CN113528164A - System and process for co-producing ethanol and protein by utilizing coal quality - Google Patents

System and process for co-producing ethanol and protein by utilizing coal quality Download PDF

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Publication number
CN113528164A
CN113528164A CN202110727262.8A CN202110727262A CN113528164A CN 113528164 A CN113528164 A CN 113528164A CN 202110727262 A CN202110727262 A CN 202110727262A CN 113528164 A CN113528164 A CN 113528164A
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unit
gas
fermentation
pyrolysis
coal
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王铁峰
胡永琪
蓝晓程
周理龙
金涌
王建英
刘玉敏
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Tsinghua University
Hebei University of Science and Technology
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Tsinghua University
Hebei University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • 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
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • 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
    • C10J2300/0943—Coke
    • 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
    • C10J2300/0953—Gasifying agents
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

A system for co-producing ethanol and protein by coal quality utilization, comprising: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit; wherein a solid phase outlet of the coal pyrolysis unit is in communication with the CO2/O2The solid-phase inlets of the reduction units are connected,the CO is2/O2And a gas phase outlet of the reduction unit is connected with a gas phase inlet of the CO purification unit, a liquid outlet of the biological fermentation unit is connected with a liquid inlet of the fermentation liquid separation unit, and a gas phase outlet of the coal pyrolysis unit is connected with a gas phase inlet of the pyrolysis gas separation unit.

Description

System and process for co-producing ethanol and protein by utilizing coal quality
Technical Field
The invention relates to a system and a process for co-producing ethanol and protein by utilizing coal according to quality, and belongs to the field of coal chemical industry.
Background
Coal is an important fossil resource, is one of the main energy sources for production and life of human beings, and is also one of the main raw materials of organic chemical industry. However, the large amount of mining and using coal has serious negative impact on the ecological environment of the earth, and the most important one is that a large amount of carbon element in the form of coal is converted into CO2The emission into the atmosphere causes serious greenhouse effect, and seriously threatens the sustainable development of human beings. As the government of China puts forward the targets of 'carbon peak reaching' and 'carbon neutralization', the carbon peak reaching and the carbon neutralization are used as CO2The coal chemical industry, one of the important sources, is bound to be impacted, and the comprehensive utilization of coal is an important way for realizing the sustainable development of the coal chemical industry.
In the traditional coal chemical technology, coal is generally subjected to a longer process route to prepare products such as fuel oil, methanol, dimethyl ether, olefin, ethylene glycol and the like. In the processes, coal is generally gasified into synthesis gas, and the synthesis gas is further converted into other chemicals, so that the process has the disadvantages of high production cost, large carbon dioxide emission and poor overall economic benefit.
Generally speaking, the coal chemical industry is a large-scale CO release2How to reduce or even eliminate CO discharged in the coal chemical production process2Is the key of the sustainable development of the coal chemical industry.
Disclosure of Invention
In view of the above background, the present invention provides a system and a process for co-producing ethanol and protein by utilizing coal according to quality. The system and the process utilize coal resources according to quality, and the formed coke is used as a reducing agent to reduce carbon dioxide into carbon monoxide. Further combining with a biological fermentation technology, the carbon monoxide is converted into ethanol, and simultaneously, the solid protein is co-produced. The system and process reduce CO in coal chemical industry2The emission has important significance for achieving the goals of 'carbon peak reaching' and 'carbon neutralization'.
In one aspect, to achieve the above object, the present invention provides a system for co-producing ethanol and protein by coal quality separation, including: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit; wherein a solid phase outlet of the coal pyrolysis unit and the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2And a gas phase outlet of the reduction unit is connected with a gas phase inlet of the CO purification unit, a liquid outlet of the biological fermentation unit is connected with a liquid inlet of the fermentation liquid separation unit, and a gas phase outlet of the coal pyrolysis unit is connected with a gas phase inlet of the pyrolysis gas separation unit. The coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
Further, the system for coproducing ethanol and protein by coal quality utilization also comprises a synthesis gas conversion unit, wherein the reaction process in the synthesis gas conversion unit is one or more of methanol preparation from synthesis gas, aromatic hydrocarbon preparation from synthesis gas, olefin preparation from synthesis gas and ethylene glycol preparation from synthesis gas.
Further, a hydrogen outlet of the pyrolysis gas separation unit is connected with a gas inlet of the hydrogen purification unit, and H is carried out in the pyrolysis gas separation unit2With organic productsAnd (5) separating.
