CN109506419A

CN109506419A - For producing the method and system of liquid argon and/or argon gas product

Info

Publication number: CN109506419A
Application number: CN201710831213.2A
Authority: CN
Inventors: 修国华
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-09-15
Filing date: 2017-09-15
Publication date: 2019-03-22

Abstract

This application involves the method and systems for producing liquid argon and/or argon gas product.Specifically, this application provides the method and systems of liquid argon and/or argon gas product by the admixture of gas preparation purifying comprising argon gas.The described method and system of the application can efficiently remove the constituent of air such as oxygen and nitrogen in admixture of gas to be processed, with the hydrocarbons and dust and other impurities such as carbon monoxide, carbon dioxide, water, mist of oil, to obtain the argon gas and/or liquid argon product of high-purity.

Description

For producing the method and system of liquid argon and/or argon gas product

Technical field

This application involves the productions of liquid argon and/or argon gas product, especially prepare purifying by admixture of gas to be processed Liquid argon and/or argon gas product system and method.

Background technique

It needs largely to use argon gas product as the protection gas in monocrystaline silicon stove in monocrystalline silicon production.Under normal circumstances, often Platform monocrystaline silicon stove needs to consume daily argon gas product about 100-200kg, and 1000 monocrystaline silicon stoves need to consume high-purity daily About 100-200 tons of argon gas product.Therefore, the argon gas product of high-purity has high economic value.Even if not considering argon gas The price of product, without reliable argon gas rule of origin, daily 100-200 tons of consumption is also often difficult to guarantee, this increase The uncertainty of monocrystalline silicon production.

Existing argon gas recovery technology is only capable of handling small flow and hypoxemia usually due to being limited by way of recycling The tail gas containing argon of content.Many references and help are provided for argon gas recycling using the smart argon production technology of air separation principle, But there are many more differences for the smart argon production during monocrystalline silicon production in the recycling and air separation of argon gas.For example, single Tail gas containing argon to be processed usually impurity such as the oxygen containing higher concentration and nitrogen in crystal silicon production process, and exhaust flow containing argon is not Stablize, usually fluctuate in a big way, these are all the problem of not being commonly encountered in smart argon production, and silicon vapor is in discharge process It encounters oxygen and is oxidized to SiO₂, furthermore, it is possible to generate a large amount of mist of oils using there is oil vacuum pump and be mixed into the tail gas containing argon. Therefore, the method and system of high-purity liquid argon and/or argon gas product can effectively be produced by still needing to exploitation.This method and system are then It can reduce the cost of monocrystalline silicon production, and achieve energy-saving and emission reduction purposes.

Summary of the invention

This application provides the method and system for producing liquid argon and/or argon gas product, described method and system passes through To the recycling of the mixture containing argon gas, purification process and the liquid for realizing effectively production high-purity to the comprehensive utilization of energy The purpose of argon and/or argon gas product.

On the one hand, this application provides a kind of methods of liquid argon for being used to prepare purifying and/or argon gas product.The method Can include: a) make admixture of gas to be processed be subjected to pretreatment with remove mist of oil, dust and other particulate matters therein to Obtain pretreated admixture of gas；Contact pretreated admixture of gas a) with catalytic oxidation unit, To make the reducibility gas in the admixture of gas by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；c) It contacts the admixture of gas through catalysis oxidation b) with deacidification unit, and is passed through proper proportion into the deacidification unit Hydrogen so that oxygen content therein is reduced to 2ppm hereinafter, to obtain the admixture of gas of hydrogenated deoxidation；D) make c) The admixture of gas of the hydrogenated deoxidation is contacted with absorbing unit, to remove water, the carbon dioxide in the admixture of gas And/or hydrocarbon, to obtain the admixture of gas to rectification process；E) gas to rectification process of measurement d) The flow of mixture, and make by being buffered with rectifying qualification the stream of the admixture of gas to rectification process and gas is adjusted Amount is within the scope of the flow operating flexibility of rectification process；And f) make the admixture of gas to rectification process e) through low Warm rectification process is to remove nitrogen and hydrogen, to obtain the liquid argon and/or argon gas product of purifying.

