阅读说明：本技术 一种高效率工业尾气发酵制醇工艺 (High-efficiency industrial tail gas fermentation alcohol preparation process ) 是由 佟淑环 莫志朋 晁伟 陈超超 贾伟 于 2021-07-09 设计创作，主要内容包括：本发明提供了一种高效率工业尾气发酵制醇工艺,属于能源技术领域,所述工艺包括：将工业尾气进行加压；加压后的所述工业尾气通过气体分离膜进行一氧化碳提浓,获得反应气；将所述反应气通入微生物发酵罐进行发酵制醇,获得含醇醪液；其中,所述气体分离膜的孔径为0.33～0.35nm。该工艺能够将工业尾气中一氧化碳浓度提升至目标范围,实现一氧化碳浓度稳定控制,从而有效提高发酵反应效率、降低能耗和成本、提高反应体系运行稳定性。(The invention provides a high-efficiency industrial tail gas fermentation alcohol preparation process, belonging to the technical field of energy sources, and the process comprises the following steps: pressurizing the industrial tail gas; the pressurized industrial tail gas is subjected to carbon monoxide concentration through a gas separation membrane to obtain reaction gas; introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol, thereby obtaining alcohol-containing mash; wherein the aperture of the gas separation membrane is 0.33-0.35 nm. The process can improve the concentration of carbon monoxide in industrial tail gas to a target range, and realize the stable control of the concentration of carbon monoxide, thereby effectively improving the fermentation reaction efficiency, reducing the energy consumption and cost, and improving the operation stability of a reaction system.)

1. A high-efficiency industrial tail gas fermentation alcohol preparation process is characterized by comprising the following steps:

pressurizing the industrial tail gas;

the pressurized industrial tail gas is subjected to carbon monoxide concentration through a gas separation membrane to obtain reaction gas;

introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol, thereby obtaining alcohol-containing mash;

wherein the aperture of the gas separation membrane is 0.33-0.35 nm.

2. The process for preparing alcohol by fermenting industrial tail gas with high efficiency according to claim 1, wherein the pressurizing of industrial tail gas specifically comprises:

pressurizing the industrial tail gas to 0.5-0.6 MPa.

3. The process for preparing alcohol by fermenting industrial tail gas with high efficiency according to claim 1, wherein the pressurized industrial tail gas is subjected to carbon monoxide concentration by a gas separation membrane to obtain a reaction gas, and the process specifically comprises the following steps:

and (3) concentrating the pressurized industrial tail gas by using a gas separation membrane to obtain reaction gas, wherein the molar concentration of carbon monoxide in the reaction gas is more than or equal to 50%.

4. The process of claim 1 or 3, wherein one side of the gas separation membrane is a concentration side, and the other side of the gas separation membrane is a permeation side, the concentration side is divided into a gas inlet side and a reaction gas side, the industrial tail gas enters the concentration side from the gas inlet side, the reaction gas is gathered on the reaction gas side, and the gas pressure of the permeation side is controlled to be less than or equal to 101 kPa.

5. The process of claim 1, wherein the step of introducing the reaction gas into a microbial fermentation tank for fermentation to obtain alcohol-containing mash comprises:

and introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol to obtain alcohol-containing mash, wherein the temperature of the reaction gas is 29-37 ℃.

6. The process for preparing alcohol by fermenting industrial tail gas with high efficiency according to claim 1, wherein the industrial tail gas comprises at least one of steel industrial tail gas, biomass synthesis gas, coal gas and petroleum refining tail gas.

7. The process for preparing alcohol by fermenting industrial tail gas with high efficiency according to claim 1, wherein the gas separation membrane comprises any one of an organic high molecular polymer membrane, an inorganic membrane, a high molecular-inorganic composite membrane and a high molecular-inorganic hybrid membrane.

8. The process of claim 1, wherein the gas separation membrane comprises a rubbery membrane and a glassy membrane.

9. The process of claim 1, wherein the alcohol-containing mash comprises at least one alcohol selected from ethanol, propanol and butanol.

10. The process of claim 4, wherein the gas at the permeation side and the fermentation tail gas of the microbial fermentation tank are oxidized by an oxidation furnace.

Technical Field

The invention belongs to the technical field of energy sources, and particularly relates to a high-efficiency industrial tail gas fermentation alcohol preparation process.

