CN112111531B - Method for improving anaerobic methane production of propionic acid - Google Patents
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Abstract
The invention discloses a method for improving anaerobic methanogenesis of propionic acid, and belongs to the technical field of environmental protection. The method comprises the following steps: firstly, adding a propionic acid anaerobic reaction culture medium containing ultrapure water, sodium propionate, inorganic salt and trace elements into a reactor, and then adding inoculated sludge and a composite material Met @ Fe3O4And then adjusting the pH value of the system in the reactor to 7.0 +/-0.2, blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment, and then carrying out propionic acid anaerobic methanogenesis reaction at the temperature of 30 +/-2 ℃ for 31 d. The method is simple and convenient to operate, and the composite material Met @ Fe which is easier to contact with microorganisms is added into the propionic acid anaerobic methanogenesis system3O4The method can strengthen the direct electron transfer process, further promote the generation of methane and the degradation of propionic acid, improve the generation amount of methane and the degradation rate of propionic acid, and reduce the accumulation of propionic acid in an anaerobic digestion system.
Description
Technical Field
The invention relates to a method for improving anaerobic methanogenesis of propionic acid, and belongs to the technical field of environmental protection.
Background
In recent years, with the growth of population and the continuous development of economy, the discharge amount of wastewater and waste in China is increasing day by day, and because anaerobic digestion can realize pollutant treatment and energy substance recovery at the same time, the anaerobic digestion technology is widely applied to the treatment of organic wastewater (object). Propionic acid is an important intermediate metabolite in anaerobic digestion and if all propionic acid is bioconverted, it can produce up to 35% of the total methane. However, under anaerobic conditions, the biotransformation of propionic acid is difficult to carry out, and the accumulation of propionic acid inhibits the activity of methanogens, causing the anaerobic digestion reaction to fail. Therefore, the realization of the rapid conversion of propionic acid into methane under anaerobic conditions is crucial to the smooth proceeding of the anaerobic digestion process.
The direct electron transfer process is reported to be an effective electron transfer form and energy conservation mechanism, and is considered as an effective means for solving the problem of low degradation efficiency of propionic acid. The study of ferroferric oxide (Fe)3O4) Adding into propionic acid anaerobic digestion system, and adding ferroferric oxide (Fe)3O4) Can be used as an electric conduit to connect propionic acid oxidizing bacteria and methanogenic bacteria, so that a direct electron transfer process is formed between the two bacteria, and the maximum methane production rate is finally improved. But due to Fe3O4Has the defects of easy agglomeration, low water solubility, difficult contact with microorganisms, low electron transfer efficiency and the like, and adopts Fe3O4The effect of increasing the degradation rate of propionic acid and the amount of methane produced is not ideal.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for improving propionic acid anaerobic methanogenesis, which is simple and convenient to operate and is characterized in that a composite material Met @ Fe which is easier to contact with microorganisms is added into a propionic acid anaerobic methanogenesis system3O4The method can strengthen the direct electron transfer process, further promote the generation of methane and the degradation of propionic acid, improve the generation amount of methane and the degradation rate of propionic acid, and reduce the accumulation of propionic acid in an anaerobic digestion system.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method for improving anaerobic methanogenesis of propionic acid comprises the following steps: firstly, adding a propionic acid anaerobic reaction culture medium containing ultrapure water, sodium propionate, inorganic salt and trace elements into a reactor, and then adding inoculated sludge and a complexThe composite material Met @ Fe3O4Then, adjusting the pH value of the system in the reactor to 7.0 +/-0.2, blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment, and then carrying out propionic acid anaerobic methanogenesis reaction at the temperature of 30 +/-2 ℃ for 31 d; the composite material Met @ Fe3O4The surface modification is carried out on ferroferric oxide by methionine.
Preferably, the dosage of the sodium propionate is 2595 mg/L.
Preferably, the inorganic salt comprises the following components in percentage by weight: 1000mg/L potassium dihydrogen phosphate, 1000mg/L ammonium chloride, 100 mg/L calcium chloride and 100 mg/L magnesium chloride hexahydrate.
Preferably, the trace elements comprise the following components in percentage by weight: 1.0 mg/L of ferric chloride, 0.5 mg/L of zinc sulfate heptahydrate, 0.5 mg/L of cobalt chloride hexahydrate, 1.0 mg/L of nickel chloride hexahydrate, 0.5 mg/L of copper sulfate pentahydrate and 0.5 mg/L of manganese chloride tetrahydrate.