In some embodiments, the c of the method) in, be passed through in Xiang Suoshu deacidification unit the hydrogen of proper proportion with Oxygen content therein is set to be reduced to 0.1ppm or less.

In some embodiments, the method also includes: g) recycle and/or purify the hydrogen that is removed in f).

In some embodiments, pretreatment a) of the method includes bulk processing and accurate processing.Certain In embodiment, the bulk processing includes using selected from following one or more: adsorbing mist of oil using asphalt felt, passes through filtering Device filters dust, removes mist of oil and dust by water spray, by rotating device concentration separation removal mist of oil and dust, and/ Or it generates the water comprising microbubble and is made a return journey by spraying the water comprising microbubble to the admixture of gas to be processed Oil mist removing.In some embodiments, the accurate processing includes using following one or more: membrane filter, ceramic mistake Filter, metallic filter and/or active carbon adsorber.

In some embodiments, the method recycles and/or purifies institute by cryogenic rectification, flash distillation, and/or absorption State hydrogen.

In some embodiments, the b of the method) in, urge the pretreated admixture of gas with described Before changing oxidation unit contact, the oxygen concentration in the pretreated admixture of gas is measured；And/or keep the warp pre- Before the admixture of gas of processing is contacted with the catalytic oxidation unit, the oxygen in the pretreated admixture of gas is measured Concentration；And/or before contacting the pretreated admixture of gas with the catalytic oxidation unit, remove the warp Water and carbon dioxide in pretreated admixture of gas.

In some embodiments, when the measured oxygen concentration is more than 4% (v/v), by being located described in advance At least part of the admixture of gas of reason discharge and be passed through deoxidation qualification buffering gas come make its oxygen concentration 4% (v/v) with Under.In some embodiments, when the measured oxygen concentration is more than 2% (v/v), by by the pretreated gas At least part of body mixture discharges and is passed through deoxidation qualification buffering gas to make its oxygen concentration 2% (v/v) below.

In some embodiments, the c of the method) in, the hydrogen that is passed through in Xiang Suoshu deacidification unit and measured The molar ratio of oxygen in the pretreated admixture of gas is 2.2:1 to 3:1.

In some embodiments, the b of the method) in, the catalysis oxidation will include hydrocarbon and an oxidation The reducibility gas of carbon is oxidized to water and carbon dioxide.

In some embodiments, the b of the method) in, when oxygen rubs in the pretreated admixture of gas When the molar fraction of oxygen needed for your score is less than the oxidation pretreated gas, then oxygen is added, locates the warp in advance The molar fraction of oxygen is 10- higher than the molar fraction of oxygen needed for the pretreated gas in the admixture of gas of reason 50%.

In some embodiments, the method it is middle b) described in catalytic oxidation unit include catalyst, and it is described Catalyst is selected from the group: Carulite catalyst, platinum catalyst, palladium catalyst and any combination thereof.

In some embodiments, the c of the method) described in deacidification unit include catalyst, and the catalyst It is selected from the group: Cu, platinum catalyst, palladium catalyst and any combination thereof.

In some embodiments, impurity to be removed in the admixture of gas to be processed of the method includes: Other particulate matters such as mist of oil, dust, silicon powder, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water and/or nytron Object etc..

In some embodiments, admixture of gas to be processed described in the method is that monocrystaline silicon stove or ingot furnace produce Raw exhaust gas.

In some embodiments, when the molar fraction of oxygen in the pretreated admixture of gas be greater than 2% or When the temperature that the pretreated admixture of gas carries out the catalysis oxidation is more than 400 degrees Celsius, the catalysis oxidation Unit includes segmentation reactor；And/or when the temperature that the deacidification unit is reacted is more than 400 degrees Celsius, described is de- Oxygen unit includes segmentation reactor.

In some embodiments, the method also includes controlling in the monocrystaline silicon stove or ingot furnace and give up before a) The discharge opportunity of gas, so that the content of argon gas is maintained at 80% in the admixture of gas to be pre-treated.

