biological fermentation unit (2) performs a fermentation process of fermentation raw material gas to generate fermentation liquor, the fermentation liquor comprises oxygen-containing organic matter products,
the coal gasification unit (1) comprises a coal gasification furnace, the gasification pressure in the coal gasification furnace is 3-6 Mpa,
the process comprises the following steps:
1) The coal is pretreated by the raw material coal pretreatment unit (6) and then is fed into the coal gasification unit (1), and the carbon dioxide unit (7) feeds carbon dioxide into the coal gasification unit (1);
2) The coal is gasified in a coal gasification furnace of a coal gasification unit (1) to generate a fermentation raw material gas, wherein the gasification temperature in the coal gasification furnace is 900-1300 ℃, and the gasification pressure is 3-6 MPa;
3) Feeding the fermentation raw material gas generated in the step (2) into a fermentation raw material gas purification unit (4) to remove impurities in the fermentation raw material gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds;
4) The fermentation raw material gas purified by the fermentation raw material gas purification unit (4) enters the biological fermentation unit (2), and the fermentation raw material gas is fermented in a biological fermentation reactor of the biological fermentation unit (2) to generate fermentation liquor, wherein the fermentation liquor contains oxygen-containing organic products;
5) The fermentation liquor generated in the step (4) enters a fermentation liquor separation unit (3) and is separated to obtain an oxygen-containing organic product and a bacterium-containing residual liquid; and
6) And (5) the bacterium-containing residual liquid generated in the step (5) enters a bacterium-containing residual liquid treatment unit (5) to carry out a bacterium-containing residual liquid treatment process.
2. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: the carbon dioxide unit (7) comprises a carbon dioxide separation subunit and a carbon dioxide compressor, and a gas phase outlet of the carbon dioxide separation subunit is connected with an inlet of the carbon dioxide compressor.
3. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: the coal gasification unit (1) comprises a coal gasification furnace, and the coal gasification furnace is one of a fixed bed gasification furnace, a moving bed gasification furnace, a fluidized bed gasification furnace and a fluidized bed gasification furnace.
4. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: fermentation raw gas purification unit (4) contain gas-solid separation subunit, gas washing subunit and gas and inhale the monkshood unit, gas-solid separation subunit contains the cyclone dust remover, gas washing subunit contains the gas scrubbing tower.
5. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: the biological fermentation unit (2) comprises a biological fermentation reactor, and the biological fermentation reactor is one or the combination of a bubbling bed reactor, an airlift loop reactor and a stirred tank reactor.
6. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: the fermentation liquor separation unit (3) comprises a rectifying tower, and the rectifying tower is one or a combination of a packed tower, a sieve plate tower and a composite tower.
7. The process for producing oxygenated organics from carbon dioxide and coal according to any one of claims 1, 3, 4, 6, further comprising: a solid waste/wastewater treatment unit (8) and a bacteria-containing raffinate treatment unit (5); wherein the content of the first and second substances,
a solid waste outlet in the coal gasification unit (1) is connected with a solid waste inlet in the solid waste/wastewater treatment unit (8);
a solid waste outlet in the fermentation raw material gas purification unit (4) is connected with a solid waste inlet in the solid waste/wastewater treatment unit (8);
a wastewater outlet in the fermentation raw material gas purification unit (4) is connected with a wastewater inlet in the solid waste/wastewater treatment unit (8); and
and a bacterium-containing residual liquid outlet in the fermentation liquid separation unit (3) is connected with an inlet of the bacterium-containing residual liquid treatment unit (5).
8. The process for producing oxygenated organic matter from carbon dioxide and coal according to claim 1, further comprising a fermentation tail gas treatment unit (10), wherein a gas phase inlet of the fermentation tail gas treatment unit (10) is connected to a gas phase outlet of the biological fermentation unit (2); the fermentation tail gas treatment unit (10) comprises a hydrogen purification subunit and is used for purifying the fermentation tail gas to obtain hydrogen.
9. Process for the production of oxygenated organics from carbon dioxide and coal according to claim 1 or 6,
the bacteria-containing residual liquid treatment unit (5) comprises a concentration subunit and a drying subunit; and/or the presence of a gas in the gas,
the bacteria-containing raffinate treatment unit (5) comprises an anaerobic fermentation subunit.
10. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by:
the gasifying agent in the coal gasifying process in the step (2) comprises carbon dioxide, and also comprises one or a combination of oxygen and water;
the fermentation raw material gas in the step (2) comprises carbon monoxide and one or a combination of carbon dioxide and hydrogen;
the oxygenated organics comprise one or a combination of ethanol, acetic acid, butanol, and butanediol.
11. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, wherein:
adding a coal gasification catalyst in a coal gasification furnace for increasing the coal gasification rate, wherein the coal gasification catalyst comprises one or a combination of an alkali metal compound, an alkaline earth metal compound and a transition metal compound.
12. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, characterized by: the bioreactor comprises a microorganism of the genus clostridium, which comprises one or a combination of clostridium, clostridium ljunii and clostridium magnum.
13. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, wherein: and the gasification ash in the coal gasification unit (1) and the wastewater in the fermentation raw material gas purification unit (4) enter a solid waste/wastewater treatment unit (8) for solid waste and wastewater treatment.
14. The process of claim 1 for producing oxygenated organics from carbon dioxide and coal, wherein: fermentation tail gas of the biological fermentation unit (2) enters a fermentation tail gas treatment unit (10), and the fermentation tail gas is purified in the fermentation tail gas treatment unit (10) to obtain hydrogen.
15. The process of producing an oxygenated organic from carbon dioxide and coal according to claim 1,
the strain-containing raffinate is concentrated and dried in a strain-containing raffinate treatment unit (5) to generate solid protein; and/or the presence of a gas in the gas,
the bacteria-containing residual liquid is subjected to anaerobic fermentation in an anaerobic fermentation subunit of the bacteria-containing residual liquid treatment unit (5) to generate biogas.
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