Background

With the growing tension of global fossil fuels and the increasing severity of environmental pollution, the energy and environmental crisis has become a major obstacle to the sustainable development of human society in the 21 st century. Ethanol is not only a good solvent, but also can be used as a raw material for preparing various chemical products, and because grain ethanol is seriously dependent on agricultural grain crops, the development of the policy of 'not competing for grains and land with people' is the direction of developing fuel ethanol in China and even the world, so that the development of non-grain ethanol and biomass ethanol is the development trend of ethanol production in the future. At present, the production cost of non-grain ethanol and biomass ethanol is always high, and the main cost is the raw materials.

The biomass ethanol is prepared by using carbon monoxide in industrial tail gas as a carbon source through microbial fermentation. The industrial tail gas has wide sources, the effective component is carbon monoxide in the industrial tail gas, the content of the carbon monoxide is greatly different according to different gas sources, and certain fluctuation exists, which influences the reaction efficiency and stability of the fermentation alcohol preparation system. The lower the concentration of carbon monoxide in the raw material gas, the larger the gas amount required by fermentation reaction, the larger the design scale of the gas inlet pipeline and the reactor is, and the investment cost and the operation cost are increased.

Disclosure of Invention

In order to solve the technical problem of fluctuation of the content of carbon monoxide in the industrial tail gas, the invention provides a high-efficiency industrial tail gas fermentation alcohol preparation process, which can improve the concentration of the carbon monoxide in the industrial tail gas to a target range and realize stable control of the concentration of the carbon monoxide, thereby effectively improving the fermentation reaction efficiency, reducing the energy consumption and the cost and improving the operation stability of a reaction system.

The invention is realized by the following technical scheme:

the application provides a high efficiency industry tail gas fermentation system mellow wine technology, technology includes:

pressurizing the industrial tail gas;

the pressurized industrial tail gas is subjected to carbon monoxide concentration through a gas separation membrane to obtain reaction gas;

introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol, thereby obtaining alcohol-containing mash;

wherein the aperture of the gas separation membrane is 0.33-0.35 nm.

Optionally, the pressurizing the industrial tail gas specifically includes:

pressurizing the industrial tail gas to 0.5-0.6 MPa.

Optionally, the pressurized industrial tail gas is subjected to carbon monoxide concentration through a gas separation membrane to obtain a reaction gas, and the method specifically includes:

and (3) concentrating the pressurized industrial tail gas by using a gas separation membrane to obtain reaction gas, wherein the molar concentration of carbon monoxide in the reaction gas is more than or equal to 50%.

Optionally, one side of the gas separation membrane is a concentration side, the other side of the gas separation membrane is a permeation side, the concentration side is divided into an air inlet side and a reaction gas side, the industrial tail gas enters the concentration side from the air inlet side, the reaction gas is gathered on the reaction gas side, and the gas pressure of the permeation side is controlled to be less than or equal to 101 kPa.

Optionally, the introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol to obtain alcohol-containing mash specifically comprises:

and introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol to obtain alcohol-containing mash, wherein the temperature of the reaction gas is 29-37 ℃.

Optionally, the industrial tail gas includes at least one of steel industrial tail gas, biomass synthesis gas, coal gas, and petroleum refining tail gas.

Optionally, the gas separation membrane includes any one of an organic high molecular polymer membrane, an inorganic membrane, a high molecular-inorganic composite membrane, and a high molecular-inorganic hybrid membrane.

Optionally, the gas separation membrane comprises a rubbery membrane and a glassy membrane.

Optionally, in the alcoholic mash, the alcohol substance comprises at least one of ethanol, propanol and butanol.

Optionally, the gas on the permeation side and the fermentation tail gas of the microbial fermentation tank are oxidized by an oxidation furnace.

