Gas recovery system and hydrogen ammonia recovery device

Abstract

The invention discloses a gas recovery system and a hydrogen ammonia recovery device thereof. The gas recovery system comprises a semiconductor processing device, the semiconductor processing device comprises a tail gas discharging pipeline, tail gas discharged by the tail gas discharging pipeline is mixed gas containing ammonia gas and hydrogen, and the volume fraction of the ammonia gas and the hydrogen in the tail gas is larger than 20%; the hydrogen ammonia recovery device comprises an electrochemical module, the electrochemical module comprises an exchange membrane, a first anode membrane and a first cathode membrane, the exchange membrane comprises a first side and a second side which are opposite, the first anode membrane is located on the first side, the first cathode membrane is located on the second side, and the first cathode membrane is located on the second side. The tail gas exhaust pipeline is communicated with the first anode film, a driving circuit is arranged between the first anode film and the first cathode film, and the driving circuit is used for applying a first driving voltage between the first anode film and the first cathode film so as to recover mixed gas of hydrogen and ammonia gas at the second side. The system can recover hydrogen and ammonia gas, and is low in energy consumption.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of semiconductor, in particular to a gas recovery system and hydrogen ammonia recovery device. BACKGROUND

[0002] Hydrogen and ammonia are widely used in the semiconductor industry, and at present, a large amount of waste gas is often generated in semiconductor devices, and the waste gas includes a large amount of hydrogen and ammonia. If the waste gas is directly discharged into the atmosphere, it will not only pollute the environment, but also waste a large amount of hydrogen and ammonia. Therefore, there is an urgent need for a new gas recovery system to recover the hydrogen and ammonia with low energy consumption. SUMMARY

[0003] The purpose of the present application is to provide a gas recovery system and hydrogen ammonia recovery device to recover the mixed gas of hydrogen and ammonia with low energy consumption.

[0004] To achieve the above purpose, the present application provides a gas recovery system, comprising: a semiconductor processing device including a tail gas discharge pipeline, the tail gas discharged by the tail gas discharge pipeline being a mixed gas containing ammonia and hydrogen, the volume fraction of ammonia and hydrogen in the tail gas being greater than 20%; a hydrogen ammonia recovery device including an electrochemical module, the electrochemical module including an exchange film, a first anode film and a first cathode film, the exchange film including opposite first and second sides, the first anode film being located on the first side, the first cathode film being located on the second side, the tail gas discharge pipeline being in communication with the first anode film, a driving circuit being provided between the first anode film and the first cathode film, the driving circuit being used to apply a first driving voltage between the first anode film and the first cathode film to recover the mixed gas of hydrogen and ammonia on the second side.

[0005] Optionally, the semiconductor processing device is a metal organic chemical vapor deposition device, and the tail gas further contains silane, nitrogen and trimethyl gallium gas.

[0006] Optionally, a pretreatment device is further provided between the semiconductor processing device and the hydrogen ammonia recovery device to remove the silane and trimethyl gallium gas.

[0007] Optionally, the hydrogen ammonia recovery device further includes: a total gas delivery pipeline and a plurality of branch gas delivery pipelines, two ends of the total gas delivery pipeline being respectively connected with the pretreatment device and one end of each branch gas delivery pipeline, the other end of the branch gas delivery pipeline being in communication with the electrochemical module, so that the mixed gas in the branch gas delivery pipeline is delivered to the first anode film.

[0008] Optionally, a plurality of branch delivery pipelines are respectively connected with at least two electrochemical modules, and the at least two electrochemical modules are connected in parallel with each other.

[0009] Optionally, the hydrogen-ammonia recovery device further comprises: a humidifier, which is connected to the pretreatment device and the total gas delivery pipeline respectively, for humidifying the mixed gas; a separation device, which is connected to the first cathode membrane through a gas delivery pipeline, for separating the hydrogen and ammonia; a hydrogen dryer, for drying the recovered hydrogen; a hydrogen storage container, which is connected to the hydrogen dryer, for stabilizing and storing the dried hydrogen; an ammonia dryer, for drying the recovered ammonia; and an ammonia storage container, which is connected to the ammonia dryer, for stabilizing and storing the dried ammonia.

[0010] Optionally, the separation device is a hydrogen electrochemical module, which comprises a proton exchange membrane, a second anode membrane and a second cathode membrane, the proton exchange membrane comprises opposite third and fourth sides, the second anode membrane is located on the third side, the second cathode membrane is located on the fourth side, the first cathode membrane is connected to the second anode membrane, a driving circuit is arranged between the second anode membrane and the second cathode membrane, the driving circuit is used for applying a second driving voltage between the second anode membrane and the second cathode membrane to recover hydrogen on the fourth side, and the second cathode membrane is connected to the hydrogen dryer.

[0011] Optionally, the separation device is a solution pool, the ammonia is dissolved in the solution, and the hydrogen is not dissolved in the solution, and the solution pool is connected to the hydrogen dryer.

[0012] Optionally, the solution pool is connected to an ammonia recovery device for recovering the ammonia in the solution, and the ammonia recovery device is connected to the ammonia dryer.

[0013] Optionally, the electrochemical module comprises a primary electrochemical module and a secondary electrochemical module connected in series, the branch gas delivery pipeline is connected to the first side of the primary electrochemical module, part of the hydrogen and ammonia is recovered to the second side of the primary electrochemical module, the remaining mixed gas reaches the first side of the secondary electrochemical module from the first side of the primary electrochemical module, and part of the hydrogen and ammonia is recovered to the second side of the secondary electrochemical module.

