CN113023696B - Method and device for recovering discharged argon in monocrystalline silicon preparation - Google Patents
Method and device for recovering discharged argon in monocrystalline silicon preparation Download PDFInfo
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Abstract
The invention discloses a method for purifying and recovering tail gas discharged by argon in a monocrystalline silicon preparation process, which mainly comprises the following steps: 1) A purification process; 2) A regeneration process; 3) A cooling process and 4) a replacement process. The invention also discloses a corresponding argon recovery device and a corresponding argon recovery process. The device comprises: the system comprises a chemical-looping combustion reactor (7), a heat exchanger (5), an adsorbent reactor (20), circulating water cooling devices (16) and (21), a compressor (2), a circulating fan (27), an air cooling dryer (14), an oxygen analyzer (29), heat preservation sleeves (8) and (8'), an auxiliary heating device (6) and corresponding control valves. The existing device has the advantages of simple process flow, low energy consumption and high argon recovery rate.
Description
Technical Field
The invention relates to a method and a device for purifying and recovering argon discharged in a monocrystalline silicon preparation process, belonging to the technical field of purification and recovery of inert gas.
Background
With the increasing demand for renewable clean energy, the photovoltaic power generation industry based on solar energy utilization is rapidly developing, the photovoltaic cell power generation can provide necessary power supply for families, offices and the like, and if the photovoltaic cell power generation is further incorporated into a power grid, the photovoltaic cell power generation can provide power support for industrial production. Photovoltaic cells currently used on a large scale are mainly silicon-based solar modules.
The main raw material of the process flow for producing silicon-based solar electronic components is crystalline silicon (monocrystalline or polycrystalline), which is produced by different processes. For example, a typical single crystal silicon is subjected to a high temperature condition (>1400 ℃ C.) and extracting the raw material silicon ingot into single crystal silicon by the Czochralski method. In the czochralski process, in order to ensure the quality of the product, a large amount of argon gas is required to be used for purging, and various volatile impurities generated from a material containing crucible in the refining process are removed. These impurities are mainly carbon monoxide (CO), which ranges from several thousand ppm; hydrogen gas, ranging from tens to hundreds of ppm, while a small amount of methane (CH) may be present depending on the vacuum pump used 4 ) At several to tens of ppm. In the early stage, because the demand of argon is small and the price is low, the argon in the crystal pulling process is completely emptied. In recent years, with the rapid development of the photovoltaic industry, the demand of argon gas is rapidly increased, the price is increased from hundreds of yuan per ton to 1000-2000 yuan per ton in the early period, and the price is even higher in local areas. Under the current typical Czochralski method process conditions (the argon dosage is 60-80L/min, the maintenance time is 300 h), the annual argon dosage value of one hundred single crystal furnaces is close to 600 ten thousand yuan. The crystal silicon manufacturing cost obviously increases, and photovoltaic enterprise production receives the undulant influence of argon gas supply simultaneously. Therefore, the purification and recycling of the argon tail gas in the crystal pulling process are very necessary.
At present, the argon recovery method aiming at the field of monocrystalline silicon preparation is mainly based on the following two methods: 1) The catalytic oxidation method comprises the following steps: the method is characterized in that oxygen or air is added by utilizing a catalyst, carbon monoxide can be oxidized into carbon dioxide, hydrogen can be oxidized into water, hydrocarbons can be oxidized into carbon dioxide and water under a certain temperature condition, and then the impurities after oxidation are further removed by combining an adsorption method, deep cooling or a combined strategy. Zhouzhiyong et al, CN102583281B, CN103373716B, disclose a process for removing impurities such as carbon monoxide and hydrogen in argon by using an oxygen catalytic oxidation method, then add hydrogen to remove oxygen, and remove subsequent impurities such as carbon dioxide, water and hydrogen at low temperature by combining with an air separation device. The process for removing impurities in argon tail gas by using an oxygen catalytic oxidation method is also disclosed in patents CN107428532A, CN105939961B of Xinyue semiconductor corporation, and the core of the process is to detect the concentration of the impurities on line and then measure and supply oxygen for reaction without a subsequent oxygen removal process. However, this process lacks operability in practice. Although the catalytic oxidation method has the advantages of low reaction temperature, high efficiency and the like, the method inevitably needs an additional step of removing oxygen. Meanwhile, impurities such as nitrogen and the like can be effectively removed by utilizing an air separation technology, but the recovery rate of argon is reduced in the rectification separation process. The whole process flow of the catalytic oxidation method is complex, the number of matched facilities is large, and the overall one-time investment is high.
