Oil field getter

Abstract

The invention discloses an oil field getter, and belongs to the technical field of getter materials. The prepared getter is a Zr-based getter, ZrMnFe alloy is used as an alloy target, modified graphene oxide is used as a substrate, a magnetron sputtering method is used, bonds formed between the ZrMnFe alloy and O, N and C are easier to transfer, and the adsorption performance is improved; secondly, modified graphene oxide is prepared through a series of steps, and compared with common graphene oxide, the modified graphene oxide is more excellent in adsorption performance; and finally, the magnetron sputtering method can obtain a high sputtering rate under low working voltage and sputtering air pressure, and the high-quality getter is obtained, so that the getter prepared by the method is high in getter efficiency and has important application value in the technical field of getter materials.

Description

Technical Field

[0001] The invention belongs to the technical field of getter materials, and in particular relates to an oilfield getter. Background Art

[0002] Getters are a general term for preparations or devices that can effectively absorb certain (kinds of) gas molecules, and are used to obtain or maintain vacuum and purify gases, etc. Getters are available in various forms such as powder, disc, strip, tube, ring, cup, etc. Getters are generally composed of metals or metal alloys. When introduced into an evacuated device, the metals or metal alloys show a chemical affinity for specific gases, and they adsorb the target gas molecules present, thereby creating and maintaining a proper vacuum in the device.

[0003] In recent years, with the continuous development of resources, there are more and more oil fields. Oil fields refer to areas rich in oil resources, usually including underground oil reservoirs and related mining facilities. In the related mining facilities, especially those that require vacuum, such as the insulated pipes for injecting water vapor in the production of heavy oil in the oil field, the storage and transportation Dewar containers for cryogenic liquids, and the transportation pipelines for cryogenic fluids, getters need to be added to ensure vacuum conditions. The getters used are divided into evaporative and non-evaporative types. Evaporative getter materials absorb active gases by evaporating at high temperature or evaporating and depositing thin films on the walls of vacuum devices. They are also called diffusion type or flash type. They are usually based on barium, strontium, calcium, magnesium and their alloys. Due to their evaporative properties, they will cause leakage between electrodes, equipment cannot be repaired, and vacuum device manufacturing and design are difficult. Therefore, their application fields are usually limited. Non-evaporative getter materials do not need to evaporate, but absorb gases by activating them by heating, electrifying or reducing the partial pressure of gas. They are usually metals such as titanium, zirconium, hafnium, yttrium and alloys composed of aluminum, rare earth elements or transition metal elements such as iron, cobalt and manganese. They can be made into films. Their advantages are that they can be repeatedly activated, have flexible shapes and sizes, and have a long service life. Therefore, their application range is getting wider and wider. However, the existing non-evaporative getter itself has a small specific surface area, which makes the getter's gas absorption efficiency low and the gas storage capacity small. Therefore, further improvements are needed to meet higher demands in the field of getter material technology. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide an oilfield getter.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] An oilfield getter is prepared by the following steps:

[0007] A1. Place ZrMnFe alloy as an alloy target and modified graphene oxide as a substrate in a coating device, and adjust the target distance and grazing angle;

[0008] A2. Bake and degas the coating device and evacuate it, introduce high-purity argon gas, and adjust the gas pressure;

[0009] A3. After the air pressure in the coating chamber is stable, the sputtering power is adjusted, and magnetron sputtering is performed on the ZrMnFe alloy target. The substrate temperature is continuously increased, and deposition begins.

[0010] A4. After the film deposition is completed, turn off the sputtering power supply, evacuate the coating device, wait for the sample to cool to room temperature, and open the chamber when high-purity argon gas is passed into the coating chamber to atmospheric pressure to obtain the oilfield getter.

[0011] Furthermore, in step A1, the target pole distance ranges from 50 to 100 mm; and the grazing angle ranges from 0 to 80°.

[0012] Furthermore, in step A2, the range of adjusting the air pressure is 2.0-4.0Pa.

[0013] Furthermore, in step A3, the sputtering power ranges from 100 to 130 W; and the substrate temperature ranges from 200 to 300° C.

[0014] The prepared getter is a Zr-based getter that can absorb H 2 , O 2 ,CO,N 2 , CO 2 , H 2 O and other active gases are adsorbed and removed; magnetron sputtering is used, which has the advantages of slow substrate temperature rise, fast deposition rate, small film damage, strong adhesion, good film uniformity and high purity. It can obtain a higher sputtering rate at a lower operating voltage and sputtering gas pressure, and obtain high-quality films without causing excessive substrate temperature rise.