In some embodiments, admixture of gas to be pre-treated described in the method is from two or more The exhaust gas of monocrystaline silicon stove or ingot furnace, and when any of the two or more monocrystaline silicon stoves or ingot furnace need and ring When border gaseous fluid is connected to, stop discharging tail into the admixture of gas to be pre-treated from the monocrystaline silicon stove or ingot furnace Gas.

In some embodiments, the content of argon is extremely in the liquid argon of purifying described in the method and/or argon gas product Few 99%.In some embodiments, the content of argon is at least in the liquid argon of purifying described in the method and/or argon gas product 99.999%.

In some embodiments, the d of the method) it is middle using at least two absorbing units, and work as described at least two When one of absorbing unit is adsorbed, another absorbing unit therein is regenerated, so that at least two absorption is single Member alternately absorption and regeneration, then realizes and persistently carries out adsorption treatment to the admixture of gas.

In some embodiments, oxygen content is that 0.1ppm or less argon content is not less than in the rectifying qualification buffering gas 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water and hydrocarbon.At certain In a little embodiments, the partial size that mist of oil in the rectifying qualification buffering gas is referred to substantially free of mist of oil is 0.1 μm or less. In some embodiments, refer to dust or other particulate matters in the rectifying qualification buffering gas without dust or other particulate matters Partial size be 0.1 μm or less.In some embodiments, described to refer to the rectifying qualification buffering substantially free of carbon monoxide The content of carbon monoxide is 0.1ppm or less in gas.In some embodiments, described to refer to institute substantially free of carbon dioxide The content for stating carbon dioxide in rectifying qualification buffering gas is 0.1ppm or less.In some embodiments, it is described substantially free of Water refers to that the dew-point temperature of the rectifying qualification buffering gas is -50 DEG C or less.In some embodiments, it is described substantially free of Hydrocarbon refers to that the total content of the non-methane total hydrocarbons in the rectifying qualification buffering gas is 0.1ppm or less.

In some embodiments, oxygen content is 0.1ppm hereinafter, argon content is not less than in the deoxidation qualification buffering gas 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water and hydrocarbon.At certain In a little embodiments, the partial size that mist of oil in the deoxidation qualification buffering gas is referred to substantially free of mist of oil is 0.1 μm or less. In some embodiments, it is described substantially free of dust or other particulate matters refer in the deoxidation qualification buffering gas dust or The partial size of other particulate matters is 0.1 μm or less.In some embodiments, described to refer to described take off substantially free of carbon monoxide The content that oxygen qualification buffers carbon monoxide in gas is 0.1ppm or less.In some embodiments, carbonated does not refer to institute The content for stating carbon dioxide in deoxidation qualification buffering gas is about 0.1ppm or less.In some embodiments, it is described substantially not The aqueous dew-point temperature for referring to the water in the deoxidation qualification buffering gas is lower than -40 DEG C.In some embodiments, described basic On hydrocarbon-containiproducts do not refer to that the content of non-methane total hydrocarbons in deoxidation qualification buffering gas is about 0.1ppm or less.

In some embodiments, the flow operating flexibility range of the rectification process is that the design of the rectification process is negative The 60% to 120% of lotus flow.

In some embodiments, the f of the method) in, cryogenic rectification processing includes: i) to make e) described to essence At least part for evaporating the admixture of gas of processing becomes material stream；Ii the material stream and heat source i)) is made to carry out heat Exchange, the material stream to be gasified；And iii) make ii) the gasification material stream and liquid low temperature cooling medium into Row heat exchange obtains the argon gas product of purifying；Also, at least part in the material stream of gasification ii) is condensed For phegma, liquid low temperature cooling medium of the phegma as the rectification process.

In some embodiments, the ii of the method) described in liquid low temperature cooling medium be that liquid nitrogen or liquefaction are empty Gas or liquid argon.

In some embodiments, ii) described in liquid low temperature cooling medium be liquid argon.In some embodiments, In the method, as ii) described in liquid low temperature cooling medium liquid argon be to through condensation obtain the purifying liquid argon Carry out the low pressure liquid argon obtained after throttling expansion.In some embodiments, the ii of the method) in the liquid through gasifying State cryogenic condensation medium becomes the argon gas product of purifying after re-heat.