One or more technical schemes in the invention at least have the following technical effects or advantages:

the invention relates to a high-efficiency industrial tail gas fermentation alcohol preparation process, which comprises the steps of pressurizing industrial tail gas, improving the gas separation rate of a gas separation membrane, concentrating carbon monoxide of the industrial tail gas through the gas separation membrane, wherein the pore diameter of the gas separation membrane is 0.33-0.35 nm and is between the pore diameter of CO₂The molecular diameter of (0.33nm) and CO (0.369nm) is between, and the size sieving effect is utilized to ensure that the CO with smaller size in the industrial tail gas₂And H₂Selectively permeable and larger size CO, N₂The carbon monoxide concentration in the industrial tail gas can be increased to a target range, and the stable control of the carbon monoxide concentration is realized, so that the fermentation reaction efficiency is effectively improved, the energy consumption and the cost are reduced, and the operation stability of a reaction system is improved.

The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.

Drawings

In order to more clearly illustrate the technical solutions in the present application, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a flow diagram of a high efficiency industrial tail gas fermentation alcohol production process of the present invention;

FIG. 2 is a schematic structural diagram of a high-efficiency industrial tail gas fermentation alcohol production device.

Detailed Description

The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.

Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

It should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.

In order to solve the technical problems, the general idea is as follows:

according to an exemplary embodiment of the present invention, a high-efficiency industrial tail gas alcohol fermentation process is provided, as shown in fig. 1, the process includes:

s1, pressurizing industrial tail gas;

s2, concentrating the pressurized industrial tail gas by carbon monoxide through a gas separation membrane to obtain reaction gas;

s3, introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol, so as to obtain alcohol-containing mash;

wherein the aperture of the gas separation membrane is 0.33-0.35 nm.

In the invention, industrial tail gas is pressurized to improve the gas separation rate of a gas separation membrane, the industrial tail gas passes through the gas separation membrane to concentrate carbon monoxide, and the aperture of the gas separation membrane is 0.33-0.35 nm and is between the range of CO₂The molecular diameter of (0.33nm) and CO (0.369nm) is between, and the size sieving effect is utilized to ensure that the CO with smaller size in the industrial tail gas₂And H₂Selectively permeable and larger size CO, N₂The carbon monoxide concentration in the industrial tail gas can be increased to a target range, and the stable control of the carbon monoxide concentration is realized, so that the fermentation reaction efficiency is effectively improved, the energy consumption and the cost are reduced, and the operation stability of a reaction system is improved.

As an optional embodiment, the pressurizing the industrial tail gas specifically includes:

pressurizing the industrial tail gas to 0.5-0.6 MPa.

In the application, the industrial tail gas from which impurities such as oxygen, hydrogen sulfide and the like and liquid water are removed in advance is pressurized to 0.5-0.6 MPa, so that the gas separation rate of the gas separation membrane can be increased, and CO is promoted₂And H₂When the separation of gases is carried out forward, the CO concentration efficiency is improved, if the pressure of industrial tail gas is lower than 0.5MPa, the gas separation efficiency is difficult to improve, and if the pressure is too high, the energy consumption of a gas compressor is increased, so that the CO concentration cost is increased.

As an alternative embodiment, the pressurized industrial tail gas is subjected to carbon monoxide concentration by a gas separation membrane to obtain a reaction gas, specifically including:

and (3) concentrating the pressurized industrial tail gas by using a gas separation membrane to obtain reaction gas, wherein the molar concentration of carbon monoxide in the reaction gas is more than or equal to 50%.

In the present application, CO in the industrial exhaust gas can be separated by the gas separation membrane₂And H₂Filtering, thereby improving the molar concentration of CO in the industrial tail gas, increasing the CO to more than 50 percent according to the actual production requirement, achieving the effect of improving the reaction rate and stability of alcohol preparation by fermentation, and the concentration of CO is lower than that of CO45% of the total amount of the alcohol does not contribute to the rapid reaction for producing alcohol by fermentation.

As an alternative embodiment, one side of the gas separation membrane is a concentration side, and the other side of the gas separation membrane is a permeation side, the concentration side is divided into a gas inlet side and a reaction gas side, the industrial tail gas enters the concentration side from the gas inlet side, the reaction gas is gathered on the reaction gas side, and the gas pressure of the permeation side is controlled to be less than or equal to 101 kPa.

In the invention, before or during gas separation, the gas pressure at the permeation side can be controlled to be in a normal pressure or negative pressure state by adopting vacuum pumping equipment, so that the gas pressure difference at two sides of the gas separation membrane is increased, and further CO is promoted₂And H₂The filtering is performed rapidly.