[0014] Optionally, the device further comprises a post-treatment device, which is connected to the first side of the hydrogen-ammonia recovery device through a remaining gas pipeline, for post-treating the remaining mixed gas, and the post-treatment device is a combustion device.

[0015] Optionally, the device further comprises a valve for controlling the opening and closing of the remaining gas delivery pipeline.

[0016] Optionally, the first driving voltage is less than 0.7 volts.

[0017] Correspondingly, the application also provides a hydrogen-ammonia recovery device, comprising: an outer cavity; an electrochemical module arranged in the outer cavity, comprising an exchange film, a first anode film and a first cathode film, the exchange film comprising opposite first and second sides, the first anode film being located on the first side and the first cathode film being located on the second side, for dividing the outer cavity into a mixed gas passage located on the first side and a hydrogen-ammonia passage located on the second side, the mixed gas passage being in communication with a tail gas discharge pipeline, and the mixed gas passage making the transmission path of the mixed gas non-linear.

[0018] Optionally, the hydrogen-ammonia recovery device comprises a plurality of hydrogen-ammonia recovery units, each of which comprises the outer cavity and the electrochemical module; each recovery unit further comprises: an inner cavity located inside the outer cavity, the bottom of the inner cavity being provided with an opening, the side wall of the inner cavity being formed by the electrochemical module, and the inner side wall of the inner cavity being the first cathode film; the gap between the outer cavity and the inner cavity constitutes the mixed gas passage, and the inner cavity constitutes the hydrogen-ammonia passage.

[0019] Optionally, one electrochemical module constitutes a partition plate, a plurality of parallelly arranged partition plates being located in one outer cavity, the inner side wall of the gas passage being the first anode film constituting the mixed gas passage, and the inner side wall of the gas passage being the first cathode film constituting the hydrogen-ammonia passage.

[0020] Optionally, the hydrogen-ammonia recovery device comprises a plurality of hydrogen-ammonia recovery units, each of which comprises the electrochemical module and the outer cavity.

[0021] Optionally, it further comprises: a flow guide vane arranged on the inner side wall of the mixed gas passage, for making the mixed gas containing hydrogen and ammonia curve in the mixed gas passage.

[0022] Optionally, the inner diameter of the mixed gas passage is different in the flow direction of the mixed gas.

[0023] Optionally, the exchange film is an ammoniated treatment film; the treatment film comprises: a phenolic resin sulfonic acid type film, a polystyrene sulfonic acid type film, a polytrifluorostyrene sulfonic acid type film, a perfluorosulfonic acid type film or a composite film composed of a perfluorosulfonic acid type film and polytetrafluoroethylene; the materials of the first anode film and the first cathode film are: nickel-molybdenum, nickel-ruthenium alloy, cobalt, chromium, iron-doped nickel-molybdenum or nickel-ruthenium alloy; it further comprises: diffusion layers located on the first and second sides, the mixed gas containing hydrogen and ammonia passing through the diffusion layers, the first anode layer, the exchange film, the first cathode layer and the diffusion layers in sequence.

[0024] Optionally, the material of the diffusion layer comprises: a carbon body and polytetrafluoroethylene wrapped on the surface of the carbon body.

[0025] Compared with the prior art, the technical scheme of the present application has at least the following beneficial effects:

[0026] The gas recovery system provided by the present application, the tail gas discharged from the tail gas discharge pipeline of the semiconductor processing device contains a large amount of hydrogen and ammonia, the hydrogen and ammonia are transported to the first anode membrane of the hydrogen-ammonia recovery device, the hydrogen is ionized into hydrogen ions, the hydrogen ions combine with the ammonia to form ammonium ions, a driving circuit is arranged between the first anode membrane and the first cathode membrane, a first driving voltage is arranged between the first anode membrane and the first cathode membrane by the driving circuit, the first driving voltage drives the ammonium ions to pass through the exchange membrane to the first cathode membrane, the ammonium ions are decomposed into ammonia and hydrogen ions near the first cathode membrane, and the hydrogen ions combine with electrons to form hydrogen. That is, the recovery of hydrogen and ammonia is realized on the second side of the exchange membrane. And other components in the tail gas are difficult to pass through the exchange membrane and stay on the first side of the exchange membrane. Moreover, the first driving voltage of the driving circuit is small, so that the ammonium ions can pass through the exchange membrane to the second side, and therefore, the energy consumption of hydrogen and ammonia recovery is low. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The figure is a structural schematic diagram of a gas recovery system of the present application;

[0028] Figure 2 The figure is a structural schematic diagram of another gas recovery system of the present application;

[0029] Figure 3 The figure is a structural schematic diagram of still another gas recovery system of the present application;

[0030] Figure 4 The figure is a structural schematic diagram of a flow path of a mixed gas in a hydrogen-ammonia recovery device of the present application;

[0031] Figure 5 The figure is a structural schematic diagram of a flow path of another mixed gas in a hydrogen-ammonia recovery device of the present application;

[0032] Figure 6 The figure is a structural schematic diagram of a flow path of still another mixed gas in a hydrogen-ammonia recovery device of the present application;

[0033] Figure 7 The figure is a structural schematic diagram of still another gas recovery system of the present application;

[0034] Figure 8 The figure is a structural schematic diagram of a mixed gas channel of the present application;

[0035] Figure 9 The figure is a structural schematic diagram of another mixed gas channel of the present application. DETAILED DESCRIPTION

[0036] The technical solutions, structural features, achieved objectives and effects of the embodiments of the present application will be described in detail below. Figure 1 ~Appendix Figure 9 The technical solutions, structural features, achieved objectives and effects of the embodiments of the present application will be described in detail below.

