阅读说明：本技术 一种盐穴储氢井环空保护液及其制备方法 (Salt cavern hydrogen storage well annular protection liquid and preparation method thereof ) 是由 徐俊辉 陈留平 刘娟 赵云松 徐孜俊 王卫东 于 2021-08-25 设计创作，主要内容包括：本发明涉及氢能源利用技术领域,尤其涉及一种盐穴储氢井环空保护液,包括以质量百分比计的以下组分：有机盐类15％～40％、pH调节剂2.3％～8.0％,杀菌剂1.0～4.0％、氢气指示剂0.1～1％、气井缓蚀剂0.5～2％、除氧剂0.5％～6.0％,余量为水。本发明可以减轻套管头或封隔器承受的气藏压力,降低油管与环空之间的压差,抑制套管的腐蚀和细菌的生长,能够吸收/释放部分注采过程中热量,从而提高生产套管和封隔器的使用寿命。当盐穴中有微量的氢气泄漏时,保护液的颜色会变成蓝色,可提前采取预防措施,确保储氢的安全性。(The invention relates to the technical field of hydrogen energy utilization, in particular to an annular protection liquid for a salt cavern hydrogen storage well, which comprises the following components in percentage by mass: 15-40% of organic salt, 2.3-8.0% of pH regulator, 1.0-4.0% of bactericide, 0.1-1% of hydrogen indicator, 0.5-2% of gas well corrosion inhibitor, 0.5-6.0% of deoxidant and the balance of water. The invention can reduce the gas reservoir pressure born by the casing head or the packer, reduce the pressure difference between the oil pipe and the annulus, inhibit the corrosion of the casing and the growth of bacteria, and absorb/release the heat in the partial injection and production process, thereby prolonging the service life of the production casing and the packer. When a small amount of hydrogen gas leaks from the salt cavern, the color of the protective liquid can be changed into blue, and preventive measures can be taken in advance to ensure the safety of hydrogen storage.)

1. The salt pit hydrogen storage well environment protection liquid is characterized by comprising the following components in percentage by mass: 15-40% of organic salt, 2.3-8.0% of pH regulator, 1.0-4.0% of bactericide, 0.1-1% of hydrogen indicator, 0.5-2% of gas well corrosion inhibitor, 0.5-6.0% of deoxidant and the balance of water.

2. The annular space protective solution for the salt cavern hydrogen storage well as the claim 1 is characterized in that the organic salt is one or more of sodium formate, potassium formate, sodium acetate and potassium acetate.

3. The solution according to claim 1, wherein the pH modifier is carbonate and/or bicarbonate, and the carbonate is selected from sodium carbonate and/or potassium carbonate; the bicarbonate is selected from sodium bicarbonate and/or potassium bicarbonate.

4. The annular protective solution for the salt cavern hydrogen storage well as the claim 1, wherein the bactericide is one of 2, 2-dibromo-2-cyanoacetamide, kanamycin and clinafloxacin hydrochloride.

5. The annular protective liquid for a salt cavern hydrogen storage well as claimed in claim 1, wherein the hydrogen indicator is WO₃And a metal compound, said WO₃The mass ratio of the metal compound to the metal compound is either 60: the metal compound is a palladium compound or a platinum compound, the palladium compound is palladium acetate, and the platinum compound is platinum chloride.

6. The salt pit hydrogen storage well annular space protection solution as claimed in claim 1, wherein the gas well corrosion inhibitor is one or more of molasses, sodium gluconate, zinc dihydrogen phosphate, urea, disodium silicate nonahydrate and sodium lignosulfonate.

7. The environmental protection solution for a salt cavern hydrogen storage well as defined in claim 1, wherein the oxygen scavenger is dimethyl ketoxime.

8. The annular protective solution for a salt cavern hydrogen storage well as claimed in claim 1, wherein the water is deionized water, the online conductivity of the deionized water is less than 0.3us/cm, and the content of silicon dioxide is less than 20 ppb.