As an alternative embodiment, the introducing the reaction gas into a microbial fermentation tank for fermentation to produce alcohol, so as to obtain alcohol-containing mash, specifically comprising:

and introducing the reaction gas into a microbial fermentation tank for fermentation to prepare alcohol to obtain alcohol-containing mash, wherein the temperature of the reaction gas is 29-37 ℃.

In this application, with the temperature control of reaction gas at 29-37 ℃, be close the interior reaction temperature of microbial fermentation jar, can improve fermentation system mellow wine speed, if reaction gas temperature is low excessively, get into microbial fermentation jar and then can reduce reaction system temperature, reduce the microbial enzyme and live, lead to fermentation system mellow wine speed to reduce, be unfavorable for production efficiency's promotion.

As an alternative embodiment, the industrial tail gas comprises at least one of steel industry tail gas, biomass synthesis gas, coal gas, and petroleum refining tail gas.

In the application, the industrial tail gas can adopt the waste gas from various sources, and the carbon monoxide in the industrial tail gas is promoted to the target concentration by the process, so that the high-efficiency fermentation alcohol preparation is realized, and the application range is wide.

As an alternative embodiment, the gas separation membrane includes any one of an organic high molecular polymer membrane, an inorganic membrane, a high molecular-inorganic composite membrane, and a high molecular-inorganic hybrid membrane.

As an alternative embodiment, the gas separation membrane comprises a rubbery membrane and a glassy membrane.

In the present application, the gas separation membrane is made of the above known materials, and the pore size of the gas separation membrane is controlled, and the components and microstructure of the above known materials are not described in detail herein.

As an alternative embodiment, the alcoholic substance in the alcoholic mash comprises at least one of ethanol, propanol and butanol.

As an alternative embodiment, the gas at the permeation side and the fermentation tail gas of the microbial fermentation tank are oxidized by an oxidation furnace.

In the present application, the gas on the permeate side contains H₂And a small amount of CO and fermentation tail gas of the microbial fermentation tank are oxidized by the oxidation furnace, so that heat released by oxidation can be recovered to generate steam.

The following will explain the high efficiency industrial tail gas fermentation alcohol production process in detail by combining the examples, comparative examples and experimental data.

As shown in fig. 2, the embodiment of the present invention is performed based on the following means:

the utility model provides a high efficiency industry tail gas fermentation system mellow wine device, includes gas compression device 100, gas compression device 200 and fermentation system mellow wine unit 300, establish gas separation membrane 210 in the gas compression device 200, gas separation membrane 210 will gas compression device 200's inner chamber is divided into concentration side 220 and infiltration side 230, concentration side 220 one end through pipeline one 400 with gas compression device 100 is linked together, the other end through pipeline two 500 with fermentation system mellow wine unit 300 is linked together, gas separation membrane 210's aperture is 0.33 ~ 0.35nm, gas compression device 100's entry links to each other with industry tail gas pipe 600.

Optionally, the industrial tail gas pipe 600 is used for conveying industrial tail gas, and a flow meter 800 is arranged on the industrial tail gas pipe 600.

Optionally, the permeate side 230 of the gas compression device 200 is in communication with the oxidizer via conduit three 700.

Optionally, a vacuum device 710 is disposed in the middle of the third pipe 700.

Optionally, the third pipe 700 is provided with a regulating valve set 720, a pressure detection device 900 and a component detection device 1000.

Optionally, the gas separation membrane 210 includes any one of an organic high molecular polymer membrane, an inorganic membrane, a high molecular-inorganic composite membrane, and a high molecular-inorganic hybrid membrane.

Alternatively, the gas separation membrane 210 includes a rubbery membrane and a glassy membrane.

Optionally, the first pipeline 400 is provided with a pressure detection device 900 and a component detection device 1000.

Optionally, the second pipe 500 is provided with a pressure detection device 900, a component detection device 1000, and a flow meter 800.

Optionally, the fermentation alcohol production unit 300 is microorganism

The fermentation tank is provided with an exhaust pipe 310 at the top.

Examples

The embodiment provides a high-efficiency industrial tail gas fermentation alcohol preparation process, which comprises the following steps:

(1) the industrial tail gas is pressurized to 0.5-0.6 MPa through the gas compression device 100.