Preferably, the dosage of the inoculation sludge is 450 mg/L.
Preferably, the composite material Met @ Fe3O4The dosage is 200-1000 mg/L.
Further preferably, the composite material Met @ Fe3O4The dosage of (2) is 400 mg/L.
Preferably, the characteristics of the inoculated sludge are as follows: pH 7.0 +/-0.2, total suspended solid TSS 8.3 +/-1.2 g/L and volatile suspended solid particles VSS 5.6 g/L.
Preferably, the inoculated sludge is obtained by acclimating residual activated sludge through the following steps:
(1) obtaining residual activated sludge from a secondary sedimentation tank of a sewage treatment plant, wherein the sludge has the characteristics that: the pH value is 6.9 +/-0.1, the total content of suspended solid TSS is 15.6 +/-2.1 g/L, and the content of volatile suspended solid particles VSS is 10.2 +/-0.7 g/L;
(2) adding the residual activated sludge obtained in the step (1) into a semi-continuous flow reactor, and then adding a propionic acid anaerobic culture medium containing ultrapure water, sodium propionate, inorganic salts and trace elements, wherein the adding amount of the residual activated sludge is 5 g/L, the adding amount of the sodium propionate is 2595 mg/L, and the inorganic salts comprise the following components: 1000mg/L potassium dihydrogen phosphate, 1000mg/L ammonium chloride, 100 mg/L calcium chloride and 100 mg/L magnesium chloride hexahydrate; the trace elements comprise the following components in percentage by weight: 1.0 mg/L of ferric chloride, 0.5 mg/L of zinc sulfate heptahydrate, 0.5 mg/L of cobalt chloride hexahydrate, 1.0 mg/L of nickel chloride hexahydrate, 0.5 mg/L of copper sulfate pentahydrate and 0.5 mg/L of manganese chloride tetrahydrate; adjusting the pH value of a system in the reactor to 7.0 +/-0.2, keeping the temperature of the reactor to 30 +/-2 ℃, stirring at a stirring speed of 80 rpm, and blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment;
(3) taking 20 mL of the mixture out of the reactor and discarding it every day at 8:00 a.m., and adding 10 mL of the residual activated sludge of step (1) and 10 mL of concentrated propionic acid anaerobic medium to keep the concentration of the sludge and propionic acid anaerobic medium in the reactor constant; when the degradation rate of the propionic acid and the methane production rate in the reactor are basically stable, the sludge in the reactor can be used as inoculated sludge for propionic acid anaerobic methane production; wherein, the concentration of the sodium propionate in the concentrated propionic acid anaerobic culture medium is 5190 mg/L, and the components and the concentrations of the inorganic salts are as follows: 2000 mg/L of monopotassium phosphate, 2000 mg/L of ammonium chloride, 200 mg/L of calcium chloride and 200 mg/L of magnesium chloride hexahydrate; the trace elements comprise the following components in percentage by weight: 2.0 mg/L of ferric chloride, 1.0 mg/L of zinc sulfate heptahydrate, 1 mg/L of cobalt chloride hexahydrate, 2.0 mg/L of nickel chloride hexahydrate, 1.0 mg/L of copper sulfate pentahydrate and 1 mg/L of manganese chloride tetrahydrate.
Preferably, the composite material Met @ Fe3O4The preparation steps are as follows: adding 3.25 g of ferric chloride, 1.27 g of ferrous chloride and 2.98 g of methionine into a reaction vessel filled with 100 mL of ultrapure water, fully stirring, adding 2M of sodium hydroxide aqueous solution into the reaction vessel until the pH value of a system in the reaction vessel is 11 +/-0.2, then placing the reaction vessel into a water bath kettle to react for 10 hours at 90 ℃, reacting under the protection of inert gas, and centrifuging, washing and drying after the reaction is finished to obtain a black solid which is the target composite material Met @ Fe3O4。
From the above description, it can be seen that the present invention has the following advantages:
(1) the method is simple and convenient to operate, and the composite material Met @ Fe which is easier to contact with microorganisms is added into a propionic acid anaerobic methane production system3O4The cell can be promoted to form a polymer of propionic acid oxidizing bacteria-material-methanogen, so that the connection between microorganisms is tighter, the direct electron transfer process is strengthened, the generation of methane and the degradation of propionic acid are promoted, the generation amount of methane and the degradation rate of propionic acid are improved, and the accumulation of propionic acid in an anaerobic digestion system is reduced.