In some embodiments, the ii of the method) described in liquid low temperature cooling medium pressure be the low temperature The dew-point temperature of the material stream reduces corresponding liquid argon pressure at 1-7 DEG C under operating pressure in rectification process.

In some embodiments, the pressure of liquid low temperature cooling medium described in the method is at the cryogenic rectification The dew-point temperature of the material stream reduces corresponding liquid argon pressure at 2-3 DEG C under operating pressure in reason.

In some embodiments, the pressure of liquid low temperature cooling medium described in the method is 0.02-0.2MPa.

In some embodiments, the ii of the method) in the liquid low temperature cooling medium carry out heat exchange institute The pressure of material stream is stated as 0.1-1.0MPa, and the high 0.02- of pressure of cryogenic condensation medium described in the pressure ratio of the heat source 0.1MPa。

In some embodiments, the iii of the method) described in heat source be by described to rectification process to e) At least part of admixture of gas carry out pressurization and heating treatment and obtain, the pressure of the heat source is the low temperature essence The dew-point temperature for evaporating the material stream under operating pressure in processing increases the pressure of corresponding argon at 1-7 DEG C, the heat source The high 0.02-0.1MPa of the pressure of cryogenic condensation medium described in pressure ratio.

In some embodiments, the pressure of the heat source of the method is operating pressure in cryogenic rectification processing Under the dew-point temperature of the material stream corresponding argon when increasing 2-3 DEG C pressure, low temperature cold described in the pressure ratio of the heat source The high 0.02-0.1MPa of pressure of solidifying medium.In some embodiments, the pressure of the heat source of the method is 0.7- 0.15MPa, the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

In some embodiments, the i of the method) in, the admixture of gas to rectification process e) is carried out Following processing obtains the material stream: ia) make the admixture of gas to rectification process e) through compressor compresses at For the gas mixing logistics stock that high temperature and pressure is to be processed；Ib) make ia) high temperature and pressure gas mixing logistics stock to be processed It is handled in heat exchanger through cooling and becomes cryogenic high pressure gas mixing logistics stock to be processed；And ic) make ib) it is described low At least part of warm high pressure gas mixing logistics stock to be processed becomes the material stream after throttling expansion.

In some embodiments, the iii of the method) described in heat source be ib) in obtain the cryogenic high pressure A part of gas mixing logistics stock to be processed.

In some embodiments, the method is by making the liquid low temperature cooling medium through gasifying and the high temperature High pressure gas mixing logistics stock to be processed carries out heat exchange in the heat exchanger and keeps the liquid low temperature through gasifying cold Solidifying medium is become the argon gas product of purifying, and keeps the high temperature and pressure to be processed gas mixing logistics stock-traders' know-how cooling after re-heat It handles and becomes cryogenic high pressure gas mixing logistics stock to be processed.

In some embodiments, heat source described in the method and the liquid argon of the purifying obtained through condensation carried out After heat exchange, a part of the material stream is expanded into through throttling.

In some embodiments, the temperature of liquid low temperature cooling medium described in the method is -170 DEG C to -198 ℃。

In some embodiments, the i of the method) described in material stream temperature be -165 DEG C to -197 DEG C, and The temperature of the cryogenic condensation medium is at least 1-5 DEG C lower than the temperature of the material stream.

In some embodiments, the temperature of the liquid argon of the purifying obtained in the method through condensation is -160 DEG C To -196 DEG C, and the temperature of the liquid argon of the purifying is 0.5 DEG C to 5 DEG C lower than the temperature of the material stream.

In some embodiments, the temperature of the heat source of the method is -170 DEG C to -195 DEG C, and the heat source Temperature it is at least 1-5 DEG C higher than the temperature of the liquid argon of the purifying.

It in some embodiments, include adsorbent in absorbing unit described in the method, and the adsorbent includes Following is one or more: active carbon, activated alumina, modified silica-gel, carbon molecular sieve, natural zeolite, modified zeolite, sial base Molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, metal-organic framework material and their mixture.

