CN104694705B - A kind of degree of depth device for deoxidizing and application thereof - Google Patents

Abstract

The invention relates to a deep deoxidation device and its application, belonging to the technical field of chemical reaction deoxidation. The deep deoxygenation device designed in the present invention comprises a gas heating device (4), a No. 1 deoxygenation channel (1), a No. 2 deoxygenation channel (2), and a No. 3 deoxygenation channel (3) connected in sequence. The No. 1 deoxidation channel (1) is provided with a No. 1 deoxidizer, and the No. 1 deoxidizer is selected from a kind of metal copper element and copper-based alloy; the No. 2 deoxidation channel (2) is provided with 2 No. 2 deoxidizer, the No. 2 deoxidizer is selected from metal titanium element, sponge titanium, and titanium-based alloy; No. 3 deoxidizer is provided in the No. 3 deoxidation channel (3), and No. 3 deoxidizer One selected from elemental magnesium and magnesium-based alloys. The device of the invention is used to deoxidize the Ar gas with a purity of 99.999%, and the deoxidation precision can reach ^10-21 ppm. The device designed by the invention can perform high-efficiency deep deoxidation under normal pressure, and has the advantages of simple equipment, recyclable deoxidizer, and the like.

Description

A deep deoxidation device and its application

technical field

The invention relates to a deep deoxidation device and its application, belonging to the technical field of chemical reaction deoxidation.

Background technique

In the iron and steel metallurgical production process, oxygen, sulfur, phosphorus, hydrogen, nitrogen, etc. are several harmful elements that seriously damage the quality of slabs. It is the goal of the 21st century to reduce the total content of such non-metallic elements within the range of 30ppm. Among them, oxygen not only reduces the hot brittleness of steel, but also can significantly reduce the surface tension of molten steel. According to page 389 of the third edition of "Principles of Iron and Steel Metallurgy" compiled by Huang Xihu, the bibliography, it is clearly pointed out that the dissolved oxygen content in boiling steel should be reduced to 250-300ppm; the dissolved oxygen content in killed steel should be less than 50ppm. Committed to the study of the wetting behavior of molten steel and inclusions by the lying drop method, it is necessary to obtain a partial pressure of gaseous oxygen that is lower than the equilibrium oxygen content in molten steel. Generally, the oxygen content in the atmosphere is controlled within the range below the decomposition pressure of iron oxides (the reason is that the existence of iron oxides causes the surface tension of molten steel to drop sharply and spread on the substrate), so as to simulate the wetting of tiny molten steel in all directions. Behavior of wet inclusions. In the area where the steel sample exists stably, the equilibrium oxygen content in the atmosphere is within 10 ^-22 to 10 ^-13 ppm, and it increases with the increase of temperature (for specific calculation, refer to pages 250 to 251 of the third edition of Principles of Iron and Steel Metallurgy).

At present, the application patents and related documents of the preparation method of deoxidizer mainly include the following four deoxidation methods: carbonaceous deoxidizer; metal and metal oxide deoxidizer; hydrogenation and deoxygenation of active catalyst; oxidation deoxidation of organic acid salt at room temperature (limited to normal temperature and pressure use, for example publication number is that CN1411905A discloses a kind of food deoxidizer of silicon, phenolic organic matter).

In the patent with the publication number CN103007880A, after impregnating 91-93% activated carbon with 4-8% strong alkali KOH and NaOH, after drying and removing ash, it shows higher deoxygenation activity. Although the carbonaceous deoxidizer has a large high-temperature deoxidation capacity, low cost, and flexible production, its deoxidation effect has not been pointed out in the literature; and the escape of a large amount of CO gas and dust requires the improvement of post-treatment processes such as tail gas emission and dust removal, which undoubtedly increases The process cost is increased; with the continuous consumption of carbon, the amount of ash produced will gradually increase, which will easily block the gas pipeline and pollute the furnace environment; carbonaceous materials are consumable materials, and their consumption speed and replacement frequency are unknown. In summary, this deoxidation method is not suitable for widespread use.