[0037] It should be noted that the drawings are greatly simplified and all use non-precise proportions, only to facilitate, clear and assist in the purpose of explaining the embodiments of the present application, and not to limit the defined conditions of the present application, so it does not have the technical significance, any modification of the structure, change of the proportion relationship or adjustment of the size, without affecting the effects and purposes of the present application, should still fall within the scope of the disclosed technical content.

[0038] It should be noted that in the present application, the relationship terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between the entities or operations. Moreover, the terms "include", "contain" or any other variants thereof are intended to cover non-exclusive inclusion, so that the process, method, article or equipment including a series of elements not only includes the explicitly listed elements, but also includes other elements not explicitly listed, or includes the elements inherent in such process, method, article or equipment.

[0039] As described in the background, the existing gas recovery system has high energy consumption. To solve this technical problem, the present application provides a gas recovery system and a hydrogen ammonia recovery device thereof. The hydrogen and ammonia are recovered by the electrochemical module in the hydrogen ammonia recovery device, and the energy consumption is low. The detailed description is as follows:

[0040] Figure 1 The structure of the present application is shown in the structure diagram of the gas recovery system.

[0041] Please refer to Figure 1The gas recovery system 1 comprises: a semiconductor processing device 10, which comprises an exhaust pipe 101, the exhaust gas discharged from the exhaust pipe 101 being a mixed gas containing hydrogen and ammonia; and a hydrogen-ammonia recovery device 11, which comprises an electrochemical module 111, the electrochemical module 111 comprising an exchange membrane 111a, a first anode membrane 111b, and a first cathode membrane 111c, the exchange membrane 111a comprising a first side A and a second side B opposite to each other, the first anode membrane 111b being located on the first side A, and the first cathode membrane 111c being located on the second side B, the exhaust pipe 101 facing the first anode membrane 111b, so that the mixed gas is delivered to the first anode membrane 111b. Since a driving circuit is arranged between the first anode membrane 111b and the first cathode membrane 111c, the driving circuit is used to apply a first driving voltage 111d between the first anode membrane 111b and the first cathode membrane 111c, so that hydrogen and ammonia are recovered on the second side B.

[0042] The exhaust gas discharged from the exhaust pipe 101 of the semiconductor processing device 10 contains a large amount of hydrogen and ammonia, specifically, the volume fraction of hydrogen and ammonia in the exhaust gas is greater than 20%, if directly discharged into the atmospheric environment, not only the environment is affected, but also the hydrogen and ammonia are wasted, and the hydrogen-ammonia recovery device 11 is used to recover the hydrogen and ammonia in the exhaust gas discharged from the semiconductor processing device 10.

[0043] The hydrogen-ammonia recovery device 11 comprises an electrochemical module 111, the electrochemical module 111 comprising: an exchange membrane 111a, which is a thin film with a thickness of 5um-180um. It provides a channel for ion transmission, and at the same time separates the first anode membrane 111b and the first cathode membrane 11c as a diaphragm, and has the functions of diaphragm and electrolyte, only allowing ammonium ions to pass through, and not allowing molecules and other ions to pass through. The following membranes are usually ammoniated and used as the material of the exchange membrane 111a: phenolic resin sulfonic acid type membrane, polystyrene sulfonic acid type membrane, polytrifluorostyrene sulfonic acid type membrane, and perfluorosulfonic acid type membrane, preferably a composite membrane composed of perfluorosulfonic acid type membrane and polytetrafluoroethylene, wherein polytetrafluoroethylene is a microporous medium for reinforcement, and perfluorosulfonic acid material forms a proton transmission channel in the micropore. The ammoniated membrane only allows ammonium ions to pass through, and other ions or gases are difficult to pass through the exchange membrane 111a and stay on the first side A.

[0044] The electrochemical module 111 further comprises the first anode film 111b on the first side A of the exchange film 111a and the first cathode film 111c on the second side B of the exchange film 111a; in consideration of the conductivity, corrosion resistance and cost saving, the first anode film 111b and the first cathode film 111c are usually made of nickel-molybdenum, nickel-ruthenium alloy, cobalt, chromium, iron-doped nickel-molybdenum or nickel-ruthenium alloy, which has very good catalytic ability for oxidation and reduction of hydrogen and ammonia.

[0045] In the embodiment, the electrochemical module 111 further comprises the diffusion film 111d on both sides of the first anode film 111b and the first cathode film 111c, the diffusion film 111d is made of carbon paper or carbon cloth treated with polytetrafluoroethylene and carbon black, and has a thickness of about 0.1-0.4 mm. In the diffusion layer, the macropores covered by polytetrafluoroethylene are hydrophobic pores, and the uncovered pores are hydrophilic pores. Since no water is generated in the process of hydrogen purification and recovery, reducing the amount of polytetrafluoroethylene with strong drainage in the diffusion layer is beneficial to improve the conductivity of the diffusion layer 111d and reduce the resistance.