9. The preparation method of the salt cavern hydrogen storage well annular protection fluid as claimed in claim 1 to 8, comprising the following steps:

s1, weighing the raw materials according to the weight percentage of the components of the annular space protection liquid at normal temperature;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, sequentially adding organic salts, a pH regulator, a bactericide, a hydrogen indicator, a gas well corrosion inhibitor and an oxygen scavenger into the solution obtained in the step S3, uniformly stirring until the solids are completely dissolved, and obtaining the annular space protection liquid suitable for the salt cavern hydrogen storage well.

10. The method for preparing the annular protection fluid according to claim 9, wherein the annular protection fluid has a density of 1.00 to 1.05g/cm³The corrosion rate of the annular protection liquid is less than or equal to 0.025mm/aAnd the pH value of the annular protection liquid is 9.0-12.

Technical Field

The invention relates to the technical field of hydrogen energy utilization, in particular to salt cavern hydrogen storage well annular protection liquid and a preparation method thereof.

Background

The underground storage of hydrogen is continuously explored and researched by various countries, artificial gas is prepared by mixing 50-60% of hydrogen and methane in an early stage and is injected into an underground storage, and the underground storage of pure hydrogen (95% of hydrogen and 3-4% of carbon dioxide) is also developed in a later stage, wherein more researches and practices are carried out in the aspect of underground storage of hydrogen in European and American countries such as France, Germany, Britain, America and the like, and the researches in the aspect of the hydrogen are relatively less in China. At present, in order to deal with the energy crisis, energy strategic reserve strategies are actively implemented by various countries, an underground salt cavern reserve is the most important part in energy strategic reserve work, a salt rock underground reserve has the advantages of large storage capacity, high peak regulation speed, safety, economy and the like, and is an internationally recognized underground storage place with the best strategic energy sources such as natural gas, petroleum and the like.

During the salt cavern storage of natural gas, hydrogen gas is a small and light molecule, and has strong permeability and diffusivity, which results in strong fluidity and high leakage of hydrogen gas. Moreover, hydrogen has a wide explosion range in air, so that the risk of hydrogen leakage must be warned at any time, and therefore the sealing of the salt cavern wellhead is very important, the existing salt cavern hydrogen storage wellhead is usually sealed by a casing and a packer, however, certain heat is generated in the processes of hydrogen storage, gas injection and gas production, hydrogen is easy to diffuse, and the diffused hydrogen can accelerate the corrosion rate of the casing and the packer.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: in order to solve the technical problem that a sleeve and a packer are easy to corrode in the process of salt cavern hydrogen storage in the prior art, the invention provides an annular protection liquid for a salt cavern hydrogen storage well and a preparation method thereof. In order to reduce the risk of hydrogen leakage, a hydrogen indicator is added into the annular protection liquid, when trace hydrogen leaks from the salt cavern, the color of the protection liquid is changed into blue, preventive measures can be taken in advance, and the safety of hydrogen storage is ensured.

The technical scheme adopted by the invention for solving the technical problems is as follows: to provide a method for manufacturing a semiconductor device: the salt pit hydrogen storage well environment protection liquid is characterized by comprising the following components in percentage by mass: 15-40% of organic salt, 2.3-8.0% of pH regulator, 1.0-4.0% of bactericide, 0.1-1% of hydrogen indicator, 0.5-2% of gas well corrosion inhibitor, 0.5-6.0% of deoxidant and the balance of water.

Further, the organic salt is one or more of sodium formate, potassium formate, sodium acetate and potassium acetate.

Further, the pH regulator is carbonate and/or bicarbonate, and the carbonate is selected from sodium carbonate and/or potassium carbonate; the bicarbonate is selected from sodium bicarbonate and/or potassium bicarbonate.

Further, the bactericide is one of 2, 2-dibromo-2-cyanoacetamide, kanamycin and clinafloxacin hydrochloride.

Further, the hydrogen indicator is WO₃And a metal compound, said WO₃The mass ratio of the metal compound to the metal compound is either 60: the metal compound is a palladium compound or a platinum compound, the palladium compound is palladium acetate, and the platinum compound is platinum chloride.

Further, the gas well corrosion inhibitor is composed of one or more of molasses, sodium gluconate, zinc dihydrogen phosphate, urea, disodium silicate nonahydrate and sodium lignosulfonate.