2) A method of chemical looping combustion. Using the oxidation state (M) of the metal oxide ox ) As an oxygen carrier, carbon monoxide is oxidized to carbon dioxide, hydrogen to water, and hydrocarbons to carbon dioxide and water at a certain temperature. The purpose of purifying argon is achieved by removing carbon dioxide and water in combination with the adsorption process. Reduced metal (M) after combustion R ) The oxygen carrying capacity is restored by oxygen/air oxidation, so that the next cycle is carried out. The main patent is US2012/0308462A1. The chemical-looping combustion technology does not need an additional deoxygenation process, is simple in process matching, but cannot overcome the problem of nitrogen accumulation in a long-term circulation process. The current argon recovery method and device disclosed in US2012/0308462A1 have the defects of large energy consumption, low argon recovery rate and the like in the operation process of equipment.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for purifying and recovering argon tail gas discharged in a monocrystalline silicon preparation process, which is economical, efficient and has industrial large-scale processing capacity, aiming at the requirement of large-scale purification and recovery of a monocrystalline silicon manufacturing factory; meanwhile, the invention provides a corresponding argon recovery device for a method for purifying and recovering argon.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for purifying and recovering tail gas discharged by argon in a monocrystalline silicon preparation process comprises the following steps:
a) Purification process, utilizationThe oxygen carrier adopts a chemical looping combustion method to remove impurities (CO, hydrogen and hydrocarbons (such as CH) in the argon tail gas 4 ) To carbon dioxide and water; then removing carbon dioxide and water in the argon tail gas by adopting an adsorbent;
b) The regeneration process specifically comprises the following steps:
b1 Utilizing mixed gas containing certain oxygen concentration to regenerate reduced oxygen carrier; and regenerating the adsorbent by using hot air;
b2 A cooling process, wherein the adsorbent is cooled by adopting a fan internal circulation mode;
b3 Replacing the air in the system by using clean argon through pressurization and decompression until the oxygen concentration is reduced to the required requirement.
In the purification process of a), the oxygen carrier mainly reacts with impurities in the argon tail gas in the manufacturing process of monocrystalline silicon, wherein the impurities in the argon tail gas are mainly carbon monoxide, a small amount of hydrogen and hydrocarbons, and the specific reaction principle is shown in equations (1), (2) and (3). After the reaction, all impurities are converted to carbon dioxide and water. The oxygen carrier used is mainly non-noble metal oxide, such as copper oxide, nickel oxide, iron oxide, manganese oxide, cobalt oxide, etc., see in particular chinese patent 201811425084.8. In the purification process of a), carbon dioxide and water in the argon tail gas impurities are mainly adsorbed by using an adsorbent. The adsorbent can be a molecular sieve or a mixture of a molecular sieve and alumina, wherein the alumina accounts for 10-20% of the total mass; as the molecular sieve, one or more kinds of 13X,4A, 5A or the like may be used.
(2n+m)M x O y +C n H 2m ＝(2 n +m)M x O y-1 +mH 2 O+nCO 2 (1)
CO+MO＝M+CO 2 (2)
H 2 +MO＝M+H 2 O (3)
When the oxygen carrier is consumed, the regeneration operation is required, and the regeneration process of b) mainly utilizes the oxygen carrier oxidized and reduced by the oxygen in the air to regenerate, and the reaction principle is shown as equation (4). In the regeneration process, because the reaction of the reduced oxygen carrier and oxygen belongs to exothermic reaction, the air can be diluted by inert gas according to the property of the oxygen carrier and the exothermic condition, so as to reduce the concentration of the oxygen, thereby avoiding the condition that the oxygen carrier is sintered under the condition of violent exothermic. The diluent gas used may be argon or more economically nitrogen. And in the regeneration process of the oxygen carrier, the adsorbent is heated at the same time to remove carbon dioxide and water in the adsorbent, so that the regeneration process of the oxygen carrier and the adsorbent is completed.