[0046] The hydrogen-ammonia recovery device 11 can purify hydrogen and ammonia by the principle that hydrogen is ionized into hydrogen ions and electrons near the exchange film 111a, the hydrogen ions combine with ammonia to form ammonium ions, the ammonium ions pass through the exchange film 111a under the driving of the driving circuit, and the electrons pass through the driving circuit to the second side B of the exchange film 111a, the ammonium ions are decomposed into ammonia and hydrogen ions on the second side B, and the hydrogen ions and the electrons on the side combine to form hydrogen. The main chemical reactions are as follows:

[0047] First anode film side: H2→2H + +2e -

[0048] 2NH3+2H + →2NH4 +

[0049] First cathode film side: 2NH4 + →2NH3+2H +

[0050] 2H + +2e→H2

[0051] Other gases are difficult to pass through the exchange membrane 111a, and thus stay on the first side A, only ammonium ions pass through the exchange membrane 111a, and purified hydrogen and ammonia are obtained on the second side B.

[0052] In the embodiment, the first driving voltage of the driving current is less than 0.7 volt, the first driving voltage can be less than 0.5 volt, and the first driving voltage can be less than 0.3 volt. It can be seen that the first driving voltage is small, i.e., only a small first driving voltage between the first anode film 111b and the first cathode film 111c is needed to enable ammonium ions to pass through the exchange membrane 111a. Because the first driving voltage is small, the driving circuit generates less heat, and the flow of the mixed gas containing hydrogen and ammonia is large, the mixed gas containing hydrogen and ammonia can take away part of the heat, so that the hydrogen-ammonia recovery device 11 is not easy to accumulate heat, and thus the hydrogen-ammonia recovery device can reduce the heat dissipation requirement of the heat dissipation device, and even the heat dissipation device can not be provided.

[0053] In addition, because the diffusion films 111d on both sides of the first anode film 111b and the first cathode film 111c are used for hydrogen and ammonia components, the pore size of the diffusion film 111d on the side of the first cathode film 111c can be the same as the pore size of the diffusion film on the side of the first anode film 111b.

[0054] Figure 2 Structure diagram of another gas recovery system of the present application.

[0055] Please refer to Figure 2 The gas recovery system 2 includes a semiconductor processing device 20, which includes a process gas delivery pipeline 201 for providing process gas into a reaction chamber of the semiconductor processing device 20, and an exhaust pipeline 202 for discharging exhaust gas, which is a mixed gas containing hydrogen and ammonia. The hydrogen-ammonia recovery device 29 includes an electrochemical module 23, which includes a first anode film, a first cathode film, and an exchange membrane. The electrochemical module is the same as the electrochemical module of the above-mentioned embodiments, and will not be described here.

[0056] In the embodiment, the semiconductor processing device 20 is a metal organic chemical vapor deposition device, and the exhaust gas is a mixed gas containing hydrogen, ammonia, silane, and trimethyl gallium. A pretreatment device 21 is further provided between the semiconductor processing device 20 and the hydrogen-ammonia recovery device 29. The pretreatment device 21 can be a thermal decomposition device for thermally decomposing and removing silane and trimethyl gallium in the exhaust gas, so as to prevent silane and trimethyl gallium from reaching the hydrogen-ammonia recovery device 29 and damaging the first anode film and the first cathode film.

[0057] In the embodiment, the hydrogen-ammonia recovery device 29 further comprises a humidifier 22 for humidifying the gas from the pretreatment device 21, and the humidification can be achieved by spraying water vapor into the tail gas. The humidification is beneficial for the subsequent ammonium ion to pass through the exchange membrane. The humidified mixed gas is delivered by a total gas delivery pipeline 27, and the total gas delivery pipeline 27 is connected with a plurality of branch gas delivery pipelines 28.

[0058] In order to better recover hydrogen and ammonia, the electrochemical module 23 is provided in plurality, and the plurality of electrochemical modules 23 are connected in parallel with each other, and each of the plurality of branch gas delivery pipelines 28 is connected with the electrochemical module 23.

[0059] In the embodiment, the number of the branch gas delivery pipelines 28 is equal to the number of the electrochemical modules 23, that is, one branch gas delivery pipeline 28 is connected with one electrochemical module 23, and the different electrochemical modules 23 are connected in parallel with each other. In fact, the number of the branch gas delivery pipelines 28 is not limited to the number of the electrochemical modules 23, and the number of the branch gas delivery pipelines 28 can be greater than the number of the electrochemical modules 23, and then a plurality of branch gas delivery pipelines 28 are connected with one electrochemical module 23.

[0060] The mixed gas reaches the first side A' of the electrochemical module 23, and the hydrogen and ammonia are ionized to form ammonium ions at the first side A'. The ammonium ions pass through the exchange membrane under the driving of the driving circuit between the first cathode membrane and the first anode membrane to reach the second side B' of the exchange membrane, and form ammonia and hydrogen ions. The hydrogen ions and electrons recombine to form hydrogen, and other gases are difficult to pass through the exchange membrane and stay at the first side A'. That is, the hydrogen and ammonia are recovered at the second side B' of the electrochemical module 23.

[0061] In the embodiment, the hydrogen-ammonia recovery device 29 further comprises a solution pool 25 connected with the second side B' of the electrochemical module 23 by a gas delivery pipeline 207. The solution pool 25 contains an aqueous solution, and the solution pool 25 is used for dissolving the ammonia in the ammonia and hydrogen, and the hydrogen escapes because it is not soluble in the solution.