In the patent with the publication number CN1090221A, the rare metal molybdenum is used for deoxidation, and the oxygen content in the common inert gas or the mixed atmosphere containing alkane or the atmosphere containing sulfur and CO can be reduced to 0.1ppm within 200 °C. The noble metal molybdenum can be directly used for deoxidation, which not only reduces the complicated treatment process, but also avoids the possibility of catalyst poisoning in the atmosphere containing sulfur or CO. In the patents with publication numbers CN1973994A and CN102850159A, low-valent manganese oxides are used as deoxidizers to obtain residual oxygen contents lower than 1 ppm and lower than 0.01 ppm respectively. Its applicable temperature range is within 150-250°C and 100°C respectively, and the high-valent manganese oxides produced can be reduced in the mixed gas containing H ₂ for recycling. Metal molybdenum or low-valent manganese oxide can be used for direct deoxidation at low temperature. Although it is suitable for deoxidation of all common inert gases or alkane gases containing sulfur or carbon monoxide, the cost of metal molybdenum is high, and the low-temperature deoxidation efficiency of molybdenum and low-valent manganese oxide is unknown. , the depth of deoxidation can only reach 0.01ppm.

In the patent with the publication number CN1130542A, three mixed oxides of CuO, ZnO and Cr ₂ O ₃ are used to catalyze the cracking of gaseous methanol into CO and H ₂ . The oxygen content in the inert atmosphere containing oxygen volume fraction ≤ 5% is reduced to less than 1ppm. However, the deoxidized gas contains 1-10% _H2 and CO and a trace amount of _CO2 less than 5ppm. The innovation of this method lies in the use of high-pressure decomposition of organic matter to generate a reducing atmosphere, but in this method, a large amount of H ₂ -CO is entrained in the deoxidized product, which not only reduces the utilization rate of the reducing atmosphere, but also is not conducive to continuous and stable control Oxygen content in the atmosphere. In addition, the residual oxygen content in the gas product obtained by this method is too high (1 ppm), thereby greatly limiting its application range.

In the patent with the publication number CN1631530A, platinum sulfide (PtSx) is used to catalyze the hydrogen-containing inert atmosphere. Under the conditions of temperature of 25-450°C and pressure of 1-15MPa, carbonyl sulfide and oxygen volume fraction are not more than 5%. The oxygen content in the atmosphere is reduced to 1ppm. The patent with publication number CN1070128A combines the advantages of low-priced manganese oxide and noble metal Pt to catalyze _H2 double deoxidation, and reduces the final residual oxygen content to below 0.003ppm in the temperature range from room temperature to 450°C. Compared with the above direct deoxygenation methods, the catalytic hydrodeoxygenation method is more effective, but the residual oxygen content is still high; and the platinum catalyst is expensive, and it is extremely sensitive to the atmosphere containing carbonyl sulfide and high oxygen content, and is easy to be poisoned.

To sum up, the existing deoxygenation technology has low deoxygenation capacity, or the deoxygenation precision is not deep enough, or the deoxygenation efficiency is low, or the deoxidation method of catalytic reducing gas is easy to be poisoned, or some reaction systems are preferably carried out under high pressure conditions, resulting in safety. One or more problems with low coefficients. Therefore, there is an urgent need for a deoxidation technology with deep deoxidation precision, long service life, low cost and safety.

Contents of the invention

The invention aims at the deficiencies in the existing deoxidation technology, and provides a deep deoxidation device and its application.

A deep deoxygenation device of the present invention comprises a gas heating device (4), a No. 1 deoxygenation channel (1), a No. 2 deoxygenation channel (2), and a No. 3 deoxygenation channel (3) connected in sequence; the No. 1 deoxygenation channel ( 1) No. 1 deoxidizer is provided inside, and the No. 1 deoxidizer is selected from a kind of metal copper element and copper-based alloy; No. 2 deoxidizer is provided in the No. 2 deoxidation channel (2), and the No. 2 deoxidizer No. 1 deoxidizer is selected from metal titanium element, sponge titanium, titanium-based alloy (such as titanium aluminum alloy, etc.); No. 3 deoxidizer is provided in the No. 3 deoxidation channel (3), and No. 3 deoxidizer One selected from elemental magnesium and magnesium-based alloys (such as magnesium-lithium alloys, etc.).