On the other hand, this application provides the system of a kind of liquid argon for being used to prepare purifying and/or argon gas product, the systems System includes: pretreatment unit, and gas mixing fluid communication to be processed and removes mist of oil therein, dust and other Grain object is to obtain pretreated admixture of gas；Catalytic oxidation unit is in fluid communication with the pretreatment unit, described Catalytic oxidation unit makes the reducibility gas in the pretreated admixture of gas by catalysis oxidation, to obtain through being catalyzed oxygen The admixture of gas of change；Deacidification unit is in fluid communication with the catalytic oxidation unit, and it is appropriate to be passed through in Xiang Suoshu deacidification unit After the hydrogen of ratio, the deacidification unit make the oxygen content in the admixture of gas through catalysis oxidation be reduced to about 2ppm with Under, to obtain the admixture of gas of hydrogenated deoxidation；Absorbing unit is in fluid communication, the absorption with the deacidification unit Unit includes water, carbon dioxide and/or the hydrocarbon in admixture of gas of the adsorbent to remove the hydrogenated deoxidation, To obtain the admixture of gas to rectification process；First buffer cell, with the gas mixing logistics to rectification process Body is connected to and includes the flow rate-measuring device for measuring the flow of the admixture of gas to rectification process, and described first is slow It rushes in unit and buffers gas comprising rectifying qualification, it is mixed that the rectifying qualification buffering gas is used to adjust for the gas to rectification process The flow of object is closed, and makes the flow within the scope of flow operating flexibility of rectification process；And cryogenic rectification unit, with institute It states absorbing unit and first buffer cell is in fluid communication, it is described to the nitrogen in the admixture of gas of rectification process to remove And hydrogen, to obtain the liquid argon and/or argon gas product of purifying.

In some embodiments, the deacidification unit of the system makes in the admixture of gas through catalysis oxidation Oxygen content be reduced to 0.1ppm hereinafter, to obtain the admixture of gas of hydrogenated deoxidation.

In some embodiments, the system also includes hydrogen retrieval unit, the hydrogen retrieval unit and low temperature essences Unit is evaporated to be in fluid communication and be used to recycle the hydrogen being removed in the cryogenic rectification unit.

In some embodiments, the pretreatment unit of the system includes bulk processing device and accurate processing dress It sets.

In some embodiments, the bulk processing device of the system includes selected from following one or more: being inhaled Malthoid, dust filtering device and/or water spray system and/or rotation for removing mist of oil and dust removing means simultaneously simultaneously Rotary device.

In some embodiments, the water spray system of the system generates the water comprising microbubble and by institute The admixture of gas spray water comprising microbubble to be processed is stated to make a return journey oil mist removing.

In some embodiments, the accurate processing unit of the system includes one of the following or a variety of: film Filter, ceramic filter, metallic filter and/or active carbon adsorber.

In some embodiments, the hydrogen retrieval unit of the system includes selected from following device: cryogenic rectification Device, flash distillation plant and/or adsorbent equipment.

In some embodiments, the system also includes oxygenation measurement unit, the oxygenation measurement unit and the pretreatments Unit is in fluid communication and can measure the oxygen concentration in the pretreated admixture of gas.

In some embodiments, the system also includes various impurity measurement units, the impurity measurement unit and institutes Pretreatment unit is stated to be in fluid communication and can measure the impurity concentration in the pretreated admixture of gas.The impurity measurement Unit can remove the water and carbon dioxide in the pretreated admixture of gas.

In some embodiments, the system also includes the second buffer cell, second buffer cell includes deoxidation Qualification buffering gas and with the pretreated gas mixing fluid communication, when the oxygen concentration measured is more than 4% (v/v) When, at least part of the pretreated admixture of gas is discharged and from second buffer cell to described through pre- Deoxidation qualification buffering gas is passed through in the admixture of gas of processing to make oxygen concentration 4% (v/v) therein below.

In some embodiments, in the system, when the oxygen concentration measured is more than 2% (v/v), by the warp At least part of pretreated admixture of gas discharges and from second buffer cell to the pretreated gas Deoxidation qualification buffering gas is passed through in mixture to make oxygen concentration 2% (v/v) therein below.

In some embodiments, the hydrogen and the measured warp being passed through in the system into the deacidification unit The molar ratio of oxygen in pretreated admixture of gas is 2.2:1 to 3:1.