1/2O 2 +M＝MO (4)
A purification recovery unit that is arranged in above-mentioned monocrystalline silicon preparation technology to discharge argon tail gas, the device includes: a chemical looping combustion reactor (7) and a sorbent reactor (20); an argon gas source is connected with an air inlet of the chemical-looping combustion reactor (7) through a valve; an air source is connected with an air inlet of the chemical-looping combustion reactor (7) through a valve and an air cooling dryer (14); argon tail gas sequentially passes through a compressor (2) and a heat exchanger (5) and then is connected with an air inlet of a chemical-looping combustion reactor (7); an oxygen carrier is filled in the chemical looping combustion reactor (7), and an air outlet of the chemical looping combustion reactor (7) is connected with an air inlet of the adsorbent reactor (20) through a first pipeline (a) in sequence by a heat exchanger (5) and a first circulating water cooling device (16); the gas outlet of the chemical-looping combustion reactor (7) is connected with the gas inlet of the adsorbent reactor (20) through a second pipeline (b) by a valve; the adsorbent reactor (20) is filled with adsorbent, the air outlet of the adsorbent reactor (20) is connected with an argon storage device through a third pipeline (c) by a second circulating water cooling device (21) through a valve, is emptied through a fourth pipeline (d) through the valve, and is connected with the air inlet of the adsorbent reactor (20) through a fifth pipeline (e) through a valve and a circulating fan (27).
The reactor in the purification device is provided with a chemical-looping combustion reactor and an adsorbent reactor, and adopts an internal heating mode for heat supply, namely, an electric heating element (one or more than two of an electric heating rod, an electric heating wire, an electric heating belt and an electric heating block) is arranged in the reactor for supplying heat to the oxygen carrier or the adsorbent in the reactor. Because the oxygen carrier and the adsorbent are generally poor thermal conductors, the internal heating mode is adopted to facilitate rapid heating to the required temperature, and the energy consumption is reduced. Argon tail gas passes through the heat exchanger and the auxiliary heating device before entering the chemical-looping combustion reactor, so that energy consumption can be effectively saved, and the reaction temperature of the upper bed layer of the chemical-looping combustion reactor can be guaranteed. In the purification process, after the argon tail gas is purified as shown in the attached figure 1, the carbon dioxide concentration at the outlet is less than 1ppm. According to the properties of the oxygen carrier, in particular to the patent 201811425084.8, the working temperature range of the chemical looping combustion reactor is 150-400 ℃; in order to ensure the effect of the adsorbent, during the purification process, the working temperature range of the adsorption reactor (2) is less than 100 ℃, and preferably 20-50 ℃; the outlet pressure is greater than or equal to 0.3MPa, preferably 0.5MPa;
when the oxygen carrier is consumed, the purification device is switched to a regeneration process, the fifth valve (12), the sixth valve (13), the fourth valve (10), the third valve (9), the ninth valve (19), the tenth valve (22) and the fourteenth valve (28) are opened, and the rest valves are in a closed state. Depending on the nature of the reaction of the oxygen carrier, mainly the severity of the exotherm during the reaction, the oxygen carrier and the adsorbent can be regenerated with air or air diluted with an inert gas, for example argon or nitrogen. Wherein the volume concentration range of the oxygen is 0.1-21%. In the regeneration process, the working temperature range of the chemical-looping combustion reactor (7) is 150-300 ℃; the working temperature of the adsorption reactor (2) is 150-300 ℃, and the hot air flow is 10-30 m 3 H is used as the reference value. The regeneration process can be finished when the concentration of the carbon dioxide in the hot air is reduced to 600 ppm.
And after the regeneration process is finished, the temperature reduction process of the adsorbent is carried out, the tenth valve (22), the thirteenth valve (26) and the eighth valve (18) are opened, and the rest valves are in a closed state. And starting a fan (27), performing circulating cold blowing on the adsorbent by using the residual gas in the system, and cooling to a temperature lower than 100 ℃ in the adsorbent bed. The gas flow of the fan can be maintained at 10-40 m according to the amount of different adsorbents filled 3 /h。
When the temperature of the adsorbent is reduced to be below 100 ℃, the purification device performs the operation of the replacement process, opens the fifth valve (12), the fourth valve (10), the third valve (9), the seventh valve (17), the second valve (4), the tenth valve (19), the twelfth valve (23), and closes the other valves. In order to ensure the replacement effect, the system pressure is at least more than or equal to 0.3MPa, preferably 0.6MPa, then the fourteenth valve (28) is opened to release the pressure to 0.12-0.15 MPa, preferably 0.12-0.13 MPa, and the operation is repeated until the oxygen at the air outlet of the adsorbent reactor (20) is reduced to 0.5-2 ppm.