The copper-based alloy is selected from one of copper-manganese, copper-lead alloy, copper-nickel-cobalt and other alloys, preferably copper-manganese alloy.

The titanium-based alloy is selected from one of alloys such as titanium-aluminum alloy, titanium-nickel alloy, titanium-aluminum-vanadium alloy, preferably titanium-aluminum alloy.

The magnesium-based alloy is selected from one of magnesium-lithium alloys, magnesium-aluminum, magnesium-zinc and other alloys, preferably magnesium-lithium alloys.

The invention relates to a deep deoxidation device, wherein the No. 1 deoxygenation channel (1), the No. 2 deoxygenation channel (2) and the No. 3 deoxygenation channel (3) form horizontal deoxygenation channels connected in series.

The present invention is a deep deoxidation device, wherein the No. 1 deoxidizer, No. 2 deoxidizer and No. 3 deoxidizer are loaded into the deoxidation channel in the shape of a net or chips.

In order to prevent the oxide powder falling off during the oxidation process from clogging the gas flow pipe and to ensure a stable air flow, it is generally necessary to add barbed wire at both ends of each section of the channel.

After the barbed wire is added in the No. 1 deoxidation channel, the barbed wire and the No. 1 deoxidizer exist in the end of the No. 1 deoxidation channel near the gas outlet according to the pattern of barbed wire/No. 1 deoxidizer/barbed wire. In order to ensure a better deoxidation effect, the filling volume of the No. 1 deoxidizer is generally 60%-80% of the volume of the No. 1 deoxidation channel; preferably 70%-80%, more preferably 75%-80%.

After the barbed wire is added in the No. 2 deoxidation channel, the barbed wire and the No. 2 deoxidizer exist at the end of the No. 2 deoxidation channel near the air inlet according to the pattern of barbed wire/No. 2 deoxidizer/barbed wire. In order to ensure a better deoxidation effect, the filling volume of the No. 2 deoxidizer is generally 60%-80% of the volume of the No. 2 deoxidation channel; preferably 70%-80%, more preferably 75%-80%.

After the barbed wire is added in the No. 3 deoxidation channel, the barbed wire and the No. 3 deoxidizer exist in the mode of barbed wire/No. 3 deoxidizer/barbed wire at the end of the No. 3 deoxidation channel near the gas outlet. In order to ensure a better deoxidation effect, the filling volume of No. 3 deoxidizer is generally 60%-80% of the volume of No. 3 deoxidation channel; preferably 75%-80%, more preferably 80%.

In order to ensure a good deoxygenation effect and prevent the blockage of the deoxygenation channel, the No. 1 deoxygenation channel, the No. 2 deoxygenation channel, and the No. 3 deoxygenation channel are generally arranged in series-horizontal arrangement.

In order to maintain the deoxidation temperature of the active metal and reduce heat loss; generally, refractory materials are also required in the deoxidation channel.

The application of a kind of deep deoxidation device of the present invention, its embodiment is:

After the raw gas is heated to 250°C-600°C by the gas heating device (4), it flows through the No. 1 deoxygenation channel (1), the No. 2 deoxygenation channel (2), and the No. 3 deoxygenation channel (3).

The invention relates to an application of a deep deoxidation device, wherein the volume percentage of N ₂ in the raw gas is ≤1%, and the volume percentage of oxygen is ≤1%. The reason why the present invention limits the volume percentage of N ₂ in the raw gas is that when the gas temperature is greater than or equal to 300°C, the active deoxidizer Mg can combine with N ₂ to form Mg ₃ N ₂ , which will lead to a decrease in its deoxidation ability, and in severe cases Until the deoxidation device loses the ability of deoxidation.

The application of a deep deoxidation device of the present invention, the raw material gas can be matched with gas types according to the requirements of the docking equipment for gas components; the deoxidation device is not affected by the sulfur-containing atmosphere.

The application of the deep deoxygenation device of the present invention, the raw material gas is selected from at least one of helium, neon, argon, krypton, xenon, radon, hydrogen, and carbon monoxide. It is preferably at least one of argon, helium, hydrogen, CO ₂ gas and a mixed gas composed of argon/helium and hydrogen. It is further preferably one of industrial argon, industrial helium and their mixed gas with hydrogen.