Further, a first CO outlet of the CO purification unit is connected with a gas phase inlet of the biological fermentation unit, a second CO outlet of the CO purification unit is connected with a CO inlet of the synthesis gas conversion unit, and an H outlet of the hydrogen purification unit is connected with a hydrogen inlet of the synthesis gas conversion unit2The first outlet is connected with the biological fermentation unit, and the H of the hydrogen purification unit2Second outlet and H of the syngas conversion unit2The inlets are connected. .
Further, the reactor used in the coal pyrolysis unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor and a fluidized bed reactor.
Furthermore, the separation equipment used by the pyrolysis gas separation unit comprises one or more of pressure swing adsorption, a rectifying tower, a heat exchanger and a refrigerator; h2The purification unit comprises equipment including one or more of a cyclone separator, a heat exchanger, a desulfurizing tower and a washing tower; CO 22/O2The reactor used by the reduction unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor and a fluidized bed reactor; the equipment used by the CO purification unit comprises one or more of a cyclone separator, an absorption tower, an adsorption tower, a heat exchanger and a condenser.
Further, the reactor adopted by the biological fermentation unit is one or more of a bubbling bed reactor, a stirred tank reactor and a packed bed reactor; the fermentation liquor separation unit comprises one or more of a concentrator, a filter, a centrifuge, a washing tower, a dryer, an extractor, a rectifying tower and an absorption tower.
Further, the system for coproducing ethanol and protein by utilizing coal quality based on different qualities also comprises a fermentation tail gas treatment unit and a bacterium-containing residual liquid treatment unit; a gas outlet of the biological fermentation unit is connected with a gas inlet of the fermentation tail gas treatment unit, and a bacterium-containing residual liquid outlet of the fermentation liquid separation unit is connected with the bacterium-containing residual liquid treatment unit; the bacteria-containing residual liquid treatment unit comprises one or more of a filter, a centrifuge, a fermentation tank and a dryer.
On the other hand, the invention provides a process for coproducing ethanol and protein by utilizing coal quality, which comprises the following steps:
(1) pyrolyzing coal in a coal pyrolysis unit to obtain semicoke and pyrolysis gas, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit;
(2) separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons;
(3) semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds;
(4) the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol;
(5) the fermentation liquor generated in the step (3) enters a fermentation liquor separation unit, ethanol, mycoprotein and bacteria-containing residual liquor are obtained through separation, and the bacteria-containing residual liquor enters a bacteria-containing residual liquor treatment unit;
further, the oxidizing gas of step (3) contains CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2，O2From air or pure oxygen.
Further, H contained in the product separated in the step (2)2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds; a part H2Purified gas enters a biological fermentation unit to participate in the fermentation process in the step (4), and part of H2The purified gas enters a syngas conversion unit.
Further, a portion of the CO purge gas generated in step (3) enters a syngas conversion unit; and carrying out one or more reaction processes of preparing methanol from synthesis gas, preparing aromatic hydrocarbon from synthesis gas, preparing olefin from synthesis gas and preparing ethylene glycol from synthesis gas in the synthesis gas conversion unit.
Further, the pyrolysis temperature of the coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
The invention has the beneficial effects that:
in order to realize the aim of 'carbon neutralization' in the coal chemical industry, the invention firstly carries out pyrolysis and quality separation on coal, and the obtained semi coke and coke are used for reducing CO2CO production, ethanol and mycoprotein are produced by CO through a biological fermentation process, and CO is a byproduct2Can be returned to CO2Reduction or avoidance of CO during reduction2Discharge of (2), coal quality separation of produced H2With CO2The CO generated by reduction is used as synthesis gas, and can be further synthesized into methanol, aromatic hydrocarbon, olefin, ethylene glycol and the like. Carbon balance and energy balance calculations indicate that an external supply of CO is also required to proceed with the process2And the sustainability of production is realized, so that the process of coal chemical industry is changed from a carbon emission process to a carbon sink process.
Drawings
FIG. 1 is a schematic diagram of a coal quality utilization co-production ethanol and protein system according to an embodiment of the invention.
FIG. 2 is a schematic diagram of a coal quality utilization co-production ethanol and protein system according to another embodiment of the invention.
FIG. 3 is a schematic diagram of a coal quality utilization co-production ethanol and protein system according to another embodiment of the invention.