The device adopts an one-on one-standby mode to operate under the actual working condition, namely, when one set of device purifies the argon tail gas of the single crystal furnace, the other set of device is regenerated.
The device also comprises a set of automatic control system for the device, wherein the control system is respectively connected with the valves, the gas mass flow controllers, the cooling water circulating pump, the gas compressor, the electric heating element, the air cooling and drying machine and the fan in the device by control signals; temperature sensors are arranged in the chemical looping combustion reactor and the adsorbent reactor, and a control system is in signal connection with the temperature sensors and the oxygen analyzer.
The device has the advantages of low energy consumption and high argon recovery rate.
The beneficial effects of the invention are:
the invention adopts the chemical chain combustion principle to remove the argon tail gas impurities in the monocrystalline silicon manufacturing process, and the carbon dioxide and water are removed in combination with the adsorption process, so that the matched process flow is simple;
the invention adopts an internal heating mode, can quickly heat required media (oxygen carrier and adsorbent) and has the advantage of low energy consumption;
the gas is preheated by adopting the heat exchanger and the auxiliary heating device, so that the temperature of the gas inlet can be effectively ensured, and the reaction effect of the oxygen carrier at a lower temperature is ensured;
the invention adopts the mode of internal circulation of the fan to cool the adsorbent, can efficiently and quickly cool the adsorbent, shortens the time of the regeneration process and reduces the energy consumption and the gas consumption in the cooling process.
Drawings
FIG. 1 is a flow diagram of a preferred embodiment of the present invention, wherein the various components are illustrated as follows: 1,4,9, 10, 12, 13, 17, 18, 19, 22, 23, 25, 26, 28-first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, tenth, eleventh, twelfth, thirteenth, fourteenth (electrically or pneumatically controlled) valve; 3, 11, 15, 24-first, second, third, and fourth gas mass flow controllers (e.g., gas mass flow meters with controllers); 16 21 is a first circulating water-cooling temperature-reducing device and a second circulating water-cooling temperature-reducing device (such as a circulating water cooler, a cooling pipeline with a circulating water cooling jacket, or a cooling pipeline with a circulating water cooling coil); 2-a gas compressor; 5-a heat exchanger; 6-heating belt (auxiliary heating device); 7-oxygen carrier reactor (chemical chain combustion reactor), 8' -first, second heat preservation cover (heat preservation jacket set on the outer wall surface); 14-air cooling and drying machine; 20-an adsorbent reactor; 27-a fan; 29-oxygen analyzer; a, b, c, d, e-are respectively a first pipeline, a second pipeline, a third pipeline, a fourth pipeline and a fifth pipeline
FIG. 2 shows the preferred result of the cooling process of the present invention. Description of the drawings: it can be seen from the temperature drop curves of the adsorbent reactor detected by different temperature probes that the middle bed course temperature of the adsorbent can be reduced to below 100 ℃ within 120min, and the bottom bed course temperature can be reduced to 100 ℃ within 250 min. This substantially meets the handover requirements.
FIG. 3 shows the preferred result of the permutation procedure of the present invention.
FIG. 4 shows the preferred results of the present invention before and after argon off-gas cleanup. Before purification, the content of carbon monoxide impurities in the argon tail gas is (upper); the content of carbon dioxide impurities in the purified argon tail gas is lower.
Table 1 average energy consumption monitoring of the purification plant.
Detailed Description
The following method and apparatus for purifying and recovering argon off-gas discharged from the single crystal silicon production process are further described in detail by way of examples:
working condition: the argon flow of a single crystal furnace is 60-80L/min, the oxygen carrier dosage of the chemical chain combustion reactor is 10-15 Kg, the adsorbent dosage is 30-40 Kg, and at most, one purifying device can simultaneously treat the argon tail gas of 4 single crystal furnaces at present. The specific embodiment is as follows: the composition of oxygen carrier filled in chemical chain combustion is shown in ChinaInventive application patent application 201811425084.8 example 4, specifically, the content of CuO is 30.5wt%, zrO 2 2 The content of (A) was 1.3% by weight, and the content of Pd was 0.03% by weight.
The adsorbent filled in the adsorbent reactor is a molecular sieve 13X.