The application of a deep deoxidation device of the present invention uses industrial argon as the raw material gas, and the raw material gas is heated to 250°C to 600°C by the gas heating device (4); then it flows through No. 1 deoxidation channel (1), No. No. deoxygenation channel (2) and No. 3 deoxygenation channel (3) obtain oxygen volume percentage not exceeding 10 ^-11 ppm, preferably 10 ^-11 ~ 10 ^-21 ppm, more preferably 10 ^-16 ~ 10 ^-19 ppm of argon.

In order to achieve a better deoxidation effect, it is generally necessary to control the flow rate (gas flow rate) of the raw material gas in the deoxidation channel, and the specific flow rate is set according to the size of the equipment connected to the third deoxygenation channel (3). For example: when the equipment connected to No. 3 deoxidation channel (3) is a cylindrical tube furnace; the length of the cylindrical tube furnace is 1086.0mm, the diameter is 74.94mm, and the volume of the furnace is V=(1/4)πD ^2. Calculated by H (where D is the diameter and H is the length of the furnace tube), it is about 4787.70ml, the gas flow rate is Q=V/t, assuming that the time t for the gas to be discharged from the furnace is 20~25min, then Q=190~240ml/min , the preferred range of flow meter in this experiment is 250ml/min.

In the application of a deep deoxidation device of the present invention, the pressure of the raw material gas in the equipment can be normal pressure.

The application of a deep deoxidation device of the present invention, when the equipment is used for a period of time, the deoxidizer can be reactivated with an activator; that is, No. 1, 2 and 3 deoxidizers can be reduced; after activation, the device can still have high efficiency Deep deoxygenation; the activator is composed of argon and hydrogen according to the volume ratio, argon: hydrogen=90-98:2-10. The activated metal can be combined with oxygen to achieve the effect of deep deoxidation, and there is no need to frequently update the metal deoxidizer.

The invention is a deep deoxidation device, which is especially suitable for providing deep precision deoxidation atmosphere for small and medium-sized atmosphere furnaces.

Principles and advantages

The present invention provides a device that can complete deep-precision deoxidation under normal pressure, and its deoxidizer does not need to be frequently updated; after being treated by the device of the present invention, the residual oxygen content is lower than 10 ^-11 ppm, and the lowest can reach 10 ^-21 ppm (volume percentage). The principle is as follows:

The selection of the active metal deoxidizer of the present invention is mainly based on its deoxidizing ability and melting point, and the oxygen potential diagram can intuitively reflect these two properties (see the 249th page of Huang Xihu's third edition "Metallurgical Principles", located at the bottom of the oxygen potential diagram Metals and oxygen have a very strong binding force), and three metals with different deoxidation strengths were selected comprehensively: magnesium, titanium, and copper. , 1083°C.

The horizontal series channel for containing metal in the present invention includes a part loaded with metal and a part filled with refractory material. The metal is cut into filaments or scraps and loaded into the channel to increase the surface area of the active deoxidizer to speed up the deoxidation reaction; the two ends of the metal wire are separated by barbed wire to prevent the oxide powder falling off during the oxidation process from blocking the air flow channel. Ensure stable airflow. The purpose of filling the refractory material is to maintain the deoxidation temperature of the active metal, reduce the heat transfer to the air and the heat loss carried away by the air flow, so as to ensure the deoxidation efficiency.

In the present invention, according to the flow direction of the gas, it passes through three channels of copper, titanium, and magnesium successively. The reason is that the oxygen content of the gas has gradually decreased when passing through the previous channel. Make the furnace atmosphere obtain ultra-low oxygen content.

The temperature range of the gas in the present invention is 250-600°C, and the upper limit should not exceed 649°C, the melting point of metal magnesium, otherwise the temperature will be too high to cause the metal to melt and block the gas circulation pipeline. The temperature heating system is completed by the temperature control box, and its working principle is raised to the specified temperature according to the set value, and then the gas temperature is kept constant at a certain temperature point according to the compensation method. The purpose of heating the gas is to activate the metal and the gas and increase the ability of the metal to bind oxygen. When the equipment is used for a period of time, when the deoxidizer is reactivated with an activator; since the temperature of the raw material gas entering the deoxidation channel is limited by the present invention to 300-600°C; this not only ensures the efficiency of hydrogen reduction of metal oxides, but also avoids A series of problems caused by the melting of the deoxidizer, such as blockage of the pipeline, etc. are eliminated.