(2) The invention relates to the treatment of ferroferric oxide (Fe) by methionine (Met)3O4) Carrying out surface modification to obtain Met @ Fe3O4Composite material, obtained Met @ Fe3O4The composite material does not destroy the original ferroferric oxide (Fe)3O4) The methionine (Met) group on the surface of the ferroferric oxide can prevent the aggregation of the composite particles, so that the composite particles have good biocompatibility and the conductivity of the composite material can be improved.
Drawings
FIG. 1 shows the composite Met @ Fe3O4And Fe3O4X-ray diffraction patterns of (a);
FIG. 2 shows the composite Met @ Fe3O4And Fe3O4A Fourier infrared spectrogram of (1);
FIG. 3 shows the composite Met @ Fe3O4And Fe3O4Thermogravimetric analysis of (a);
FIG. 4 shows the composite Met @ Fe3O4And Fe3O4Impedance graph of (a);
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1
A method for improving anaerobic methanogenesis of propionic acid comprises the following steps: firstly, 778.5 m of ultrapure water is added into an anaerobic bottleSodium propionate, 300 mg potassium dihydrogen phosphate, 300 mg ammonium chloride, 30 mg calcium chloride, 30 mg magnesium chloride hexahydrate, 0.3 mg ferric chloride, 0.15 mg zinc sulfate heptahydrate, 0.15 mg cobalt chloride hexahydrate, 0.3 mg nickel chloride hexahydrate, 0.15 mg copper sulfate pentahydrate, 0.15 mg manganese chloride tetrahydrate in propionic acid anaerobic reaction medium, 135mg inoculated sludge and 60mg composite Met @ Fe3O4Forming an anaerobic reaction system with the volume of 300mL, adjusting the pH value of the reaction system in the anaerobic bottle to 7.0 +/-0.2, blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the anaerobic bottle to be in an anaerobic environment, placing the anaerobic bottle in a constant-temperature shaking table with the temperature of 30 +/-2 ℃ and the rotating speed of 150rpm to perform propionic acid anaerobic methanogenesis reaction, wherein the reaction time is 31 d. And detecting the propionic acid content and the methane accumulation amount in the reaction bottle at different moments in the reaction process. The results showed that the propionic acid degradation rate was 70.5% after 31d of the reaction, and the cumulative yield of methane (maximum cumulative yield of methane) was 191.8. + -. 9.6 mg/g COD; the maximum methane production rate was 13.1. + -. 0.8 mL/g COD/d after the time-dependent change in methane accumulation was fitted to the Gompertz equation.
In this example, the characteristics of the inoculated sludge are: pH 7.0 +/-0.2, total suspended solid TSS 8.3 +/-1.2 g/L and volatile suspended solid particle VSS 5.6 g/L, wherein the inoculated sludge is obtained by acclimating residual activated sludge through the following steps:
(1) obtaining residual activated sludge from a secondary sedimentation tank of a sewage treatment plant, wherein the sludge has the characteristics that: the pH value is 6.9 +/-0.1, the total content of suspended solid TSS is 15.6 +/-2.1 g/L, and the content of volatile suspended solid particles VSS is 10.2 +/-0.7 g/L;
(2) adding 5g of the residual activated sludge in the step (1) into a semi-continuous flow reactor, then adding a propionic acid anaerobic culture medium containing ultrapure water, 2595 mg of sodium propionate, 1000mg of monopotassium phosphate, 1000mg of ammonium chloride, 100 mg of calcium chloride, 100 mg of magnesium chloride hexahydrate, 1.0 mg of ferric chloride, 0.5 mg of zinc sulfate heptahydrate, 0.5 mg of cobalt chloride hexahydrate, 1.0 mg of nickel chloride hexahydrate, 0.5 mg of copper sulfate pentahydrate and 0.5 mg of manganese chloride tetrahydrate to form a working system with the volume of 1L, adjusting the pH of the system in the reactor to be 7.0 +/-0.2, keeping the temperature of the reactor to be 30 +/-2 ℃, stirring at a stirring speed of 80 rpm, and blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment;
(3) taking 20 mL of the mixture out of the reactor and discarding it every day at 8:00 a.m., and adding 10 mL of the residual activated sludge of step (1) and 10 mL of concentrated propionic acid anaerobic medium to keep the concentration of the sludge and propionic acid anaerobic medium in the reactor constant; when the degradation rate of the propionic acid and the methanogenesis rate in the reactor are basically stable (about 50 d), the sludge in the reactor can be used as inoculation sludge for propionic acid anaerobic methanogenesis; wherein, 10 mL of the concentrated propionic acid anaerobic culture medium contains 51.90 mg of sodium propionate, 20 mg of potassium dihydrogen phosphate, 20 mg of ammonium chloride, 2 mg of calcium chloride, 2 mg of magnesium chloride hexahydrate, 0.02 mg of ferric chloride, 0.01 mg of zinc sulfate heptahydrate, 0.01 mg of cobalt chloride hexahydrate, 0.02 mg of nickel chloride hexahydrate, 0.01 mg of copper sulfate pentahydrate, 0.01 mg of manganese chloride tetrahydrate and the balance of ultrapure water.