[0062] The hydrogen-ammonia recovery device 29 further comprises a hydrogen dryer 203 for drying the hydrogen from the solution pool 25, and a hydrogen storage container 26 for stabilizing and storing the dried hydrogen. The hydrogen in the hydrogen storage container 26 can be delivered back to the semiconductor processing device 20.

[0063] The hydrogen ammonia recovery device 29 further comprises an ammonia gas recovery device 204 for recovering ammonia gas from the solution pool 25, an ammonia gas dryer 205 for drying the ammonia gas in the ammonia gas recovery device 204, and an ammonia gas storage container 206 for storing the dried ammonia gas. The ammonia gas in the ammonia gas storage container 206 can be re-supplied to the semiconductor processing device 20.

[0064] In this embodiment, the gas recovery system 2 further comprises a post-processing device 24 connected to the first side A' of the electrochemical module 23 through a residual gas pipe 208. In one embodiment, the post-processing device 24 is a combustion device for combusting the mixed gas remaining in the first side A' of the electrochemical module 23. In other embodiments, the post-processing device can also be a solution absorption device for absorbing the residual mixed gas, or even a thermal decomposition device.

[0065] Figure 3 A schematic diagram of another embodiment of the gas recovery system of the present application.

[0066] In this embodiment, the gas recovery system 3, the semiconductor processing device 30, the process gas delivery pipe 301, the exhaust gas discharge pipe 302, the pre-processing device 31, the humidifier 32, the total gas delivery pipe 37, the branch gas delivery pipe 38, the solution pool 35, the hydrogen gas dryer 303, the hydrogen gas storage container 36, the ammonia gas recovery device 304, the ammonia gas dryer 305, the ammonia gas storage container 306, and the post-processing device 34 are the same as those in the above embodiment, and thus will not be described again. Figure 2 The same as in the above embodiment, and thus will not be described again.

[0067] The same as in the above embodiment, and thus will not be described again. Figure 2The difference of the embodiment includes: the mixed gas containing hydrogen and ammonia is recovered by the secondary electrochemical module, specifically, the branch gas conveying pipeline 38 is communicated with the tail gas discharging pipeline 302, the mixed gas containing hydrogen and ammonia firstly reaches the primary electrochemical module 33 through the branch gas conveying pipeline 38, most of the hydrogen and ammonia form ammonium ions on the first side A" of the primary electrochemical module 33, the ammonium ions reach the second side B" through the exchange film of the primary electrochemical module 33, and the hydrogen and ammonia are formed on the second side B", which are conveyed to the solution pool 35 through the primary gas conveying pipeline 331. The mixed gas remaining on the first side A" still contains a small amount of hydrogen and ammonia, in order to recover the hydrogen and ammonia, the mixed gas remaining on the first side A" is conveyed to the first side A"' of the secondary electrochemical module 39 through the primary residual gas conveying pipeline 332, the hydrogen and ammonia in the mixed gas remaining on the first side A" are recovered to the second side B"' through the exchange film of the secondary electrochemical module 39, and are conveyed to the solution pool 35 through the secondary gas conveying pipeline 391, and the residual gas of the first side A"' of the secondary electrochemical module 39 is communicated with the post-processing device 34 through the secondary residual gas conveying pipeline 392. The separation of the ammonia and hydrogen in the solution pool 35 is the same as the above embodiment, and is not described here.

[0068] In the embodiment, the mixed gas containing hydrogen and ammonia is recovered by the two-stage hydrogen ammonia recovery device, so that the recovery of hydrogen and ammonia in the mixed gas is more complete, the residual amount of hydrogen and ammonia in the residual mixed gas is less, and the waste of hydrogen and ammonia is reduced, and the recovery rate of hydrogen and ammonia is improved.

[0069] For the secondary hydrogen recovery, the flow path of the mixed gas is more complex, in order to more clearly illustrate the flow path of the mixed gas, the following is combined Figures 4 to 6 The details are described as follows:

[0070] Figure 4 It is a structure schematic diagram of the flow path of the mixed gas in the hydrogen ammonia recovery device.

[0071] In the embodiment, the hydrogen ammonia recovery device includes: a plurality of hydrogen ammonia recovery units 431, each hydrogen ammonia recovery unit 431 includes the electrochemical module 431a, and each hydrogen ammonia recovery unit 431 further includes: an outer cavity 431b, the electrochemical module 431a is arranged in the outer cavity 431b, the electrochemical module 431a divides the outer cavity 431b into a mixed gas passage 431c on the first side and a hydrogen ammonia passage 431d on the second side, the mixed gas passage 431c is communicated with the branch gas conveying pipeline 38, and the hydrogen ammonia passage 431d is used for containing the recovered hydrogen and ammonia.

[0072] In this embodiment, the branch gas delivery pipe 38 is in communication with the mixed gas passage 431c of the primary electrochemical module, so that the mixed gas in the branch gas delivery pipe 38 can be delivered to the mixed gas passage 431c of the primary electrochemical module, most of the hydrogen and ammonia in the mixed gas reaches the hydrogen ammonia passage 431d of the primary electrochemical module through the electrochemical module 431a of the primary electrochemical module, the remaining mixed gas is delivered along the mixed gas passage 431c of the primary electrochemical module to the mixed gas passage 431c of the secondary electrochemical module, the hydrogen and ammonia in this part of the mixed gas reaches the hydrogen ammonia passage 431d of the secondary electrochemical module through the electrochemical module 431a of the secondary electrochemical module, the hydrogen ammonia passage 431d of the primary electrochemical module and the hydrogen ammonia passage 431d of the secondary electrochemical module are in communication with each other, and in communication with the solution pool 35 (see Figure 3 ) for dissolving the ammonia in the ammonia and hydrogen, and the hydrogen escapes because it is not dissolved in the solution. The remaining mixed gas passage 431c on the first side of the secondary electrochemical module is in communication with the post-processing device 34 (see Figure 3 ) for burning the remaining mixed gas.

