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CN-120608106-B - Method for inhibiting sulfate reducing bacteria in salt cavern hydrogen storage engineering

CN120608106BCN 120608106 BCN120608106 BCN 120608106BCN-120608106-B

Abstract

The invention discloses a method for inhibiting Sulfate Reducing Bacteria (SRB) in salt cavern hydrogen storage engineering, and belongs to the technical field of hydrogen energy storage. The halophilic hydrogen-producing microorganism is used for carrying out anaerobic fermentation on the inner wall of a salt pit by utilizing a glycerol-polyacrylamide-glycerol loop layer to produce hydrogen and volatile acid metabolites, thereby inhibiting sulfate reducing bacteria. Wherein, the volatile fatty acid has remarkable inhibiting effect on SRB in a high-salt environment. The invention provides a high-efficiency and environment-friendly SRB inhibition method in a salt cavern hydrogen storage project, thereby reducing the generation of harmful gas hydrogen sulfide in the salt cavern and effectively reducing the corrosion risk of the hydrogen sulfide.

Inventors

  • LU JIAMIN
  • XU JUNHUI
  • WANG HAO
  • WANG WEIDONG
  • CHEN LIUPING
  • XU ZIJUN

Assignees

  • 中盐盐穴综合利用股份有限公司

Dates

Publication Date
20260512
Application Date
20250603

Claims (10)

  1. 1. The method for inhibiting sulfate reducing bacteria in salt cavern hydrogen storage engineering is characterized by comprising the following steps of: S1, mixing glycerol and brine to form a glycerol solution I, and injecting salt caves from the center; S2, introducing dry air into the salt caves through the production sleeve, and discharging the glycerol solution; s3, injecting the polyacrylamide solution into a salt cavity from the center; S4, introducing oxygen-controlled air containing potassium persulfate aerosol into the salt cavity from the production sleeve, and discharging the polyacrylamide solution; s5, injecting the glycerol solution II into a salt cavity from the central tube; S6, adopting a drying process to construct a glycerin-polyacrylamide-glycerin ring layer on the inner wall of the salt cavern; s7, inoculating halophilic hydrogen-producing acid-producing microorganisms on the glycerol-polyacrylamide-glycerol loop layer, wherein the halophilic hydrogen-producing acid-producing microorganisms are clostridium or enterobacter strains capable of carrying out anaerobic fermentation to metabolize glycerol to produce hydrogen and acid; S8, monitoring parameters of temperature, pH value, hydrogen concentration, volatile acid concentration and hydrogen sulfide concentration in the salt caves in real time, optimizing the fermentation environment of microorganisms according to monitoring data, injecting glycerol into the salt caves when the concentration of the volatile acid is monitored to be reduced, and adding sodium molybdate solution from the center when the activity of sulfate reducing bacteria is monitored to have an ascending trend; S9, injecting high-pressure hydrogen, and hermetically storing the hydrogen.
  2. 2. The method according to claim 1, wherein the mass fraction of the glycerol solution I in step S1 is 5% -10%.
  3. 3. The method according to claim 1, wherein the air flow rate is controlled to be 0.5-1m/S by introducing dry air in step S2.
  4. 4. The method according to claim 1, wherein the mass fraction of the polyacrylamide solution in the step S3 is 1% -2%, and the solvent is brine.
  5. 5. The method according to claim 1, wherein the oxygen-controlled air containing the potassium persulfate aerosol in the step S4 has the concentration of 0.3-0.6%, the oxygen content of 1-5% VOL and the air flow rate of 0.5-1m/S.
  6. 6. The method according to claim 1, wherein the glycerol solution II in step S5 has a mass fraction of 15% -25% and the solvent is brine.
  7. 7. The method according to claim 1, wherein the drying process in step S6 is performed by introducing dry nitrogen gas at a flow rate of 0.5-1 m/S, and the glycerol-polyacrylamide-glycerol loop layer has a thickness of 0.5-1 cm.
  8. 8. The method according to claim 1, wherein the inoculation mode in step S7 is that halophilic hydrogen-producing and acid-producing microorganisms enter salt holes along with brine, stand for 24 h, then hydrogen is introduced from a production sleeve, brine is discharged, the microorganisms are adhered to a glycerol-polyacrylamide-glycerol loop layer, and finally the anaerobic culture is carried out by sealing 48: 48 h.
  9. 9. The method according to claim 1, wherein the method for optimizing the fermentation environment of the microorganism according to the monitoring data in the step S8 comprises injecting glycerol and molybdate solution when the volume fraction of the volatile acid is monitored to be reduced to 10 ppm, injecting glycerol into the salt cavern, and adding molybdate solution from the center pipe when the inhibitory effect of glycerol on acid formation reaches the extreme value.
  10. 10. The method of claim 9, wherein the concentration of the molybdate solution is 10 to 50 μmol/L.