A purification recovery unit that is arranged in above-mentioned monocrystalline silicon preparation technology to discharge argon tail gas, the device includes: a chemical looping combustion reactor 7 and a sorbent reactor 20; an argon gas source is connected with an air inlet of the chemical-looping combustion reactor 7 through a valve; an air source is connected with an air inlet of the chemical looping combustion reactor 7 through a valve and an air cooling dryer 14; the argon tail gas sequentially passes through a compressor 2 and a heat exchanger 5 and then is connected with an air inlet of a chemical looping combustion reactor 7; an oxygen carrier is filled in the chemical looping combustion reactor 7, and an air outlet of the chemical looping combustion reactor 7 is connected with an air inlet of the adsorbent reactor 20 through a first pipeline a, a heat exchanger 5 and a first circulating water cooling device 16 in sequence; the gas outlet of the chemical-looping combustion reactor 7 is connected with the gas inlet of the adsorbent reactor 20 through a second pipeline b by a valve; the adsorbent reactor 20 is filled with adsorbent, the gas outlet of the adsorbent reactor 20 is connected with the argon storage device through the second circulating water cooling device 21, the third pipeline c and the valve, the fourth pipeline d and the valve are used for emptying, and the fifth pipeline e and the valve are used for connecting the gas inlet of the adsorbent reactor 20 through the circulating fan 27.
Example 1, purification plant preparation procedure: heating the chemical looping combustion reactor (7) to 270 ℃, heating the adsorbent reactor (20) to 250 ℃, opening the fifth valve (12), the fourth valve (10), the third valve (9), the ninth valve (19), the eleventh valve (23), the twelfth valve (25), and closing the rest valves. And adjusting an argon flow meter to 11-10L/min, keeping for 5h, and removing impurities of the oxygen carrier and the adsorbent. Cooling process: the tenth valve (22), the thirteenth valve (26), the eighth valve (18) are opened, and the remaining valves are closed. And starting a fan (27) and a second circulating water cooling device (21) to cool the adsorbent in the adsorbent reactor (20), wherein a specific cooling curve refers to the attached figure 2.
And (3) a replacement process, namely opening a fifth valve (12), a fourth valve (10), a third valve (9), a second valve (4), a seventh valve (17), a ninth valve (19) and an eleventh valve (23), closing the other valves, adjusting the flow meter to 11-80L/min, boosting the pressure to 5bar, and stabilizing for 5min. The third valve (9) is closed, and the fourteenth valve (28) is opened to release the pressure to 1.3bar. The above operation was repeated until the oxygen analyzer showed an oxygen content below 1ppm. The results of the specific number of replacements and oxygen content are shown in FIG. 3.
A purification process: opening the first valve (1), the second valve (4), the seventh valve (17), the eleventh valve (23) and the twelfth valve (25). Turning on the compressor (2), and turning on the first and second circulating condensed water cooling devices (16) and (21); adjusting the inlet pressure to 5bar, opening the first flowmeter (3) to the required flow, controlling the outlet pressure of the adsorbent reactor to be not lower than 0.5MPa, and closing the rest valves. The impurity content of the argon tail gas and the purified impurity content are shown in figure 4.
Example 2, regeneration scheme: and opening the fifth valve (12), the sixth valve (13), the fourth valve (10), the third valve (9), the ninth valve (19), the tenth valve (22) and the fourteenth valve (28), and closing the rest valves. The second gas mass flow meter (11) is adjusted to 50L/min. And adjusting the third gas mass flow meter (15) to 10L/min, starting an air cooling dryer (14), cooling the second circulating condensed water by a cooling device (21), heating the adsorbent reactor (20) to 250 ℃, and keeping the temperature for 2h. And then closing the second gas mass flow meter (11), adjusting the third gas mass flow meter (15) to 100L/min, keeping for 2h, and ending the regeneration process. And repeating the cooling process and the replacement process in the subsequent process.
Example 3: the specific comparison results of the overall energy consumption monitoring after 152h of reactor operation are shown in table 1.
TABLE 1 average energy consumption monitoring of a purification plant
Description of the drawings: the purification plant was operated for 152h with 10 switching operations, and it was checked that the average energy consumption during the operation of the plant was about 4.5kW/h. Without a purging device, about 547m of argon gas is required 3 And use the medicineAfter the device, only 47m of argon gas is needed 3 。
It will be readily understood by those skilled in the art that the present invention may be combined or modified without departing from the spirit of the materials and methods disclosed in the foregoing description, and such modifications are intended to be included within the scope of the present invention. Accordingly, the particular embodiments specifically described above are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.