The calculation principle of the gas flow in the present invention is aimed at obtaining an ideal deoxidation effect. The gas flow rate should be based on the size of the docking equipment (such as the furnace). If it is too large, the deoxidation effect will be poor, and if it is too small, it will take a lot of time to remove the air in the docking equipment.

Compared with existing industrial oxygen removal methods, the present invention has the advantages

Compared with the technology using molybdenum and platinum sulfide as deoxidizers/catalytic deoxidizers, the present invention has large deoxidation capacity, fast deoxidation speed, strong deoxidation ability (deoxidation depth can reach ^10-21 ppm), and can handle sulfur-containing or CO-containing Gas, no poisoning, wide temperature range and other advantages.

Compared with other industrial oxygen removal methods, the present invention has the following advantages:

1) Deep precision deoxidation. The invention adopts active metal copper, magnesium and titanium to chemically deoxidize at 250-600 DEG C, and the deoxidizing effect is much lower than that of the prior art. For example, at 300°C, only Ar gas is passed through, and the deoxidation depth can reach 10 ^-11 ppm. At 300°C, only argon-hydrogen mixed gas is introduced, and the deoxygenation depth can reach 10 ^-19 ppm.

2) Selection and arrangement of active metal deoxidizers. This device deoxidizes in order according to the strength of the metal deoxidation ability. The purpose is: first, a stable and long-lasting ultra-low oxygen content gas flow can be obtained by means of combination. If you only rely on the active metal Mg for deoxidation, the deoxidation effect is only effective for a period of time, and the dense MgO layer formed on the surface of Mg chips will greatly weaken its deoxidation ability and cause the oxygen content to gradually rise; Frequency of updating metal deoxidizers. After the airflow passes through Cu, Ti, and Mg in sequence, the oxygen content decreases before entering the next channel, so that each section absorbs the oxygen content, and the degree of powdering of magnesium chips is greatly reduced, thereby reducing the frequency of active metal renewal.

3) The deoxidizer has a long service life. Each section of the channel containing the metal wire is narrow and long, and the seal is good. After the experiment is completed, the residual argon can protect the deoxidized metal and reduce the possibility of oxidation failure caused by contact with air. Again, when the metal is at 300-600°C, the mixed gas of Ar and 2-10% _H2 can be introduced to reactivate the metal (after half a year of use of the oxygen removal equipment, the mid-term inspection results show that the surface of the magnesium removal is gray and powdered. In addition, the surface of the other two metals is glossy), so the service life is prolonged, and there is no problem that metal oxides are easy to sinter into agglomerates.

4) Dynamically adjust the oxygen content. Changing the gas temperature when the gas flow rate is constant can dynamically adjust the oxygen content in the gas flow into the furnace; or control the oxygen content by adjusting the hydrogen flow rate, and the time interval is generally within 1.5h.

5) Safe and feasible. The entire oxygen removal system is completed under normal pressure, hydrogen flows in slowly and then flows out, and the gas outlet avoids a high-temperature sealed environment, which will not affect the personal safety of the experimenters.

In summary, the present invention can complete deep-precision deoxidation under normal pressure, and the deoxidizer does not need to be frequently updated, and has the advantages of low cost, easy control, safety, and extremely low residual oxygen in the obtained gas.

Description of drawings

Accompanying drawing 1 is the structural diagram of deep deoxidation device designed by the present invention;

Accompanying drawing 2 is the enlarged view of part A in accompanying drawing 1;

Accompanying drawing 3 is the schematic diagram after the deep deoxidation device designed by the present invention is docked with the furnace;

Accompanying drawing 4 is in comparative example 1, when not heating, pass through Ar-10%H ₂ , namely Ar flow rate 200ml/min, H ₂ flow rate 20ml/min, the oxygen volume percentage content of furnace inlet and outlet changes with time ;

Accompanying drawing 5 is the schematic diagram of the oxygen volume percent content change with time at both ends of the furnace inlet and outlet in the embodiment 1 and 2;

Accompanying drawing 6 is the schematic diagram of the oxygen volume percentage change with time at both ends of the furnace inlet and outlet in embodiment 3;

Accompanying drawing 7 is the schematic diagram of the change of oxygen volume percentage content at both ends of the furnace inlet and outlet with time in Example 4.