Description

Method for inhibiting sulfate reducing bacteria in salt cavern hydrogen storage engineering Technical Field The invention belongs to the technical field of hydrogen energy storage. In particular to a method for inhibiting Sulfate Reducing Bacteria (SRB) in salt pit hydrogen storage engineering, which uses hydrogen-producing microorganisms to carry out anaerobic fermentation on the inner wall of salt pit by utilizing a glycerol-polyacrylamide-glycerol loop layer to produce hydrogen and volatile acid metabolites. The method for inhibiting the growth of sulfate reducing bacteria and the generation of hydrogen sulfide in salt caves by generating volatile fatty acid through metabolism is suitable for controlling the microbial corrosion in the salt cavern hydrogen storage engineering. Background Hydrogen is an important carrier of a new energy system, and in four links of preparation, transportation, storage and application of a hydrogen energy industrial chain, hydrogen storage and hydrogen transportation are main difficulties, and salt cavern gas storages have high gas injection and production efficiency because of strong peak regulation capability, low gas demand on cushion layers, high sealing capability of rock salt and flexible operation, and are currently considered as one of the most promising underground hydrogen storage modes. The salt cavern hydrogen storage is selected as a high-efficiency and environment-friendly hydrogen storage mode, and has wide application prospect in the field of energy storage. Microorganisms in salt caverns are closely related to hydrogen circulation consumption, production and corrosion. Many frequently occurring microorganisms are considered to be major hydrogen consumers, such as methanogens, sulfate Reducing Bacteria (SRB), acetic acid bacteria, and the like. Wherein the presence of SRB in the salt cavern environment can pose a serious hazard to the hydrogen storage system. SRB can reduce sulfate into hydrogen sulfide under anaerobic condition, and hydrogen sulfide is not only a harmful gas, but also can pollute stored hydrogen, reduce the quality of hydrogen, has strong corrosiveness, depolarizes steel, induces serious pitting corrosion, and can promote the occurrence of Hydrogen Induced Cracking (HIC) and Sulfide Stress Corrosion Cracking (SSCC), thereby influencing the safety of hydrogen storage. And presents a risk for hydrogen storage. At present, most of the methods for inhibiting SRB in salt caverns have the problems of low efficiency, high cost, potential harm to the environment and the like. Common methods for preventing and treating SRB corrosion can be classified into physical methods, corrosion-preventing material methods, cathodic protection methods, chemical methods and microbial control methods according to factors such as growth and propagation conditions, corrosion activity mechanisms and action objects of SRB. The physical method inhibits the SRB activity by changing the physical conditions such as the temperature, the pH value, the mineralization degree, the dissolved oxygen, the ultraviolet rays, the ultrasonic waves and the like of the environment, but the physical method has high energy consumption, difficult control of the process, poor sterilization effect and higher implementation difficulty for the SRB treatment in salt caves. Although the chemical bactericide can inhibit the growth of SRB to a certain extent, secondary pollution can be caused to salt pit environment and a hydrogen storage system, and the SRB is easy to generate drug resistance after long-term use. Therefore, the development of the SRB inhibition method with high efficiency and environmental protection has important significance for guaranteeing the safe and stable operation of the salt cavern hydrogen storage engineering. Disclosure of Invention The invention aims to solve the technical problems of overcoming the defects of the prior art and providing a method for inhibiting growth of salt pit sulfate reducing bacteria in salt pit hydrogen storage engineering so as to solve the problems of hydrogen sulfide pollution and corrosion caused by SRB in the salt pit hydrogen storage engineering. The invention provides a method for inhibiting growth of salt cavern sulfate reducing bacteria in salt cavern hydrogen storage engineering, which comprises the following steps: S1, mixing glycerol and brine to form a glycerol solution I, and injecting salt caves from the center; S2, introducing dry air into the salt caves through the production sleeve, and discharging the glycerol solution; s3, injecting the polyacrylamide solution into a salt cavity from the center; S4, introducing oxygen-controlled air containing potassium persulfate aerosol into the salt cavity from the production sleeve, and discharging the polyacrylamide solution at the same time, wherein the potassium persulfate and the oxygen-controlled air are helpful for the solidification of the glycerin polyacrylamide. The trace O 2 c