[0015] Furthermore, the ZrMnFe alloy is prepared by the following steps:

[0016] High-purity zirconium particles, high-purity manganese flakes and high-purity iron were added to the arc melting furnace, the arc voltage was set to 350V, and the pressure in the furnace was reduced to 10 before melting. -7 mbar, and then filled with argon until the pressure increased to 800mbar, the smelting was completed, and after repeated remelting 3 times, it was crushed and ground into 60-120 mesh powder to obtain ZrMnFe alloy.

[0017] Furthermore, the mass ratio of the high-purity zirconium particles, the high-purity manganese sheets, and the high-purity iron is 1:1:1.

[0018] Zr is a transition metal with 4 valence electrons and an electronegativity of 1.33. It has a high affinity for oxygen. When Fe and Mn are added to make an alloy, the ligands that form bonds between Fe and Mn are more easily formed, rearranged and cleaved. The prepared getter contains these three elements, and the bonds between O, N and C can be more easily transferred, thereby improving the adsorption performance.

[0019] Furthermore, the modified graphene oxide is prepared by the following steps:

[0020] S1. Add graphite powder, potassium nitrate and potassium permanganate to concentrated sulfuric acid solution (mass fraction 98%) in sequence, stir for 10 minutes, then heat to 45°C, continue stirring for 30 minutes, gradually add distilled water, and dropwise add hydrogen peroxide aqueous solution (mass fraction 21%), observe that the solution turns bright yellow, stop dropping, filter, wash sulfate ions with hydrochloric acid solution (mass fraction 8%) and distilled water, and vacuum dry to obtain graphene oxide; the ratio of concentrated sulfuric acid solution, graphite powder, potassium nitrate, potassium permanganate, and distilled water is 25mL:1g:0.5g:2g:50mL;

[0021] Graphene oxide is prepared by oxidizing graphite through the Hummers modified method;

[0022] S2, graphene oxide and N, N-dimethylformamide (DMF) were mixed, and ultrasonic treatment was performed for 30 min to uniformly disperse the graphene oxide, and tartaric acid was added. After ultrasonic treatment for 2 h, a suspension was obtained, and the suspension was placed in a constant temperature oscillator, the temperature was set to 60 ° C, and the reaction was stirred for 4 h. Then, the suspension was placed in a rotary evaporator, the temperature was set to 80 ° C, and the reaction was performed for 2 h. After the reaction was completed, the mixture was washed with water for several times until neutral, and vacuum dried to obtain tartaric acid-modified graphene oxide; the ratio of graphene oxide, N, N-dimethylformamide, and tartaric acid was 1 g: 100 mL: 3.4 g;

[0023] By modifying graphene oxide with tartaric acid, a large number of hydroxyl and carboxyl functional groups can be introduced on the surface of graphene oxide;

[0024] S3. In a three-necked flask equipped with a stirring device, the tartaric acid-modified graphene oxide and the ethanol aqueous solution are mixed, and after ultrasonic dispersion, KH-550 is added to the device. After mixing and stirring, the temperature of the system is maintained at 75°C and the reaction is carried out for 4 hours. After the reaction is completed, the modified graphene oxide is filtered, freeze-dried, and ground to obtain the modified graphene oxide; the ratio of the tartaric acid-modified graphene oxide, the ethanol aqueous solution, and the KH-550 is 1g:100mL:4.7g;

[0025] KH-550 can react with the hydroxyl groups on the surface of tartaric acid-modified graphene oxide to obtain modified graphene oxide;

[0026] The prepared modified graphene oxide is an intermediate product of graphene prepared by an oxidation-reduction method. The oxidation process produces a variety of oxygen-containing functional groups on its surface. It is precisely because of these oxygen-containing functional groups that it has excellent adsorption performance. At the same time, the graphene oxide also has a large specific surface area, rapid adsorption, and can be used multiple times. First, tartaric acid is used to preliminarily modify the graphene oxide, and the introduced active groups can greatly improve the adsorption performance of the graphene oxide. In addition, the modified graphene oxide molecules also contain silicon and nitrogen elements. The introduction of silicon element makes it easier to form a single-layer structure, forming wrinkles on its surface, increasing the specific surface area of ​​the graphene oxide, and thus enhancing its adsorption performance. Moreover, when the modified graphene is aggregated, the wrinkles on its surface make its structure looser, forming large-diameter through holes, and further enhancing its adsorption performance through the large-diameter through holes; by doping nitrogen element, the introduction of nitrogen element significantly increases the number of defect points and vacancies in the graphene oxide plane, further improving the adsorption performance of the modified graphene oxide.