In this example, the composite Met @ Fe3O4The preparation steps are as follows: adding 3.25 g of ferric chloride, 1.27 g of ferrous chloride and 2.98 g of methionine into a reaction vessel filled with 100 mL of ultrapure water, fully stirring, adding a 2M sodium hydroxide aqueous solution into the reaction vessel until the pH value of a mixture in the reaction vessel is 11 +/-0.2, then placing the reaction vessel into a water bath kettle to react for 10 hours at 90 ℃, reacting under the protection of inert gas, and centrifuging, washing and drying after the reaction is finished to obtain a black solid which is the target composite material Met @ Fe3O4。
Example 2
The same procedure as in example 1 was followed, except that the composite Met @ Fe was used3O4The dosage of (2) is 400 mg/L. The results showed that the propionic acid degradation rate was 95.3%, the cumulative methane yield was 263.0. + -. 9.0 mg/g COD and the maximum methanogenic rate was 23.2. + -. 2.4 mL/g COD/d.
Example 3
The same procedure as in example 1 was followed, except that the composite Met @ Fe was used3O4The dosage of (A) is 800 mg/L. The results showed that the propionic acid degradation rate was 94.2% and the cumulative yield of methane was 273.0. + -. 19.9 mg/g COD, maximum methanogenesis rate 23.3. + -. 2.6 mL/g COD/d.
Example 4
The same procedure as in example 1 was followed, except that the composite Met @ Fe was used3O4The dosage of (A) is 1000 mg/L. The results showed that the propionic acid degradation rate was 95.6%, the cumulative methane yield was 272.6. + -. 10.1 mg/g COD and the maximum methane production rate was 23.0. + -. 2.6 mL/g COD/d.
Comparative example 1
The same procedure as in example 1 was followed, except that the composite material Met @ Fe was used3O4Replacement by Fe3O4，Fe3O4The dosage of (A) is 200 mg/L, Fe3O4The preparation steps are as follows: adding 3.25 g of ferric chloride and 1.27 g of ferrous chloride into a reaction vessel filled with 100 mL of ultrapure water, fully stirring, adding 2M of sodium hydroxide aqueous solution into the reaction vessel until the pH value of the mixture in the reaction vessel is 11 +/-0.2, then placing the reaction vessel into a water bath kettle to react for 10 hours at 90 ℃, reacting under the protection of inert gas, and after the reaction is finished, centrifuging, washing and drying to obtain a black solid, namely Fe3O4。
The results showed that the propionic acid degradation rate was 67.3%, the cumulative methane yield was 158.4. + -. 5.1 mg/g COD and the maximum methane production rate was 10.8. + -. 0.7 mL/g COD/d.
Comparative example 2
The same procedure as in comparative example 1 was used, differing only by Fe3O4The dosage of (2) is 400 mg/L. The results showed that the propionic acid degradation rate was 71.7%, the cumulative methane yield was 191.2. + -. 5.2 mg/g COD and the maximum methane production rate was 12.7. + -. 0.8 mL/g COD/d.
Comparative example 3
The same procedure as in comparative example 1 was used, differing only by Fe3O4The dosage of (A) is 800 mg/L. The results showed that the propionic acid degradation rate was 68.8%, the cumulative methane yield was 185.0. + -. 6.5 mg/g COD and the maximum methane production rate was 12.3. + -. 0.8 mL/g COD/d.