[0073] Figure 5 is another structure diagram of the flow path of the mixed gas in the hydrogen ammonia recovery device of the present application.

[0074] In this embodiment, the hydrogen ammonia recovery device comprises a plurality of hydrogen ammonia recovery units 531, each of which comprises the electrochemical module, and each of which further comprises: an outer cavity 531a and an inner cavity 531b located inside the outer cavity 531a, the bottom of the inner cavity 531b is provided with an opening, the side wall of the inner cavity 531b is composed of the electrochemical module, and the inner side wall of the inner cavity 531b is the first cathode film; the gap between the outer cavity 531a and the inner cavity 531b serves as a mixed gas passage and is in communication with the branch gas delivery pipe 38.

[0075] In the embodiment, the branch gas conveying pipe 38 communicates with the outer cavity 531a of the primary electrochemical module, so that the hydrogen and ammonia in the mixed gas are recovered into the inner cavity 531b through the inner side wall of the inner cavity 531b during the transmission of the mixed gas in the outer cavity 531a of the primary electrochemical module. The outer cavity 531a of the secondary electrochemical module communicates with the outer cavity 531a of the primary electrochemical module, so that the mixed gas remaining in the outer cavity 531a of the primary electrochemical module is conveyed into the outer cavity 531a of the secondary electrochemical module, and the mixed gas is purified through the side wall of the inner cavity 531b of the secondary electrochemical module and recovered into the inner cavity 531b. The inner cavity 531b of the secondary electrochemical module communicates with the inner cavity 531b of the primary electrochemical module, and the inner cavity 531b of the secondary electrochemical module communicates with the solution pool 35 (see Figure 3 ) for dissolving the ammonia in the mixed gas, and the hydrogen escapes because it is not dissolved in the solution. The outer cavity 531a of the secondary electrochemical module communicates with the post-processing device 34 (see Figure 3 ) for post-processing the residual mixed gas.

[0076] Figure 6 is another structure diagram of the flow path of the mixed gas in the hydrogen-ammonia recovery device.

[0077] In the embodiment, one electrochemical module constitutes a partition plate, the hydrogen-ammonia recovery device comprises an outer cavity 631 and a plurality of parallelly arranged partition plates 634 arranged in the outer cavity 631, a gas passage is formed between adjacent partition plates 634, and the gas passage defines a mixed gas passage 632 with the inner side wall of the gas passage being a first anode film, and a hydrogen-ammonia passage 633 with the inner side wall of the gas passage being a first cathode film; and the mixed gas passage 632 communicates with the branch gas conveying pipe 38.

[0078] In the embodiment, the electrochemical module 63 comprises a primary electrochemical module and a secondary electrochemical module connected in series, the mixed gas passage 632 of the primary electrochemical module communicates with the mixed gas passage 632 of the secondary electrochemical module, and the hydrogen-ammonia passage 633 of the secondary electrochemical module communicates with the hydrogen-ammonia passage 633 of the secondary electrochemical module, so as to recover the hydrogen and ammonia in the mixed gas in two stages, which is beneficial to improve the recovery rate of the hydrogen and ammonia and reduce the waste of the hydrogen and ammonia.

[0079] In the embodiment, the side walls of adjacent gas passages can be shared, so as to reduce the floor area of the electrochemical module 63.

[0080] Figures 4 to 6 In the embodiment, the hydrogen-ammonia recovery device further comprises a humidifier 32, a total gas conveying pipe 37, and a branch gas conveying pipe 38.

[0081] Figure 7 is a schematic diagram of another gas recovery system according to the present application.

[0082] Please refer to Figure 7 , in the gas recovery system 4, the semiconductor processing device 40, the process gas delivery pipeline 401, the exhaust gas discharge pipeline 402, the pretreatment device 41, the humidifier 42, the total gas delivery pipeline 47, the branch gas delivery pipeline 48, the post-treatment device 44, the gas delivery pipeline 408 and the remaining gas pipeline 409 are the same as Figure 2 or Figure 3 the same as in the above embodiments, which will not be repeated here.

[0083] In this embodiment, the mixed gas containing hydrogen and ammonia reaches the left side of the electrochemical module 43 through the branch gas delivery pipeline 48, and hydrogen and ammonia form ammonium ions on the left side of the electrochemical module 43, the ammonium ions pass through the electrochemical module 43, and ammonia and hydrogen are formed on the right side of the electrochemical module 43, achieving the recovery of hydrogen and ammonia.