[0027] Beneficial effects of the present invention:

[0028] The prepared getter is a Zr-based getter, with a ZrMnFe alloy as an alloy target, modified graphene oxide as a substrate, and a magnetron sputtering method, wherein the bonds formed between the ZrMnFe alloy and O, N and C are more easily transferred, thereby improving the adsorption performance; secondly, the modified graphene oxide is prepared through a series of steps, and the adsorption performance is better than that of ordinary graphene oxide; finally, the magnetron sputtering method can obtain a higher sputtering rate under a lower working voltage and sputtering gas pressure, and obtain a high-quality getter, therefore, the getter prepared by the invention has high air absorption efficiency and has important application value in the field of the getter material technology. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Embodiment 1

[0031] Preparation of modified graphene oxide:

[0032] S1. Add 1 g of graphite powder, 0.5 g of potassium nitrate and 2 g of potassium permanganate to 25 mL of concentrated sulfuric acid solution (mass fraction 98%) in sequence, stir for 10 min, then heat to 45 ° C, continue stirring for 30 min, gradually add 50 mL of distilled water, and dropwise add an aqueous hydrogen peroxide solution (mass fraction 21%). When the solution turns bright yellow, stop dropping, filter, wash sulfate ions with hydrochloric acid solution (mass fraction 8%) and distilled water, and vacuum dry to obtain graphene oxide;

[0033] S2, 1g of graphene oxide was mixed with 100mL of N,N-dimethylformamide, and ultrasonicated for 30min to uniformly disperse the graphene oxide, and then 3.4g of tartaric acid was added, and a suspension was obtained after ultrasonication for 2h. The suspension was placed in a constant temperature oscillator, the temperature was set to 60°C, and the reaction was stirred for 4h, and then placed in a rotary evaporator, the temperature was set to 80°C, and the reaction was carried out for 2h. After the reaction was completed, the mixture was washed with water several times until neutral, and vacuum dried to obtain tartaric acid-modified graphene oxide;

[0034] S3. In a three-necked flask equipped with a stirring device, 1 g of tartaric acid-modified graphene oxide was mixed with 100 mL of ethanol aqueous solution. After ultrasonic dispersion, 4.7 g of KH-550 was added to the device. After mixing and stirring, the temperature of the system was maintained at 75 ° C. The reaction was carried out for 4 hours. After the reaction was completed, the modified graphene oxide was filtered, freeze-dried, and ground to obtain the modified graphene oxide.

[0035] Embodiment 2

[0036] Preparation of ZrMnFe alloy:

[0037] 1g of high-purity zirconium particles, 1g of high-purity manganese sheets and 1g of high-purity iron were added to the arc melting furnace. The arc voltage was set to 350V. The pressure in the furnace was reduced to 10mbar before melting, and then argon was filled until the pressure increased to 800mbar. The melting was completed, and the remelting was repeated 3 times. After crushing and grinding into 60-mesh powder, ZrMnFe alloy was obtained.

[0038] Embodiment 3

[0039] A1. The ZrMnFe alloy prepared in Example 2 is used as an alloy target, and the modified graphene oxide prepared in Example 1 is used as a substrate and placed in a coating device, and the target distance is adjusted to 50 mm and the grazing angle is 40°;

[0040] A2. Bake and degas the coating device and evacuate it, introduce high-purity argon gas, and adjust the gas pressure to 2.0Pa;

[0041] A3. After the air pressure in the coating chamber is stable, the sputtering power is adjusted to 100W, and magnetron sputtering is performed on the ZrMnFe alloy target. The substrate temperature is continuously increased to 200°C, and deposition begins;

[0042] A4. After the film deposition is completed, turn off the sputtering power supply, evacuate the coating device, wait for the sample to cool to room temperature, and open the chamber when high-purity argon gas is passed into the coating chamber to atmospheric pressure to obtain the oilfield getter.

[0043] Comparative Example 1

[0044] Use a commercially available getter.

[0045] Comparative Example 2

[0046] Ordinary graphene oxide was used to replace the modified graphene oxide in Example 3, and the remaining steps were the same as those in Example 3 to prepare a getter.