In Fig. 1; 1 is No. 1 deoxidation channel, No. 1 deoxidizer is housed in No. 1 channel; 2 is No. 2 deoxidation channel, No. 2 deoxidizer is housed in No. 2 channel; There is No. 3 deoxidizer; No. 4 is a gas heating device. The raw material gas passes through the connecting gas heating device (4), No. 1 deoxygenation channel (1), No. 2 deoxygenation channel (2), and No. 3 deoxygenation channel (3).

In Fig. 2; 1 is No. 1 deoxidation channel, No. 1 deoxidizer is housed in No. 1 channel; 2 is No. 2 deoxidation channel, No. 2 deoxidizer is housed in No. 2 channel; There is No. 3 deoxidizer; the shaded part in Figure 2 is loaded with metal wire (the two ends of the metal wire are blocked by barbed wire to prevent the debris in the metal wire from blocking the pipeline with the airflow, especially magnesium metal shavings), the blank part is filled with refractory asbestos, and the channel The outer end is sealed with a rubber ring and an iron cover. After the barbed wire is added in the No. 1 deoxidation channel, the barbed wire and the No. 1 deoxidizer exist in the end of the No. 1 deoxidation channel near the gas outlet according to the pattern of barbed wire/No. 1 deoxidizer/barbed wire. After the barbed wire is added in the No. 2 deoxidation channel, the barbed wire and the No. 2 deoxidizer exist at the end of the No. 2 deoxidation channel near the air inlet according to the pattern of barbed wire/No. 2 deoxidizer/barbed wire. After the barbed wire is added in the No. 3 deoxidation channel, the barbed wire and the No. 3 deoxidizer exist in the mode of barbed wire/No. 3 deoxidizer/barbed wire at the end of the No. 3 deoxidation channel near the gas outlet. At the same time, it can also be seen from Fig. 2 that No. 1 deoxygenation channel, No. 2 deoxygenation channel, and No. 3 deoxygenation channel are arranged in series-horizontal configuration.

In Fig. 3, the deoxygenated gas enters the docking equipment (furnace) through the pipeline with the oxygen probe B, and then is discharged through the pipeline with the oxygen probe C; the oxygen probe B can measure the oxygen volume percentage in the deoxygenated gas; the oxygen probe C can measure the oxygen volume percentage in the gas obtained after the docking equipment (furnace).

Fig. 4 is when not heating, feeds Ar-10%H ₂ mixed gas, promptly Ar flow rate 200ml/min, H Flow rate 20ml/min, the oxygen volume percent content change schematic diagram of furnace inlet and _outlet with time; Wherein No. 1 The curve represents the time-varying schematic diagram of the oxygen volume percentage at the furnace inlet measured by the oxygen probe B; the No. 2 curve represents the time-varying schematic diagram of the oxygen volume percentage at the furnace outlet measured by the oxygen probe C.

Figure 5 is a schematic diagram of the volume percentage of oxygen at both ends of the furnace inlet and outlet changing with time when the gas temperature is 300°C and 400°C respectively, and the flow rate of Ar is 250ml/min; Schematic diagram of the measured oxygen content at the furnace outlet varying with time; Curve No. 4 represents a schematic diagram of the oxygen content at the furnace inlet measured by oxygen probe B varying with time.

Fig. 6 is a gas temperature at 300 DEG C, feeds Ar- ₁₀ %H Mixed gas, i.e. Ar flow rate 250ml/min, H Flow rate 25ml/min, the oxygen volume percentage change schematic diagram of furnace inlet and _outlet with time; Curve No. 5 represents the change of oxygen volume percentage at the furnace outlet measured by oxygen probe C over time; curve No. 6 represents the change of oxygen volume percentage at the furnace inlet measured by oxygen probe B over time. .