Further, the oxygen scavenger is dimethyl ketoxime.

Furthermore, the water is deionized water, the online conductance of the deionized water is less than 0.3us/cm, and the content of silicon dioxide is less than 20 ppb.

The invention also provides a preparation method of the salt cavern hydrogen storage well annular protection liquid, which comprises the following steps:

s1, weighing the raw materials according to the weight percentage of the components of the annular space protection liquid at normal temperature;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, sequentially adding organic salts, a pH regulator, a bactericide, a hydrogen indicator, a gas well corrosion inhibitor and an oxygen scavenger into the solution obtained in the step S3, uniformly stirring until the solids are completely dissolved, and obtaining the annular space protection liquid suitable for the salt cavern hydrogen storage well.

The invention has the beneficial effects that the salt cavern hydrogen storage well environment protection liquid has the following advantages:

1. the annular protection fluid has the density of 1.00-1.05 g/cm3, the corrosion rate of less than or equal to 0.025mm/a, the pH value of 9.0-12, the oxygen removal rate of more than 98 percent and the sterilization rate of more than 99 percent, has the influence on the volume, hardness and tensile strength change rate before and after the rubber sleeve of the packer is aged less than +/-2.0 percent and the elongation of less than 5 percent, thereby slowing the aging of the packer and prolonging the service life of the packer.

2. The annular space protection liquid has good thermal stability and higher specific heat capacity, can absorb the heat generated in the hydrogen injection and production process, and can not rapidly rise due to the temperature of the sleeve and the packer, thereby avoiding the long-time thermal deformation of the sleeve and the packer, and improving the service life and the use stability of the sleeve and the packer.

3. Appear ageing when the packer, lead to sealed effect variation to produce the leakage of hydrogen, when trace hydrogen gets into annular space protection liquid, can be absorbed by annular space protection liquid, simultaneously under the catalytic action, the colour of annular space protection liquid can change, thereby in time take remedial action, prevent the leakage of hydrogen, ensure safety.

4. The annular space protection liquid has the advantages of simple preparation process, low cost, strong product stability, excellent corrosion inhibition, sterilization and deoxidization effects, and is suitable for popularization and application.

Drawings

The invention is further illustrated with reference to the following figures and examples.

FIG. 1 is a schematic flow diagram of a method of preparing an annular space protecting fluid of the present invention.

Detailed Description

To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

When the environment-controlled protection liquid is used in the salt cavern hydrogen storage, the production casing and the injection production casing are communicated with the inside of the salt cavern, the production casing is sleeved on the injection production casing, a packer for sealing is arranged between the production casing and the injection production casing, an annular protection liquid is filled between the production casing and the injection production casing, and the annular protection liquid is positioned above the packer.

Example 1: with reference to the figure 1, weighing the following raw materials in percentage by weight: sodium acetate 15%, sodium carbonate 2.3%, kanamycin 1.0%, WO₃And palladium acetate 0.1%, zinc dihydrogen phosphate and disodium silicate nonahydrate 0.5%, dimethyl ketoxime 0.5%, WO₃The mass ratio of the palladium acetate to the palladium acetate is 60: 1;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, adding sodium acetate, sodium carbonate, kanamycin and WO in sequence into the solution obtained in the step S3₃Mixing with palladium acetate, zinc dihydrogen phosphate, disodium silicate nonahydrate and dimethyl ketoxime, stirring until the solid is completely dissolved to obtain annular space protection solution suitable for salt-cavern hydrogen storage well, and making into annular space protection solution with density of 1.01g/cm³The annular space protection liquid.

The performance of the prepared annular protection liquid is tested by using N80 and P110 steel, and various performances of the annular protection liquid can be obtained as follows: the pH value is 9.7, the corrosion rate is 0.013mm/a, the oxygen removal rate is 99.1%, the sterilization rate is 99.2%, the influence of the volume, hardness and tensile strength change rate before and after aging of the rubber sleeve of the packer is less than +/-1.5%, and the elongation is less than 4%.