Claims (10)
1. A method for purifying and recovering tail gas discharged by argon in a monocrystalline silicon preparation process comprises the following steps:
a) The purification process comprises the steps of converting impurities such as CO, hydrogen and hydrocarbons in the argon tail gas into carbon dioxide and water by using an oxygen carrier through a chemical looping combustion method; then removing carbon dioxide and water in the argon tail gas by adopting an adsorbent;
b) The regeneration process specifically comprises the following steps:
b1 Air diluted with air or inert gas) regenerates the reduced oxygen carrier; and regenerating the adsorbent by using hot air;
b2 A cooling process, wherein the adsorbent is cooled by adopting a fan internal circulation mode;
b3 Replacement process, replacing air in the system by clean argon through pressurization and decompression until the oxygen concentration is reduced to the required requirement;
the oxygen carrier in the step a) is a metal oxide, the oxygen carrier comprises AxByCz, wherein A is at least one non-noble metal transition metal oxide, B is a VIIIB group metal or an oxide thereof, and C metal is selected from one or more of La, zr and Ce; the carrier is one or more of alumina, silica, zirconia, titania, magnesia or a silicon-aluminum molecular sieve; based on the mixed metal oxide and an oxygen carrier, the content X of the metal oxide A in the oxygen carrier is 1-65wt%, the content y of the metal B in the oxygen carrier is 0.001-10 wt%, and the content z of the metal oxide C in the oxygen carrier is 0.1-10 wt%; the rest is a carrier;
the preparation method of the oxygen carrier comprises the following steps:
(a) Preparing one or more soluble metal salts required by the oxygen carrier AxByCz into a solution, impregnating the solution on the carrier, drying and roasting the carrier;
(b) Drying, wherein the drying temperature is 80 to 120 ℃, and the drying time is 4 to 6h;
(c) Roasting: the baking temperature is 300 to 800 ℃; the roasting time is 2 to 10 hours;
the adsorbent is a molecular sieve or a mixture of the molecular sieve and alumina, wherein the alumina accounts for 10 to 20 percent of the total mass; the molecular sieve is selected from 13X,4A or 5A.
2. The purification and recovery method of the tail gas discharged from the monocrystalline silicon preparation process according to claim 1, characterized in that: the inert gas in the step b 1) refers to one or two of argon or nitrogen, wherein the volume of oxygen is 0.1-21%; the air refers to anhydrous air subjected to water removal by the cold dryer.
3. A purification and recovery device for discharging argon tail gas in the monocrystalline silicon preparation process of any one of claims 1-2, which is characterized in that: the device comprises: a chemical looping combustion reactor (7) and a sorbent reactor (20); an argon gas source is connected with an air inlet of the chemical-looping combustion reactor (7) through a valve; an air source is connected with an air inlet of the chemical-looping combustion reactor (7) through a valve and an air cooling dryer (14); argon tail gas sequentially passes through a compressor (2) and a heat exchanger (5) and then is connected with an air inlet of a chemical-looping combustion reactor (7); an oxygen carrier is filled in the chemical looping combustion reactor (7), and an air outlet of the chemical looping combustion reactor (7) is sequentially connected with the heat exchanger (5) and the first circulating water cooling device (16) through a first pipeline (a) and then is connected with an air inlet of the adsorbent reactor (20); the gas outlet of the chemical-looping combustion reactor (7) is connected with the gas inlet of the adsorbent reactor (20) through a second pipeline (b) and a valve; an adsorbent is filled in the adsorbent reactor (20), and an air outlet of the adsorbent reactor (20) is connected with an argon storage device through a third pipeline (c) by a valve through a second circulating water cooling device (21); emptying through a fourth pipeline (d) through a valve; is connected with the air inlet of the adsorbent reactor (20) through a fifth pipeline (e) and a circulating fan (27) through a valve.