[0084] In this embodiment, the electrochemical module 43 is connected to a hydrogen electrochemical module 45 through a gas delivery pipeline 408, the hydrogen electrochemical module 45 includes a proton exchange membrane, a second anode membrane and a second cathode membrane, the proton exchange membrane includes a third side C and a fourth side D opposite to each other, the second anode membrane is located on the third side C, and the second cathode membrane is located on the fourth side D, the first cathode membrane and the second anode membrane are in communication, and a driving circuit is arranged between the second anode membrane and the second cathode membrane, the driving circuit is used to apply a second driving voltage between the second anode membrane and the second cathode membrane, so as to recover hydrogen on the fourth side D. The hydrogen ammonia recovery device 49 further comprises a hydrogen dryer 403 and a hydrogen storage container 46. The hydrogen dryer 403 and the hydrogen storage container 46 are the same as the above Figure 2 or Figure 3 the same as in the above embodiments, which will not be repeated here.

[0085] Meanwhile, the third side C of the second anode membrane is in communication with a solution pool 407, the solution pool 407 is used to dissolve the remaining gas, most of which is ammonia, and only a very small amount of hydrogen remains, wherein the ammonia is dissolved in the solution in the solution pool 407, and an opening is arranged above the solution pool 407, the opening is used to release a small amount of hydrogen. The hydrogen ammonia recovery device 49 further comprises an ammonia recovery device 404, an ammonia dryer 405 and an ammonia storage container 406, and the ammonia recovery device 404, the ammonia dryer 405 and the ammonia storage container 406 are the same as the above Figure 2 or Figure 3 the same as in the above embodiments, which will not be repeated here.

[0086] After the hydrogen and ammonia are recovered from the second side of the electrochemical module 43, the separation of the hydrogen and ammonia is not limited to Figure 2 、 Figure 3 and Figure 7 The hydrogen and ammonia can also be separated by taking advantage of the different boiling points of the hydrogen and ammonia. In fact, the separation of the hydrogen and ammonia is not limited in this regard.

[0087] In the above Figure 2 、 Figure 3 and Figure 7 Embodiments, a valve (not shown in the figures) is provided in the remaining gas passage (208, 392, 409). The valve is used to control the opening and closing of the remaining gas passage. When the flow rate of the hydrogen and ammonia in the tail gas is low, the valve can be closed to allow the tail gas to stay in the hydrogen and ammonia recovery device for a longer period of time, which is conducive to better converting the hydrogen and ammonia into ammonium ions through the electrochemical module and improving the recovery rate of the hydrogen and ammonia.

[0088] In the above embodiments, as shown in Figure 8 A guide vane 701 can be provided on the inner side wall of the mixed gas passage 700. The provision of the guide vane 701 is conducive to increasing the roughness of the inner side wall of the mixed gas passage 700, increasing the contact area between the mixed gas and the electrochemical module, guiding the flow of the mixed gas, making the transmission path of the mixed gas a curve, and prolonging the contact time between the mixed gas and the electrochemical module 702, which is conducive to more fully recovering the hydrogen.

[0089] In the above embodiments, as shown in Figure 9 The inner diameter of the mixed gas passage 800 varies along the flow direction G of the mixed gas, so that the mixed gas travels in a curve within the mixed gas passage 800 rather than straight out of the mixed gas passage 800, which is conducive to prolonging the contact time between the mixed gas and the electrochemical module 801 and more fully recovering the hydrogen.

[0090] Although the present application has been described in detail through the above preferred embodiments, it should be recognized that the above description should not be considered as limiting the present application. After reading the above, various modifications and alternatives to the present application will be apparent to those skilled in the art. Therefore, the scope of protection of the present application should be defined by the appended claims.

Claims

1. A gas recovery system characterized by, The application relates to a semiconductor processing device, which comprises an exhaust pipe, wherein the exhaust gas discharged by the exhaust pipe is a mixed gas containing ammonia and hydrogen, and the volume fraction of ammonia and hydrogen in the exhaust gas is greater than 20%; a hydrogen-ammonia recovery device, which comprises an electrochemical module, wherein the electrochemical module comprises an exchange film, a first anode film and a first cathode film, the exchange film comprises opposite first and second sides, the first anode film is located on the first side, the first cathode film is located on the second side, the exhaust pipe is communicated with the first anode film, a driving circuit is arranged between the first anode film and the first cathode film, and the driving circuit is used for applying a first driving voltage between the first anode film and the first cathode film to recover a mixed gas of hydrogen and ammonia on the second side. The semiconductor processing device is a metal organic chemical vapor deposition device, and the exhaust gas further contains silane, nitrogen and trimethyl gallium gas. The semiconductor processing device is further provided with a pretreatment device between the semiconductor processing device and the hydrogen-ammonia recovery device, which is used for removing the silane and trimethyl gallium gas.

2. The gas recovery system of claim 1, wherein, The hydrogen-ammonia recovery device further comprises a total gas conveying pipe and a plurality of branch gas conveying pipes, two ends of the total gas conveying pipe are respectively connected with the pretreatment device and one end of each branch gas conveying pipe, and the other end of the branch gas conveying pipe is communicated with the electrochemical module, so that the mixed gas in the branch gas conveying pipe is conveyed to the first anode film.

3. The gas recovery system of claim 2, wherein, The plurality of branch conveying pipes are respectively connected with at least two electrochemical modules, and the at least two electrochemical modules are connected in parallel with each other.

4. The gas recovery system of claim 3, wherein, The hydrogen-ammonia recovery device further comprises a humidifier, which is respectively communicated with the pretreatment device and the total gas conveying pipe and is used for humidifying the mixed gas; a separation device, which is communicated with the first cathode film through a gas conveying pipe and is used for separating the hydrogen and ammonia; a hydrogen dryer, which is used for drying the recovered hydrogen; a hydrogen storage container, which is communicated with the hydrogen dryer and is used for stabilizing and storing the dried hydrogen; an ammonia dryer, which is used for drying the recovered ammonia; and an ammonia storage container, which is communicated with the ammonia dryer and is used for stabilizing and storing the dried ammonia.