Example 2: with reference to the figure 1, weighing the following raw materials in percentage by weight: 40% of sodium acetate, 8.0% of sodium carbonate, 4.0% of kanamycin and WO₃And palladium acetate 1.0%, zinc dihydrogen phosphate and disodium silicate nonahydrate 2.0%, dimethyl ketoxime 6.0%, WO₃The mass ratio of the palladium acetate to the palladium acetate is 60: 1;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, adding sodium acetate, sodium carbonate, kanamycin and WO in sequence into the solution obtained in the step S3₃And palladium acetate, zinc dihydrogen phosphate, disodium silicate nonahydrate and dimethyl ketoxime are stirred uniformly until the solid is completely dissolved to obtain the product with the density of 1.07g/cm³The annular space protection liquid.

The performance of the prepared annular protection liquid is tested by using N80 and P110 steel, and various performances of the annular protection liquid can be obtained as follows: the pH value is 10.8, the corrosion rate is 0.006mm/a, the oxygen removal rate is 99.7%, the sterilization rate is 99.5%, the influence of the volume, hardness and tensile strength change rate before and after aging of the rubber sleeve of the packer is less than +/-1.3%, and the elongation is less than 3%.

Example 3: with reference to fig. 1, the environmental control protection solution is prepared by the following steps:

s1, weighing the following raw materials in percentage by weight: sodium acetate 32%, sodium carbonate 3.3%, kanamycin 1.0%, WO₃And palladium acetate 0.5%, zinc dihydrogen phosphate and disodium silicate nonahydrate 1%, dimethyl ketoxime 0.5%, WO₃The mass ratio of the palladium acetate to the palladium acetate is 60: 1;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, adding sodium acetate, sodium carbonate and kanamycin WO in sequence into the solution obtained in the step S3₃And palladium acetate, zinc dihydrogen phosphate, disodium silicate nonahydrate and dimethyl ketoxime are stirred uniformly until the solid is completely dissolved to obtain the product with the density of 1.03g/cm³The annular space protection liquid.

The performance of the prepared annular protection liquid is tested by using N80 and P110 steel, and various performances of the annular protection liquid can be obtained as follows: the density was 1.03g/cm³The pH value is 9.5, the corrosion rate is 0.015mm/a, the oxygen removal rate is 99.1 percent, the sterilization rate is 99.2 percent, the influence of the volume, hardness and tensile strength change rate before and after the aging of the rubber sleeve of the packer is less than +/-1.5 percent, and the elongation is less than 3 percent.

Example 4: with reference to fig. 1, the environmental control protection solution is prepared by the following steps:

s1, weighing the following raw materials in percentage by weight: 35% of potassium acetate, 3.6% of potassium carbonate, 1.0% of kanamycin and WO₃And 0.5% of palladium acetate, 0.5% of sodium gluconate, 0.5% of dimethyl ketoxime, WO₃The mass ratio of the palladium acetate to the palladium acetate is 60: 1;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, sequentially adding potassium acetate, potassium carbonate, kanamycin and WO to the solution obtained in the step S3₃And palladium acetate, sodium gluconate and dimethyl ketoxime are uniformly stirred until the solid is completely dissolved, so that the annular space protection liquid suitable for the salt cavern hydrogen storage well is obtained, and the density is 1.02g/cm³The annular space protection liquid.

The performance of the prepared annular protection liquid is tested by using N80 and P110 steel, and various performances of the annular protection liquid can be obtained as follows: the density was 1.02g/cm³pH value of 9.0, corrosion rate of 0.013mm/a, oxygen removal rate of 99.5%, sterilization rate of 99.1%, and influence on volume, hardness and tensile strength change rate before and after aging of rubber sleeve of packer less than +/-1.8%The elongation is less than 4%.