4. The purification and recovery device for the tail gas discharged by the monocrystalline silicon preparation process according to claim 3, characterized in that: the working temperature of the chemical-looping combustion reactor (7) in the step a) is 150-400 ℃; the working temperature range of the adsorption reactor (2) is less than 100 ℃; the outlet pressure is more than or equal to 0.3MPa;
the working temperature interval of the chemical-looping combustion reactor (7) in the step b 1) is 150 to 300 ℃; the working temperature range of the adsorption reactor (20) is 150 to 300 ℃, and the hot air flow is 10 to 30m 3 H, ending the regeneration process until the concentration of carbon dioxide in the hot air is not more than 600 ppm;
in the b 2) cooling process, the gas in the pipeline is circulated by a fan (27) among the adsorbent reactor (20), the second circulating water cooling device (21), the fan (27) and the fifth pipeline (e) to cool the adsorbent, and the flow rate of the gas circulated by the fan is 10 to 40m 3 /h；
In the replacement process of b 3), boosting the pressure of the reaction device by using clean argon, wherein the system pressure is more than or equal to 0.3MPa, then decompressing to 0.12 to 0.15MPa, and repeatedly operating until the oxygen at the air outlet of the adsorbent reactor (20) is reduced to 0.5 to 2ppm.
5. The purification and recovery device for the tail gas discharged by the monocrystalline silicon preparation process according to claim 3, characterized in that: the working temperature range of the adsorption reactor (2) is 20 to 50 o C; the outlet pressure is 0.5MPa;
in the replacement process of b 3), boosting the pressure of the reaction device by using clean argon, wherein the system pressure is 0.6MPa, then decompressing to 0.12-0.13MPa, and repeatedly operating until the oxygen at the air outlet of the adsorbent reactor (20) is reduced to 0.5-2ppm.
6. The purification and recovery device for the tail gas discharged by the monocrystalline silicon preparation process according to claim 3, characterized in that: the chemical looping combustion reactor (7) and the adsorbent reactor (20) adopt an internal heating mode for heat supply, an electric heating element is arranged in the reactor for supplying heat to oxygen carriers or adsorbents in the reactor, and the electric heating element is one or more than two of an electric heating rod, an electric heating wire, an electric heating belt and an electric heating block.
7. The purification and recovery device for the tail gas discharged by the monocrystalline silicon preparation process according to claim 3, characterized in that: an auxiliary heating device (6) is arranged on a pipeline connecting the argon tail gas with the gas inlet of the chemical-looping combustion reactor (7) after passing through the heat exchanger (5);
in the purification process a 1), argon tail gas enters a chemical-looping combustion reactor (7) after being preheated by a heat exchanger (5) and an auxiliary heating device (6);
in the regeneration scheme b 1), the hot gas from the chemical looping combustion reactor (7) enters the sorbent reactor (20) through a valve via a second line (b).
8. The purification and recovery device for the tail gas discharged by the monocrystalline silicon preparation process according to claim 3, characterized in that: an oxygen analyzer (29) is arranged on a connecting pipeline between the gas outlet of the adsorbent reactor (20) and the argon storage device; the outer wall surface of the chemical looping combustion reactor (7) is provided with a first heat preservation sleeve (8), and the outer wall surface of the adsorbent reactor (20) is provided with a second heat preservation sleeve (8').
9. The purification and recovery device for the tail gas discharged from the process of manufacturing single crystal silicon according to any one of claims 3 to 8, wherein: the device comprises two sets of purification and recovery devices for discharging argon tail gas in the monocrystalline silicon preparation process according to any one of claims 3 to 7, the purification and recovery devices operate in a one-on one-standby mode, and one set of the purification and recovery devices is used for purifying the argon tail gas of the monocrystalline furnace, and the other purification and recovery device is used for regenerating.
10. The purification and recovery device for the tail gas discharged from the process of manufacturing single crystal silicon according to any one of claims 3 to 8, wherein: the device also comprises a set of automatic control system for the device, wherein the control system is respectively connected with the valves, the gas mass flow controllers, the cooling water circulating pump, the gas compressor, the electric heating element, the air cooling and drying machine and the fan in the device in a signal mode; temperature sensors are arranged in the chemical looping combustion reactor and the adsorbent reactor, and a control system is in signal connection with the temperature sensors and the oxygen analyzer.
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| CN109539284A (en) * | 2018-11-27 | 2019-03-29 | 中国科学院大连化学物理研究所 | It is a kind of for the oxygen carrier of inert gas purification and its preparation and application |
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| CN109539284A (en) * | 2018-11-27 | 2019-03-29 | 中国科学院大连化学物理研究所 | It is a kind of for the oxygen carrier of inert gas purification and its preparation and application |
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