FIG. 4 is a schematic diagram of a coal quality utilization co-production ethanol and protein system according to another embodiment of the 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 shows the coal qualitySchematic diagram of a system for co-production of ethanol and protein. In the system of this embodiment, it includes: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit.
As shown in FIG. 1, the solid phase outlet of the coal pyrolysis unit is connected with the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2And a gas phase outlet of the reduction unit is connected with a gas phase inlet of the CO purification unit, a liquid outlet of the biological fermentation unit is connected with a liquid inlet of the fermentation liquid separation unit, and a gas phase outlet of the coal pyrolysis unit is connected with a gas phase inlet of the pyrolysis gas separation unit. The coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
In the system of this embodiment, the hydrogen outlet of the pyrolysis gas separation unit is connected to the gas inlet of the hydrogen purification unit, and H is carried out in the pyrolysis gas separation unit2Separation from the organic product.
In the system of this embodiment, a syngas conversion unit is included, and the reaction process in the syngas conversion unit is one or more of syngas to methanol, syngas to aromatics, syngas to olefins, and syngas to ethylene glycol.
In the system of this embodiment, the first CO outlet of the CO purification unit is connected to the gas phase inlet of the biological fermentation unit, the second CO outlet of the CO purification unit is connected to the CO inlet of the syngas conversion unit, and the H outlet of the hydrogen purification unit is connected to the H inlet of the syngas conversion unit2The first outlet is connected with the biological fermentation unit, and the H of the hydrogen purification unit2Second outlet and H of the syngas conversion unit2The inlets are connected.
In the system of this embodiment, the reactor used in the coal pyrolysis unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor, and a entrained flow reactor.
In the system of the embodiment, the separation equipment used by the pyrolysis gas separation unit comprises one or more of pressure swing adsorption, a rectifying tower, a heat exchanger and a refrigerator; h2The purification unit comprises equipment including one or more of a cyclone separator, a heat exchanger, a desulfurizing tower and a washing tower; CO 22/O2The reactor used by the reduction unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor and a fluidized bed reactor; the equipment used by the CO purification unit comprises one or more of a cyclone separator, an absorption tower, an adsorption tower, a heat exchanger and a condenser.
In the system of the embodiment, the reactor adopted by the biological fermentation unit is one or more of a bubbling bed reactor, a stirred tank reactor and a packed bed reactor; the fermentation liquor separation unit comprises one or more of a concentrator, a filter, a centrifuge, a washing tower, a dryer, an extractor, a rectifying tower and an absorption tower.
The system comprises a fermentation tail gas treatment unit and a bacteria-containing raffinate treatment unit; a gas outlet of the biological fermentation unit is connected with a gas inlet of the fermentation tail gas treatment unit, and a bacterium-containing residual liquid outlet of the fermentation liquid separation unit is connected with the bacterium-containing residual liquid treatment unit; the bacteria-containing residual liquid treatment unit comprises one or more of a filter, a centrifuge, a fermentation tank and a dryer.
Example 2
FIG. 2 is a schematic diagram of a system for co-production of ethanol and protein by coal quality separation utilization. In the system of this embodiment, it includes: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit.
As shown in FIG. 2, the solid phase outlet of the coal pyrolysis unit is connected with the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2The gas phase outlet of the reduction unit is connected with the gas phase inlet of the CO purification unit, and the liquid of the biological fermentation unitAnd the gas outlet of the coal pyrolysis unit is connected with the gas inlet of the pyrolysis gas separation unit. The coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
In the system of this embodiment, the hydrogen outlet of the pyrolysis gas separation unit is connected to the gas inlet of the hydrogen purification unit, and H is carried out in the pyrolysis gas separation unit2Separation from the organic product.
In the system of this embodiment, a syngas conversion unit is included, and the reaction process in the syngas conversion unit is one or more of syngas to methanol, syngas to aromatics, syngas to olefins, and syngas to ethylene glycol.
In the system of this embodiment, the first CO outlet of the CO purification unit is connected to the gas phase inlet of the biological fermentation unit, the second CO outlet of the CO purification unit is connected to the CO inlet of the syngas conversion unit, and the H outlet of the hydrogen purification unit is connected to the H inlet of the syngas conversion unit2Outlet and H of the syngas conversion unit2The inlets are connected.
In this reaction system, the pyrolysis gas separation unit, the product fermentation unit, the fermentation tail gas generation treatment unit, and the bacteria-containing raffinate treatment unit were the same as in example 1.