Comparative example 4
The same procedure as in comparative example 1 was adoptedBy the process of (1), which differs only in Fe3O4The dosage of (A) is 1000 mg/L. The results showed that the propionic acid degradation rate was 70.1%, the cumulative methane yield was 192.5. + -. 8.0 mg/g COD and the maximum methane production rate was 13.1. + -. 0.9 mL/g COD/d.
Comparative example 5
The same procedure as in example 1 was followed, except that the composite Met @ Fe was used3O4The addition amount of (2) is 0. The results showed that the propionic acid degradation rate was 62.4%, the cumulative methane yield was 145.1. + -. 6.7 mg/g COD, and the maximum methane production rate was 9.2. + -. 0.5 mL/g COD/d.
FIGS. 1 to 4 are respectively a composite material Met @ Fe of the present invention3O4And Fe in comparative example3O4X-ray diffraction analysis, fourier infrared spectroscopy analysis, thermogravimetric analysis and impedance analysis. From the X-ray diffraction diagram of FIG. 1, it can be seen that only the characteristic peak of ferroferric oxide appears in the sample Fe3O4And Met @ Fe3O4In the formula, methionine is used for modifying the ferroferric oxide, and the crystal structure of the ferroferric oxide is not changed. As can be seen from the Fourier infrared spectrogram in FIG. 2, the Fourier infrared spectrogram is at 580 cm-1And 3401 cm-1The peak value is the stretching vibration of Fe-O and O-H; the sample Met @ Fe was determined as a function of O-H in the carboxyl group of methionine3O4At 3401 cm-1Shows strong broadband; furthermore, sample Met @ Fe3O4The FTIR spectrum of (1) is increased by-1525 cm-1And 1637 cm-1Two characteristic peaks, caused by C = O and C-O stretching vibrations in the methionine carboxyl group. From the thermogravimetric analysis chart in FIG. 3, the modified Met @ Fe composite material can be obtained3O4The surface methionine accounted for 8.16% of its total mass. From the impedance plot of FIG. 4, the composite Met @ Fe can be derived3O4Is less than Fe3O4。
From the data of the examples and comparative examples, it can be seen that the composite Met @ Fe3O4The optimal adding concentration is 400 mg/L. Among them, the propionic acid degradation rate in example 2 was 95.3%, which was 52.7% higher than that (62.4%) in comparative example 5, which was comparative example 2The propionic acid degradation rate (71.7%) is improved by 32.9%; the maximum cumulative methane yield in example 2 is 263.0 +/-9.0 mg/g COD, which is 81.4% higher than the maximum cumulative methane yield in comparative example 5 (145.1 +/-6.7 mg/g COD), and is 37.7% higher than the maximum cumulative methane yield in comparative example 2 (191.2 +/-5.2 mg/g COD); the maximum methanogenesis rate in example 2 was 23.2. + -. 2.4 mL/g COD/d, which was increased by 152.2% compared to the maximum methanogenesis rate in comparative example 5 (9.2. + -. 0.5 mL/g COD/d) and 82.7% compared to the maximum methanogenesis rate in comparative example 2 (12.7. + -. 0.8 mL/g COD/d).
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A method for improving anaerobic methanogenesis of propionic acid is characterized by comprising the following steps: firstly, adding a propionic acid anaerobic reaction culture medium containing ultrapure water, sodium propionate, inorganic salt and trace elements into a reactor, and then adding inoculated sludge and a composite material Met @ Fe3O4Then, adjusting the pH value of the system in the reactor to 7.0 +/-0.2, blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment, and then carrying out propionic acid anaerobic methanogenesis reaction at the temperature of 30 +/-2 ℃ for 31 d; the composite material Met @ Fe3O4The surface modification is carried out on ferroferric oxide by methionine.
2. The method of claim 1, wherein the amount of sodium propionate added is 2595 mg/L.
3. The method of claim 1, wherein the inorganic salt is comprised of: 1000mg/L potassium dihydrogen phosphate, 1000mg/L ammonium chloride, 100 mg/L calcium chloride and 100 mg/L magnesium chloride hexahydrate.