Figure 7 is a schematic diagram of the change of oxygen volume percentage at the inlet and outlet of the furnace with time when the Ar-2% _H2 mixed gas is introduced at 300°C, that is, the Ar flow rate is 250ml/min, and the _H2 flow rate is 25ml/min. Curve No. 7 represents a schematic diagram of the oxygen volume percentage at the furnace outlet measured by oxygen probe C versus time; curve No. 8 represents the oxygen volume percentage at the furnace inlet measured by oxygen probe B versus time schematic diagram.

detailed description

The following comparative examples and examples will illustrate the present invention in conjunction with accompanying drawings 1 to 7. The raw material gas Ar used is an ultra-high-purity gas with a purity of 99.999%. The docking equipment used in the examples of the present invention and comparative examples is this experiment Chamber tube furnace; the instruments for measuring oxygen content at both ends of the furnace are H-M-E zirconia probes provided by Wuhan Huamin Measurement and Control Co., Ltd. The measured oxygen content is expressed in volume percentage, which has been converted into ppm here.

Comparative example 1

The gas flow rate was set at 200ml/min, and the temperature control box was not opened to preheat the gas. After 239 minutes of introducing Ar gas, the oxygen content measured by the oxygen probe C at the outlet was stable at 1.40ppm. After 4 hours, the oxygen content in each part of the furnace is close to 1ppm, which is similar to the residual oxygen content provided by general patents.

Comparative example 2

Comparative example ₂ is after comparative example 1, continues to feed Ar-10%H Mixed gas, flow rate is respectively 200ml/min, 20ml/min, and concrete oxygen content variation is shown in accompanying drawing 4. It can be seen from the figure that the oxygen content in the subsequent process fluctuates greatly and is very unstable; compared with Comparative Example 1, the deoxygenation depth is greatly reduced, falling within the range of 10 ^-18.5 to 10 ^-15.5 ppm.

Example 1

The flow rate of the raw material Ar gas was set at 250ml/min, and the temperature was kept constant at 300°C. Figure 5 is a schematic diagram of the oxygen content change after the Ar gas was introduced for 2 hours. After 184 minutes of the test, the oxygen content at the inlet and outlet of the furnace decreased to 1.79×10 ^-11 /2.34×10 ^-5 ppm respectively; after another 55 minutes, the oxygen content at both ends was basically stable at 10 ^-11 ppm, with an average of 1.442×10 ^{- 11} /5.470× ^10-11 ppm.

Example 2

Example 2 is following Example 1, and the gas temperature is changed to 400°C, that is, after Ar gas is still introduced at 250ml/min for 132 minutes, the oxygen content at the inlet and outlet is finally reduced to 10 ^-15 /10 ^-14 ppm, the specific oxygen content See Figure 5 for a schematic diagram of the changes. It can be seen from the figure that the oxygen content decreases steadily, the average oxygen content at the inlet end is 4.55×10 ^-15 ppm, and the average oxygen content at the outlet end is about 4.15×10 ^-14 ppm, which will further decrease with time.

Example 3

Compared with Example 1, the difference is that when the gas temperature is 300°C, Ar-10%H ₂ mixed gas is introduced, that is, the Ar and H ₂ flows are adjusted to 250 and 25ml/min respectively, and after 200min, the inlet and outlet The oxygen content was stable at 10 ^-19 /10 ^-18 ppm, and the schematic diagram of oxygen content change after 144 minutes is shown in Figure 6. It can be seen from the figure that the oxygen content is greatly reduced when the mixed gas of Ar and _H2 is passed through without heating, and after 344 minutes of the experiment, the oxygen content at the inlet end changes slightly, and the oxygen content at the outlet end may be affected by the mixed gas flow in the furnace. The maximum fluctuation range of logarithmic value is 0.333 (that is, the fluctuation range of oxygen content is 2.15ppm).