Example 3
FIG. 3 is a schematic diagram of a coal quality utilization co-production ethanol and protein system. In the system of this embodiment, it includes: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit.
As shown in FIG. 3, the solid phase outlet of the coal pyrolysis unit is connected to the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2The gas phase outlet of the reduction unit is connected with the gas phase inlet of the CO purification unit, and the liquid of the biological fermentation unitAnd the gas outlet of the coal pyrolysis unit is connected with the gas inlet of the pyrolysis gas separation unit. The coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
In the system of this embodiment, the hydrogen outlet of the pyrolysis gas separation unit is connected to the gas inlet of the hydrogen purification unit, and H is carried out in the pyrolysis gas separation unit2Separation from organic products, H in a hydrogen purification unit2Purifying to remove impurities to obtain H2Purifying the gasified gas.
In this reaction system, the pyrolysis gas separation unit, the product fermentation unit, the fermentation tail gas generation treatment unit, and the bacteria-containing raffinate treatment unit were the same as in example 1.
Example 4
FIG. 4 is a schematic diagram of a coal quality utilization co-production ethanol and protein system. In the system of this embodiment, it includes: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit.
As shown in FIG. 4, the solid phase outlet of the coal pyrolysis unit is connected to the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2And a gas phase outlet of the reduction unit is connected with a gas phase inlet of the CO purification unit, a liquid outlet of the biological fermentation unit is connected with a liquid inlet of the fermentation liquid separation unit, and a gas phase outlet of the coal pyrolysis unit is connected with a gas phase inlet of the pyrolysis gas separation unit. The coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
In the system of this embodiment, the hydrogen outlet of the pyrolysis gas separation unit is connected to the hydrogen inlet of the pyrolysis gas separation unitThe gas inlets of the hydrogen purification units are connected, and H is carried out in the pyrolysis gas separation unit2Separation from organic products, H in a hydrogen purification unit2Purifying to remove impurities to obtain H2Purifying the gasified gas.
In the system of this embodiment, H of the hydrogen purification unit2Outlet and H of the syngas conversion unit2The inlets are connected.
In this reaction system, the pyrolysis gas separation unit, the product fermentation unit, the fermentation tail gas generation treatment unit, and the bacteria-containing raffinate treatment unit were the same as in example 1.
Example 5
Coal was fractionated using the system described in example 1 for a process for co-production of ethanol and protein.
In the process of this example, after the coal is pyrolyzed in the coal pyrolysis unit, semicoke and pyrolysis gas are obtained, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit; separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons; semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds; the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol; and (3) allowing the fermentation liquor to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
In the process of this embodiment, the oxidizing gas comprises CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2，O2From air or pure oxygen.
In the process of this example, pyrolysis gasH in the separation unit2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds; a part H2Purified gas enters the biological fermentation unit to participate in the fermentation process in the biological fermentation unit, and part of the purified gas H2The purified gas enters a syngas conversion unit.
In the process of this embodiment, a portion of the CO purge gas generated in the CO purge unit enters the syngas conversion unit; and carrying out one or more reaction processes of preparing methanol from synthesis gas, preparing aromatic hydrocarbon from synthesis gas, preparing olefin from synthesis gas and preparing ethylene glycol from synthesis gas in the synthesis gas conversion unit.
In the process of the embodiment, the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
Example 6
Coal was fractionated using the system described in example 1 for a process for co-production of ethanol and protein.
In the process of this example, after the coal is pyrolyzed in the coal pyrolysis unit, semicoke and pyrolysis gas are obtained, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit; separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons; semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds; the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol; and (3) allowing the fermentation liquor to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
In the process of this embodiment, the oxidizing gas comprises CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2And H2O，O2From air or pure oxygen.
In the process of this example, the pyrolysis gas is separated from the hydrogen-containing gas in the unit2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds; a part H2Purified gas enters the biological fermentation unit to participate in the fermentation process in the biological fermentation unit, and part of the purified gas H2The purified gas enters a syngas conversion unit.
In the process of this embodiment, a portion of the CO purge gas generated in the CO purge unit enters the syngas conversion unit; and carrying out one or more reaction processes of preparing methanol from synthesis gas, preparing aromatic hydrocarbon from synthesis gas, preparing olefin from synthesis gas and preparing ethylene glycol from synthesis gas in the synthesis gas conversion unit.
In the process of the embodiment, the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
Example 7
Coal was fractionated using the system described in example 2 for a process for co-production of ethanol and protein.