In some embodiments, the catalytic oxidation unit of the system will include hydrocarbon and carbon monoxide Reducibility gas be oxidized to water and carbon dioxide.

In some embodiments, the catalytic oxidation unit of the system includes catalyst, and the catalyst selects From the following group: Carulite catalyst, platinum catalyst, palladium catalyst and any combination thereof.

In some embodiments, the deacidification unit of the system includes catalyst, and the catalyst is selected from down Group: Cu, platinum catalyst, palladium catalyst and any combination thereof.

In some embodiments, impurity to be removed in admixture of gas to be processed described in the system includes: Mist of oil, dust, other particulate matters, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water and/or hydrocarbon.

In some embodiments, admixture of gas to be processed described in the system is that monocrystaline silicon stove or ingot furnace produce Raw exhaust gas.

In some embodiments, the system also includes air inlet adjustment valve, the air inlet adjustment valve controls the monocrystalline Fluid communication between silicon furnace or ingot furnace and the pretreatment unit, so that in the admixture of gas to be pre-treated The content of argon gas is maintained at 80%.

In some embodiments, the system comprises air inlet adjustment valves described in two or more, wherein each air inlet Regulating valve independently controls an individual fluid communication between monocrystaline silicon stove or ingot furnace and the pretreatment unit, and When any one described monocrystaline silicon stove or ingot furnace need to be in fluid communication with environmental gas, corresponding air inlet adjustment valve blocks the monocrystalline Fluid communication between silicon furnace or ingot furnace and the pretreatment unit.

In some embodiments, the content of argon is extremely in the liquid argon of purifying described in the system and/or argon gas product Few 99%.In some embodiments, the content of argon is at least in the liquid argon of purifying described in the system and/or argon gas product 99.999%.

In some embodiments, the system comprises at least two absorbing units, and when at least two absorption is single When one of member is adsorbed, another absorbing unit therein is regenerated, so that at least two absorbing unit replaces It is adsorbed and is regenerated, then realize that the admixture of gas to the hydrogenated deoxidation persistently carries out adsorption treatment.

In some embodiments, oxygen content is 0.1ppm hereinafter, argon in the buffering of rectifying qualification described in system gas Content is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water and hydrocarbonization Close object.

In some embodiments, refer in the rectifying qualification buffering gas described in the system substantially free of mist of oil The partial size of mist of oil is 0.1 μm or less.In some embodiments, substantially free of dust or other particles described in the system Object refers to that the partial size of dust or other particulate matters is about 0.1 μm or less in the rectifying qualification buffering gas.In certain embodiments In, the content for referring to carbon monoxide in the rectifying qualification buffering gas substantially free of carbon monoxide described in the system is 0.1ppm or less.In some embodiments, refer to that the rectifying is qualified substantially free of carbon dioxide described in the system The content for buffering carbon dioxide in gas is 0.1ppm or less.In some embodiments, described in the system substantially free of Water refers to about -50 DEG C of dew-point temperature or less of the rectifying qualification buffering gas.In some embodiments, described in the system The total content for referring to the total content of non-methane total hydrocarbons in the rectifying qualification buffering gas substantially free of hydrocarbon is about 0.1ppm or less.

In some embodiments, oxygen content is 0.1 μm hereinafter, argon contains in the buffering of deoxidation qualification described in system gas Amount is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water and nytron Object.In some embodiments, refer to mist of oil in the deoxidation qualification buffering gas substantially free of mist of oil described in the system Partial size be 0.1 μm or less.In some embodiments, it is substantially free of dust or other particulate matters described in the system Refer to that the partial size of dust or other particulate matters is 0.1 μm or less in the deoxidation qualification buffering gas.In some embodiments, described Described in system substantially free of carbon monoxide refer to the content of carbon monoxide in deoxidation qualification buffering gas be 0.1ppm with Under.In some embodiments, refer in the deoxidation qualification buffering gas described in the system substantially free of carbon dioxide The content of carbon dioxide is 0.1ppm or less.In some embodiments, refer to institute substantially free of water described in the system The dew-point temperature for stating the water in deoxidation qualification buffering gas is -4 DEG C or less.In some embodiments, base described in the system Hydrocarbon-containiproducts do not refer to that the content of non-methane total hydrocarbons in the deoxidation qualification buffering gas is 0.1ppm or less in sheet.