5. The gas recovery system of claim 4, wherein, The separation device is a hydrogen electrochemical module, which comprises a proton exchange film, a second anode film and a second cathode film, the proton exchange film comprises opposite third and fourth sides, the second anode film is located on the third side, the second cathode film is located on the fourth side, the first cathode film is communicated with the second anode film, a driving circuit is arranged between the second anode film and the second cathode film, the driving circuit is used for applying a second driving voltage between the second anode film and the second cathode film to recover hydrogen on the fourth side, the second cathode film is communicated with the hydrogen dryer; and further comprises a solution pool which is communicated with the third side and is used for dissolving ammonia.

6. The gas recovery system of claim 4, wherein, The separation device is a solution pool, the ammonia is dissolved in the solution, the hydrogen is not dissolved in the solution, and the solution pool is connected with the hydrogen dryer.

7. The gas recovery system of claim 6, wherein, ​ 8. The gas recovery system of claim 6, wherein, ​ 9. The gas recovery system of claim 7 or 8, wherein, The solution pool is connected with an ammonia gas recovery device for recovering ammonia gas in the solution, and the ammonia gas recovery device is connected with the ammonia gas dryer.

10. The gas recovery system of claim 1 or 4, wherein, The electrochemical module includes a primary electrochemical module and a secondary electrochemical module connected in series, the branch gas conveying pipeline is connected with the first side of the primary electrochemical module, part of hydrogen gas and ammonia gas is recovered to the second side of the primary electrochemical module, and the remaining mixed gas reaches the first side of the secondary electrochemical module from the first side of the primary electrochemical module, and part of hydrogen gas and ammonia gas is recovered to the second side of the secondary electrochemical module.

11. The gas recovery system of claim 1, wherein, Further comprising: A post-processing device connected with the first side of the hydrogen ammonia recovery device through a remaining gas pipeline for post-processing the remaining mixed gas; and the post-processing device is a combustion device.

12. The gas recovery system of claim 11, wherein, Further comprising: A valve for controlling the opening and closing of the remaining gas conveying pipeline.

13. The gas recovery system of claim 1, wherein, The first driving voltage is less than 0.7 volts.

14. A hydrogen and ammonia recovery device for the gas recovery system according to any one of claims 1 to 13, characterized in that: Comprising: An outer cavity; An electrochemical module arranged in the outer cavity, which includes an exchange film, a first anode film and a first cathode film, the exchange film includes opposite first and second sides, the first anode film is located on the first side, and the first cathode film is located on the second side for dividing the outer cavity into a mixed gas channel on the first side and a hydrogen ammonia channel on the second side, the mixed gas channel is connected with the tail gas discharge pipeline, and the mixed gas channel makes the transmission path of the mixed gas non-linear.

15. The hydrogen ammonia recovery apparatus of claim 14, wherein The hydrogen ammonia recovery device includes a plurality of hydrogen ammonia recovery units, each of which includes the outer cavity and the electrochemical module; each recovery unit further includes: an inner cavity located inside the outer cavity, the bottom of the inner cavity is provided with an opening, the side wall of the inner cavity is formed by the electrochemical module, and the inner side wall of the inner cavity is the first cathode film; the gap between the outer cavity and the inner cavity forms the mixed gas channel, and the inner cavity is the hydrogen ammonia channel.

16. The ammonia-hydrogen recovery apparatus of claim 14, wherein One electrochemical module forms a partition plate, a plurality of parallel arranged partition plates are located in one outer cavity, the inner side wall of the gas channel which is the first anode film is the mixed gas channel, and the inner side wall of the gas channel which is the first cathode film is the hydrogen ammonia channel.

17. The ammonia-hydrogen recovery apparatus of claim 14, wherein The hydrogen ammonia recovery device includes a plurality of hydrogen ammonia recovery units, each of which includes the electrochemical module and the outer cavity.

18. The ammonia-hydrogen recovery apparatus of claim 14, wherein Further comprising: A guide vane arranged on the inner side wall of the mixed gas channel for making the mixed gas containing hydrogen gas and ammonia gas curve in the mixed gas channel.

19. The ammonia-hydrogen recovery apparatus of claim 14, wherein The inner diameter of the mixed gas channel is different along the flow direction of the mixed gas.

20. The ammonia-hydrogen recovery apparatus of claim 14, wherein The exchange membrane is an ammoniated treatment membrane; the treatment membrane includes: a phenolic resin sulfonic acid type membrane, a polystyrene sulfonic acid type membrane, a polytrifluorostyrene sulfonic acid type membrane, a perfluorosulfonic acid type membrane, or a perfluorosulfonic acid type membrane and a polytetrafluoroethylene composite membrane; the material of the first anode membrane and the first cathode membrane is: nickel molybdenum, nickel ruthenium alloy, cobalt, chromium, iron-doped nickel molybdenum or nickel ruthenium alloy; further comprising: diffusion layers located on the first side and the second side, a mixed gas containing hydrogen and ammonia sequentially passing through the diffusion layers, the first anode layer, the exchange membrane, the first cathode layer and the diffusion layers; the material of the diffusion layer includes: a carbon body and polytetrafluoroethylene wrapped on the surface of the carbon body.

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