In the process of this example, after the coal is pyrolyzed in the coal pyrolysis unit, semicoke and pyrolysis gas are obtained, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit; separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons; semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2Removing impurities from the CO-containing gas by a CO purification unit to obtain CO purified gas, wherein the impurities comprise fly ash and impurities containing COOne or more of a sulfur compound, a chlorine compound; the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol; and (3) allowing the fermentation liquor to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
In the process of this embodiment, the oxidizing gas comprises CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2，O2From air or pure oxygen.
In the process of this example, the pyrolysis gas is separated from the hydrogen-containing gas in the unit2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds; h2The purified gas enters a syngas conversion unit.
In the process of this embodiment, a portion of the CO purge gas generated in the CO purge unit enters the syngas conversion unit; and carrying out one or more reaction processes of preparing methanol from synthesis gas, preparing aromatic hydrocarbon from synthesis gas, preparing olefin from synthesis gas and preparing ethylene glycol from synthesis gas in the synthesis gas conversion unit.
In the process of the embodiment, the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
Example 8
Coal was fractionated using the system described in example 3 for a process for co-production of ethanol and protein.
In the process of this example, after the coal is pyrolyzed in the coal pyrolysis unit, semicoke and pyrolysis gas are obtained, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit; separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons; semi-cokeIn CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds; the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol; and (3) allowing the fermentation liquor to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
In the process of this embodiment, the oxidizing gas comprises CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2，O2From air or pure oxygen.
In the process of this example, the pyrolysis gas is separated from the hydrogen-containing gas in the unit2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds.
In the process of the embodiment, the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
Example 9
Coal was fractionated using the process for co-production of ethanol and protein using the system described in example 4.
In the process of this example, after the coal is pyrolyzed in the coal pyrolysis unit, semicoke and pyrolysis gas are obtained, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit; separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons; semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds; the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol; and (3) allowing the fermentation liquor to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
In the process of this embodiment, the oxidizing gas comprises CO2One or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment units; the oxidizing gas further contains O2，O2From air or pure oxygen.
In the process of this example, the pyrolysis gas is separated from the hydrogen-containing gas in the unit2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds; h2The purified gas enters the biological fermentation unit and participates in the fermentation process in the biological fermentation unit.
In the process of the embodiment, the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.

Claims (13)

1. A system for coproducing ethanol and protein by coal quality separation utilization is characterized by comprising: coal pyrolysis unit, pyrolysis gas separation unit, CO2/O2The device comprises a reduction unit, a biological fermentation unit, a fermentation liquor separation unit and a hydrogen purification unit; wherein,
a solid phase outlet of the coal pyrolysis unit and the CO2/O2The solid phase inlet of the reduction unit is connected, and the CO is2/O2The gas phase outlet of the reduction unit is connected with the gas phase inlet of the CO purification unit, the liquid outlet of the biological fermentation unit is connected with the liquid inlet of the fermentation liquor separation unit, and the gas phase of the coal pyrolysis unitThe outlet is connected with the gas phase inlet of the pyrolysis gas separation unit;
the coking process of coal is carried out in the coal pyrolysis unit, and the CO is2/O2Reduction of CO with coke in a reduction unit2Generating CO, and carrying out a fermentation process of CO-containing gas by the biological fermentation unit, wherein the fermentation process generates fermentation liquor containing ethanol.
2. The system of claim 1, wherein: the device also comprises a synthesis gas conversion unit, wherein the reaction process in the synthesis gas conversion unit is one or more of preparation of methanol from synthesis gas, preparation of aromatic hydrocarbon from synthesis gas, preparation of olefin from synthesis gas and preparation of ethylene glycol from synthesis gas.
3. The system of claim 1, wherein: the hydrogen outlet of the pyrolysis gas separation unit is connected with the gas inlet of the hydrogen purification unit, and H is carried out in the pyrolysis gas separation unit2Separation from the organic product.
4. The system according to any one of claims 1, 2, 3, wherein: a CO first outlet of the CO purification unit is connected with a gas phase inlet of the biological fermentation unit, a CO second outlet of the CO purification unit is connected with a CO inlet of the synthesis gas conversion unit, and an H of the hydrogen purification unit2The first outlet is connected with the biological fermentation unit, and the H of the hydrogen purification unit2Second outlet and H of the syngas conversion unit2The inlets are connected.