Example 4

Compared with Example 3, the difference is that when the gas temperature is 300°C, Ar-2%H ₂ mixed gas is introduced, that is, Ar and H ₂ flows are adjusted to 250 and 5ml/min respectively, and after 149min, the inlet and outlet The oxygen content decreased to 10 ^-18 /10 ^-16 ppm respectively, and the schematic diagram of oxygen content change after 149 minutes is shown in Figure 7. It can be seen from the figure that although the depth of deoxidation is lower than that of Example 3, the oxygen content changes slowly, indicating that _H2 can enhance the deoxidation effect, and the proportion of hydrogen gas also affects the deoxidation effect at the same time.

Claims (9)

1. A deep deoxidation device, characterized in that: comprise a gas heating device (4), No. 1 deoxygenation channel (1), No. 2 deoxygenation channel (2), No. 3 deoxygenation channel (3) connected successively; The No. 1 deoxidizer is provided in the No. 1 deoxidation channel (1), and the No. 1 deoxidizer is selected from the metal copper element and a copper-based alloy; the No. 2 deoxidizer is provided in the No. 2 deoxidation channel (2). , the No. 2 deoxidizer is selected from one of metal titanium element, sponge titanium, and titanium-based alloy; the No. 3 deoxidizer channel (3) is provided with a No. 3 deoxidizer, and the No. 3 deoxidizer is selected from magnesium One of elemental, magnesium-based alloys. 2. A deep deoxidation device according to claim 1, characterized in that: the No. 1 deoxidizer, No. 2 deoxidizer, and No. 3 deoxidizer are loaded into the deoxidation channel in the shape of a mesh or chips. 3. A kind of deep deoxidation device according to claim 1, characterized in that: There is also a barbed wire mesh in the No. 1 deoxidation channel, and the barbed wire and the No. 1 deoxidizer exist at the end of the No. 1 deoxidation channel near the gas outlet according to the pattern of barbed wire/No. 1 deoxidizer/barbed wire; The No. 2 deoxidation channel is provided with barbed wire, and the barbed wire and No. 2 deoxidizer exist in the mode of barbed wire/No. 2 deoxidizer/barbed wire at the end of the No. 2 deoxidation channel near the air inlet; The No. 3 deoxidation channel is provided with barbed wire, and the barbed wire and No. 3 deoxidizer exist in the mode of barbed wire/No. 3 deoxidizer/barbed wire at the end of the No. 3 deoxidation channel near the gas outlet. 4. A kind of deep deoxidation device according to claim 3, characterized in that: The filling volume of No. 1 deoxidizer is 60%-80% of the volume of No. 1 deoxidation channel; The filling volume of No. 2 deoxidizer is 60%-80% of the volume of No. 2 deoxidizer channel; The filling volume of the No. 3 deoxidizer is 60%-80% of the volume of the No. 3 deoxidation channel. 5. A deep deoxidation device according to claim 1, characterized in that: No. 1 deoxygenation channel, No. 2 deoxygenation channel, and No. 3 deoxygenation channel are arranged in series-horizontal. 6. A kind of application of deep deoxidation device as described in any one of claim 1-5, it is characterized in that: The raw material gas is heated to 250°C to 600°C by the gas heating device (4); it flows through No. 1 deoxygenation channel (1), No. 2 deoxygenation channel (2), and No. 3 deoxygenation channel (3); The gas is at least one selected from helium, neon, argon, krypton, xenon, radon, hydrogen, and carbon monoxide. 7. The application of a deep deoxidation device according to claim 6, characterized in that: the volume percentage of _N2 in the raw gas is ≤ 1%, and the volume percentage of oxygen is ≤ 1%. 8. The application of a deep deoxidation device according to claim 7, characterized in that: using industrial argon as the raw material gas, the raw material gas is heated to 250°C-600°C by the gas heating device (4); The argon gas with the mass percentage of oxygen less than or equal to 10 ⁻¹¹ ppm is obtained through No. 1 deoxygenation channel (1), No. 2 deoxygenation channel (2) and No. 3 deoxygenation channel (3). 9. The application of a deep deoxidation device according to claim 7, characterized in that: after the equipment has been used for a period of time, an activator is used to reduce and activate No. 1, 2, and 3 deoxidizers; after reduction and activation, the The device can still be deeply deoxygenated; the activator is composed of argon and hydrogen according to the volume ratio, argon:hydrogen=90-98:2-10.