[0047] The following performance tests were performed on Example 3, Comparative Examples 1 and 2;

[0048] The international standard GB / T 25497-2010 "Test method for gas absorption and release performance of getter" is used to measure the absorption performance;

[0049] The measured results are shown in the following table:

[0050]

[0051]

[0052] It can be seen from the above table that the getter prepared in the embodiment of the present invention has a higher air absorption capacity than the control example and has good adsorption properties for various gases. Therefore, the getter prepared in the present invention has high air absorption efficiency and has important application value in the field of getter material technology.

[0053] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0054] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An oilfield getter, characterized in that: Prepared by the following steps: A1. Place ZrMnFe alloy as an alloy target and modified graphene oxide as a substrate in a coating device, and adjust the target distance and grazing angle; A2. Bake and degas the coating device and evacuate it, introduce high-purity argon gas, and adjust the gas pressure; A3. After the air pressure in the coating chamber is stable, the sputtering power is adjusted, and magnetron sputtering is performed on the ZrMnFe alloy target. The substrate temperature is continuously increased, and deposition begins. A4. After the film deposition is completed, turn off the sputtering power supply, evacuate the coating device, wait for the sample to cool to room temperature, and open the chamber when high-purity argon gas is passed into the coating chamber to atmospheric pressure to obtain the oilfield getter.

2. An oilfield getter according to claim 1, characterized in that: In step A1, the target pole distance ranges from 50 to 100 mm; the grazing angle ranges from 0 to 80°.

3. The oilfield getter according to claim 1, characterized in that: In step A2, the air pressure is adjusted to a range of 2.0-4.0 Pa.

4. The oilfield getter according to claim 1, characterized in that: In step A3, the sputtering power ranges from 100 to 130 W; the substrate temperature ranges from 200 to 300°C.

5. The oilfield getter according to claim 1, characterized in that: The modified graphene oxide is prepared by the following steps: S1. Add graphite powder, potassium nitrate and potassium permanganate to concentrated sulfuric acid solution in sequence, stir for 10 minutes, then heat to 45°C, continue stirring for 30 minutes, gradually add distilled water, and dropwise add aqueous hydrogen peroxide solution. When the solution turns bright yellow, stop dropping, filter, wash sulfate ions with hydrochloric acid solution and distilled water, and vacuum dry to obtain graphene oxide; S2, graphene oxide and N, N-dimethylformamide were mixed, and ultrasonic treatment was performed for 30 minutes to uniformly disperse the graphene oxide, and tartaric acid was added, and a suspension was obtained after ultrasonic treatment for 2 hours. The suspension was placed in a constant temperature oscillator, the temperature was set to 60°C, and the suspension was stirred for reaction for 4 hours. The suspension was then placed in a rotary evaporator, the temperature was set to 80°C, and the reaction was performed for 2 hours. After the reaction was completed, the suspension was washed with water and vacuum dried to obtain tartaric acid-modified graphene oxide; S3. Mix the tartaric acid-modified graphene oxide with an ethanol aqueous solution, disperse them uniformly by ultrasonication, then add KH-550 into the device, stir and mix them uniformly, maintain the temperature of the system at 75°C, react for 4 hours, filter, freeze-dry and grind to obtain modified graphene oxide.

6. The oilfield getter according to claim 5, characterized in that: In step S1, the ratio of the amount of concentrated sulfuric acid solution, graphite powder, potassium nitrate, potassium permanganate, and distilled water is 25 mL: 1 g: 0.5 g: 2 g: 50 mL.

7. The oilfield getter according to claim 5, characterized in that: In step S2, the ratio of graphene oxide, N,N-dimethylformamide and tartaric acid is 1 g:100 mL:3.4 g.

8. The oilfield getter according to claim 5, characterized in that: In step S3, the ratio of the amount of tartaric acid-modified graphene oxide, ethanol aqueous solution, and KH-550 is 1 g: 100 mL: 4.7 g.

9. The oilfield getter according to claim 1, characterized in that: The ZrMnFe alloy is prepared by the following steps: High-purity zirconium particles, high-purity manganese sheets and high-purity iron are added to the arc melting furnace, the arc voltage is set to 350V, the pressure in the furnace is reduced to 10-7mbar before melting, and then argon is filled until the pressure increases to 800mbar. The melting is completed, and the remelting is repeated 3 times, and then it is crushed and ground into 60-120 mesh powder to obtain ZrMnFe alloy.

10. An oilfield getter according to claim 9, characterized in that: The mass ratio of the high-purity zirconium particles, the high-purity manganese sheets, and the high-purity iron is 1:1:1.

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