Example 5: with reference to fig. 1, the environmental control protection solution is prepared by the following steps:

s1, weighing the following raw materials in percentage by weight: 20% of sodium formate, 2.8% of sodium bicarbonate, 1.5% of clinafloxacin hydrochloride and WO₃And palladium acetate 0.5%, zinc dihydrogen phosphate and disodium silicate nonahydrate 1.1%, dimethyl ketoxime 0.9%, WO₃The mass ratio of the palladium acetate to the palladium acetate is 60: 1;

s2, adding a certain amount of deionized water into the reaction kettle;

s3, introducing nitrogen into the deionized water, bubbling and removing oxygen dissolved in the water;

s4, sequentially adding sodium formate, sodium bicarbonate, clinafloxacin hydrochloride and WO 3 into the solution₃Mixing with palladium acetate, zinc dihydrogen phosphate, disodium silicate nonahydrate and dimethyl ketoxime, stirring until the solid is completely dissolved to obtain annular space protection solution suitable for salt-cavern hydrogen storage well, and making into annular space protection solution with density of 1.04g/cm³The annular space protection liquid.

The performance of the prepared annular protection liquid is tested by using N80 and P110 steel, and various performances of the annular protection liquid can be obtained as follows: the density was 1.04g/cm³The pH value is 10.5, the corrosion rate is 0.009mm/a, the oxygen removal rate is 98.9 percent, and the sterilization rate is 99.9 percent; the influence on the volume, hardness and tensile strength change rate before and after the aging of the rubber sleeve of the packer is less than +/-1.6 percent, and the elongation is less than 3 percent.

The properties of the hollow protective solution in examples 1-4 are shown in the following table one:

watch 1

According to the table one, in the preparation methods of the embodiments 1 to 4, the influence of the annular protection fluid prepared in the embodiment 1 on the volume, hardness and tensile strength change rate before and after the aging of the rubber sleeve of the packer is minimal, and the influence on the elongation rate before and after the aging of the rubber sleeve of the packer is also minimal, and if the volume, hardness and tensile strength of the annular protection fluid before and after the aging of the rubber sleeve of the packer exceeds a certain value, the rubber sleeve of the packer is easy to age, the elasticity reduction of rubber can influence the sealing effect of a wellhead, gas can leak, and the material itself cannot achieve the expected service life. Therefore, the smaller the change rate of the volume, the hardness and the tensile strength before and after the aging of the rubber sleeve of the packer and the change rate of the elongation before and after the aging of the rubber sleeve of the packer are, the better, the smaller the change rate is, the more difficult the aging of the packer is, the longer the service life is, and the better the sealing effect is.

The annular protection liquid prepared in the embodiment 2 has the highest oxygen removal rate, and can effectively remove oxygen in the annular protection liquid, so that the production casing and the packer are prevented from being oxidized, the service lives of the production casing and the packer are prolonged, and the safety of hydrogen storage in salt caverns is improved.

The prepared annulus protection fluid in embodiment 3 has minimal corrosiveness to materials, so that the corrosion rate of the production casing and the packer can be slowed down, the service lives of the packer and the production casing can be prolonged, the times of replacing the production casing and the packer can be reduced, and the cost can be saved.

The annular space protection liquid sterilization rate among the embodiment 3 is the highest, can effectively kill the microorganism around the annular space protection liquid, the microorganism of avoiding in the air enters into the hydrogen metabolism that stores in the absorption consumption salt cave from packer department and produces impurity, thereby improve the purity of the hydrogen of storing in the salt cave, reduce the loss of the hydrogen of storing in the salt cave, in addition, the pH value can influence sheathed tube corrosivity, acid solution can accelerate sheathed tube corruption, annular space protection liquid is basicity, can improve sheathed tube life.

According to the environment-controlled protective liquid, the annular protective liquid is filled in the fluid between the injection and production casing, so that the gas reservoir pressure borne by a casing head or a packer is reduced, the pressure difference between an oil pipe and the annular is reduced, the corrosion of the casing is inhibited, and heat in a part of injection and production processes is absorbed/released;

when hydrogen in the salt cave diffuses to annular space protection liquid from the packer, the environmental control protection liquid can absorb the trace hydrogen of diffusion, and the colour of environmental control protection liquid can change simultaneously to be convenient for judge the condition that salt cave hydrogen was revealed through the colour of observing environmental control protection liquid, in time take measures, prevent that hydrogen from further revealing, thereby improve the security performance in salt cave.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined by the scope of the claims.