(2) The pressurized industrial tail gas is subjected to carbon monoxide concentration through a gas separation membrane 210 with the aperture of 0.33-0.35 nm to obtain a reaction gas, one side of the gas separation membrane is a concentration side 220, the other side of the gas separation membrane is a permeation side 230, the concentration side 220 is divided into an air inlet side and a reaction gas side, the industrial tail gas enters the concentration side 220 from the air inlet side, the reaction gas is gathered on the reaction gas side, and the gas pressure of the permeation side 230 is controlled to be less than or equal to 101 kPa.

The material of the gas separation membrane 210 is polydimethylsiloxane (organic high molecular polymer), and the molar concentration of carbon monoxide in the reaction gas is 50% at 37 ℃.

(3) The reaction gas is fed at a flow rate of 600Nm³And/min introducing into a microbial fermentation tank for fermentation to prepare alcohol, thereby obtaining alcohol-containing mash.

Based on the above process, the present invention provides 2 typical examples and provides a comparative example, which is different from the examples in that:

directly feeding industrial tail gas into a microbial fermentation tank at the same flow rate for fermentation to prepare alcohol, thereby obtaining alcohol-containing mash.

In the present application, the industrial exhaust gases used in examples 1 and 2 and comparative example 1 are steel mill converter gas, and the main chemical components are shown in table 1:

TABLE 1 Main chemical composition and concentration of Industrial exhaust gas

Gas species	Concentration of	Molecular diameter/nm
			CO	47mol％	0.369
H2	0.66mol％	0.29
			CO2	20mol％	0.33
N2	29mol％	0.364-0.38
			O2	2000ppmv	0.3467
CH4	100ppm	0.3758
			H2S	30ppm	0.2623

In the present application, the respective process parameters of examples 1, 2 and comparative example 1 are shown in table 2.

Table 2 process parameters of examples 1, 2 and comparative example 1

In Table 2, -50kPa represents negative pressure 50 kPa.

The CO concentration effect and alcohol production efficiency of examples 1 and 2 and comparative example 1 are shown in Table 3.

TABLE 3 concentration effect and alcohol production efficiency of examples 1 and 2 and comparative example 1

As can be seen from tables 1 to 3, in the embodiments 1 and 2 of the present invention, the molar concentration of carbon monoxide in the industrial tail gas can be effectively increased to more than 67% by using the gas separation membrane with the pore diameter of 0.33 to 0.35nm, and compared with the case that the industrial tail gas is directly used for preparing alcohol by fermentation in the proportion 1, in the embodiments 1 and 2, the concentration of alcohol substances generated by fermentation in the microbial fermentation tank is higher in the same reaction time, i.e., the alcohol preparation reaction efficiency is higher, which is beneficial to reducing the energy consumption and cost for preparing biomass ethanol and improving the operation stability of the reaction system.

One or more technical solutions in the present application at least have the following technical effects or advantages:

(1) the application relates to a high-efficiency industrial tail gas fermentation alcohol preparation process, which pressurizes industrial tail gas, improves the gas separation rate of a gas separation membrane, and carries out carbon monoxide concentration on the industrial tail gas through the gas separation membrane, wherein the pore diameter of the gas separation membrane is 0.33-0.35 nm and is between CO and CO₂The molecular diameter of (0.33nm) and CO (0.369nm) is between, and the size sieving effect is utilized to ensure that the CO with smaller size in the industrial tail gas₂And H₂Selectively permeable and larger size CO, N₂The carbon monoxide concentration in the industrial tail gas can be increased to a target range, and the stable control of the carbon monoxide concentration is realized, so that the fermentation reaction efficiency is effectively improved, the energy consumption and the cost are reduced, and the operation stability of a reaction system is improved.

(2) The application relates to a high-efficiency industrial tail gas fermentation alcohol preparation process, industrial tail gas is pressurized to 0.5-0.6 MPa, impurities such as oxygen and hydrogen sulfide and liquid water are removed, the gas separation rate of a gas separation membrane can be increased, and CO is promoted₂And H₂When the separation of gases is carried out forward, the CO concentration efficiency is improved, if the pressure of industrial tail gas is lower than 0.5MPa, the gas separation efficiency is difficult to improve, and if the pressure is too high, the energy consumption of a gas compressor is increased, so that the CO concentration cost is increased.

Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.