4. The method of claim 1, wherein the trace elements are selected from the group consisting of: 1.0 mg/L of ferric chloride, 0.5 mg/L of zinc sulfate heptahydrate, 0.5 mg/L of cobalt chloride hexahydrate, 1.0 mg/L of nickel chloride hexahydrate, 0.5 mg/L of copper sulfate pentahydrate and 0.5 mg/L of manganese chloride tetrahydrate.
5. The method of claim 1, wherein the inoculated sludge is dosed at 450 mg/L.
6. The method of claim 1, wherein the composite material Met @ Fe3O4The dosage is 200-1000 mg/L.
7. The method of claim 4, wherein the composite material Met @ Fe3O4The dosage of (2) is 400 mg/L.
8. The method of claim 1, wherein the inoculated sludge is characterized by: pH 7.0 +/-0.2, total suspended solid TSS 8.3 +/-1.2 g/L and volatile suspended solid particles VSS 5.6 g/L.
9. The method of claim 1, wherein the inoculated sludge is obtained by acclimating residual activated sludge by:
(1) obtaining residual activated sludge from a secondary sedimentation tank of a sewage treatment plant, wherein the sludge has the characteristics that: the pH value is 6.9 +/-0.1, the total content of suspended solid TSS is 15.6 +/-2.1 g/L, and the content of volatile suspended solid particles VSS is 10.2 +/-0.7 g/L;
(2) adding the residual activated sludge obtained in the step (1) into a semi-continuous flow reactor, and then adding a propionic acid anaerobic culture medium containing ultrapure water, sodium propionate, inorganic salts and trace elements, wherein the adding amount of the residual activated sludge is 5 g/L, the adding amount of the sodium propionate is 2595 mg/L, and the inorganic salts comprise the following components: 1000mg/L potassium dihydrogen phosphate, 1000mg/L ammonium chloride, 100 mg/L calcium chloride and 100 mg/L magnesium chloride hexahydrate; the trace elements comprise the following components in percentage by weight: 1.0 mg/L of ferric chloride, 0.5 mg/L of zinc sulfate heptahydrate, 0.5 mg/L of cobalt chloride hexahydrate, 1.0 mg/L of nickel chloride hexahydrate, 0.5 mg/L of copper sulfate pentahydrate and 0.5 mg/L of manganese chloride tetrahydrate; adjusting the pH value of a system in the reactor to 7.0 +/-0.2, keeping the temperature of the reactor to 30 +/-2 ℃, stirring at a stirring speed of 80 rpm, and blowing off oxygen in the reactor by using nitrogen to enable microorganisms in the reactor to be in an anaerobic environment;
(3) taking 20 mL of the mixture out of the reactor and discarding it every day at 8:00 a.m., and adding 10 mL of the residual activated sludge of step (1) and 10 mL of concentrated propionic acid anaerobic medium to keep the concentration of the sludge and propionic acid anaerobic medium in the reactor constant; when the degradation rate of the propionic acid and the methane production rate in the reactor are basically stable, the sludge in the reactor can be used as inoculated sludge for propionic acid anaerobic methane production; wherein, the concentration of the sodium propionate in the concentrated propionic acid anaerobic culture medium is 5190 mg/L, and the components and the concentrations of the inorganic salts are as follows: 2000 mg/L of monopotassium phosphate, 2000 mg/L of ammonium chloride, 200 mg/L of calcium chloride and 200 mg/L of magnesium chloride hexahydrate; the trace elements comprise the following components in percentage by weight: 2.0 mg/L of ferric chloride, 1.0 mg/L of zinc sulfate heptahydrate, 1 mg/L of cobalt chloride hexahydrate, 2.0 mg/L of nickel chloride hexahydrate, 1.0 mg/L of copper sulfate pentahydrate and 1 mg/L of manganese chloride tetrahydrate.
10. The method of claim 1, wherein the composite material Met @ Fe3O4The preparation steps are as follows: adding 3.25 g of ferric chloride, 1.27 g of ferrous chloride and 2.98 g of methionine into a reaction vessel filled with 100 mL of ultrapure water, fully stirring, adding 2M of sodium hydroxide aqueous solution into the reaction vessel until the pH value of a system in the reaction vessel is 11 +/-0.2, then placing the reaction vessel into a water bath kettle for reaction at 90 ℃ for 10 hours under the protection of inert gas, and after the reaction is finished, centrifuging, washing with water and drying to obtain a black solid which is the target composite material Met @ Fe3O4。
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