5. The system of claim 1, wherein: the reactor used in the coal pyrolysis unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor and a fluidized bed reactor.
6. A system according to claims 1 and 3, characterized in that: the separation equipment used by the pyrolysis gas separation unit comprises pressure swing adsorption and rectificationOne or more of a tower, a heat exchanger and a refrigerator; h2The purification unit comprises equipment including one or more of a cyclone separator, a heat exchanger, a desulfurizing tower and a washing tower; CO 22/O2The reactor used by the reduction unit is one or more of a fixed bed reactor, a moving bed reactor, a fluidized bed reactor, a circulating fluidized bed reactor and a fluidized bed reactor; the equipment used by the CO purification unit comprises one or more of a cyclone separator, an absorption tower, an adsorption tower, a heat exchanger and a condenser.
7. The system of claim 1, wherein: the reactor adopted by the biological fermentation unit is one or more of a bubbling bed reactor, a stirred tank reactor and a packed bed reactor; the fermentation liquor separation unit comprises one or more of a concentrator, a filter, a centrifuge, a washing tower, a dryer, an extractor, a rectifying tower and an absorption tower.
8. The system of claim 1, wherein: the fermentation tail gas treatment unit and the bacteria-containing residual liquid treatment unit are also included; a gas outlet of the biological fermentation unit is connected with a gas inlet of the fermentation tail gas treatment unit, and a bacterium-containing residual liquid outlet of the fermentation liquid separation unit is connected with the bacterium-containing residual liquid treatment unit; the bacteria-containing residual liquid treatment unit comprises one or more of a filter, a centrifuge, a fermentation tank and a dryer.
9. A process for the co-production of ethanol and protein from coal using the system of any one of claims 1 to 8, comprising the steps of:
1) pyrolyzing coal in a coal pyrolysis unit to obtain semicoke and pyrolysis gas, wherein the semicoke is fed with CO2/O2The reduction unit is used for sending the pyrolysis gas into the pyrolysis gas separation unit;
2) separating the pyrolysis gas by the pyrolysis gas separation unit to obtain H-containing gas2Gas and organic products comprising one or more of coal tar, gaseous hydrocarbons;
3) semicoke in CO2/O2The reduction unit reacts with an oxidizing gas comprising CO to form a CO-containing gas2The CO-containing gas is subjected to a CO purification unit to remove impurities to obtain CO purified gas, wherein the impurities comprise one or more of fly ash, sulfur-containing compounds and chlorine-containing compounds;
4) the CO purified gas enters a biological fermentation unit for fermentation process, and the CO-containing gas is converted into fermentation liquor, wherein the fermentation liquor contains ethanol;
5) and (4) allowing the fermentation liquor generated in the step (3) to enter a fermentation liquor separation unit, separating to obtain ethanol, mycoprotein and a bacterium-containing residual liquid, and allowing the bacterium-containing residual liquid to enter a bacterium-containing residual liquid treatment unit.
10. The process according to claim 9, characterized in that: the oxidizing gas further contains O2，O2From air or pure oxygen; CO contained in the oxidizing gas2The treatment unit is one or more of steel-making tail gas, power plant tail gas, heat supply plant tail gas or fermentation tail gas treatment unit.
11. The process according to claim 9, characterized in that: h contained by the separation in the step (2)2Gas admission H2The purification unit removes impurities to obtain H2Purifying the gas, the impurities comprising one or more of ash, incompletely separated organics, and sulfur-containing compounds.
12. The process according to claims 9 and 11, characterized in that: a part H2Purified gas enters a biological fermentation unit to participate in the fermentation process in the step (4), and part of H2Purified gas enters a synthesis gas conversion unit; introducing a part of the CO purified gas generated in the step (3) into a synthesis gas conversion unit; and carrying out one or more reaction processes of preparing methanol from synthesis gas, preparing aromatic hydrocarbon from synthesis gas, preparing olefin from synthesis gas and preparing ethylene glycol from synthesis gas in the synthesis gas conversion unit.
13. According to claim 9The process is characterized by comprising the following steps: the pyrolysis temperature of coal in the coal pyrolysis unit is 400-1300 ℃, and the semicoke is in CO2/O2The temperature of the reaction with the oxidizing gas in the reduction unit is 700-1400 ℃.
CN202110727262.8A 2021-06-29 2021-06-29 System and process for co-producing ethanol and protein by utilizing coal quality Pending CN113528164A (en)

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