In some embodiments, cryogenic rectification unit described in the system carries out the flow operating flexibility of rectification process Range is the 60% to 120% of the cryogenic rectification unit Design cooling load flow.

In some embodiments, cryogenic rectification unit described in the system includes one or more following components: pressure Contracting machine, throttle valve, heat exchanger, rectifying column, condenser, evaporator and/or reboiler.

In some embodiments, wherein the cryogenic rectification unit includes one or more rectifying columns, each rectifying column It is equipped with condensation reflux device and reboiler, wherein the condensation reflux device is located at the rectifying column upper end, the reboiler is located at institute State rectifying column lower end；The cryogenic rectification unit makes at least part of the admixture of gas to rectification process become material Flow stock；The material stream and the reboiler carry out heat exchange, the material stream to be gasified；The material stream of the gasification Heat exchange is carried out with the condensation reflux device, obtains the argon gas product of purifying in the rectifying column bottom end；The material of the gasification At least part in stream stock is condensed into phegma after the condensation reflux device heat exchange；The phegma is as the rectifying The liquid low temperature cooling medium of processing.

In some embodiments, the liquid low temperature cooling medium in condenser described in the system and it is described again The heat source boiled in device is mutually indepedent.

In some embodiments, the liquid low temperature cooling medium in condenser described in the system and it is described again It boils between the heat source in device by being connected to selected from following process: compression, throttling expansion and/or heat exchange.

In some embodiments, liquid low temperature cooling medium described in the system is liquid nitrogen, liquefied air or liquid argon. In some embodiments, liquid low temperature cooling medium described in the system is liquid argon.

In some embodiments, the liquid argon of liquid low temperature cooling medium described in the system is to obtain to through condensation The liquid argon of the purifying carries out the low pressure liquid argon obtained after throttling expansion.

In some embodiments, the liquid low temperature cooling medium in the system through gasifying becomes pure after re-heat The argon gas product of change.

In some embodiments, the pressure of liquid low temperature cooling medium described in the system is the cryogenic rectification list The dew-point temperature of the material stream reduces corresponding liquid argon pressure at 1-7 DEG C under operating pressure in member.In certain embodiments In, the pressure of liquid low temperature cooling medium described in the system is the material under operating pressure in the cryogenic rectification unit The dew-point temperature for flowing stock reduces corresponding liquid argon pressure at 2-3 DEG C.In some embodiments, liquid described in the system is low The pressure 0.01-0.2MPa of warm cooling medium.

In some embodiments, the material of heat exchange is carried out in the system with the liquid low temperature cooling medium The pressure of stock is flowed for 0.1-1.0MPa, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

In some embodiments, heat source described in the system be by the cryogenic rectification unit to described At least part of admixture of gas to rectification process pressurizeed and cool down processing and obtain, the pressure of the heat source is The dew-point temperature of the material stream increases the pressure of corresponding argon at 1-7 DEG C under operating pressure in the cryogenic rectification unit, And the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

In some embodiments, the pressure of heat source described in the system is operating pressure in cryogenic rectification processing Under the dew-point temperature of the material stream corresponding argon when increasing 2-3 DEG C pressure, and low temperature described in the pressure ratio of the heat source The high 0.02-0.1MPa of the pressure of cooling medium.In some embodiments, the pressure of heat source described in the system is 0.15- 0.7MPa, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

In some embodiments, cryogenic rectification unit described in the system further includes one or more compressors, changes Hot device and throttle valve, the compressor is connected to the heat exchanger fluid and the heat exchanger and the throttle valve are in fluid communication, The admixture of gas to rectification process becomes high temperature and pressure gas mixing logistics to be processed through the compressor compresses Stock, and high temperature and pressure gas mixing logistics stock to be processed handles through cooling in the heat exchanger and becomes cryogenic high pressure Gas mixing logistics stock to be processed；And at least part of cryogenic high pressure gas mixing logistics stock to be processed flows through institute Stating after throttle valve is throttled expansion becomes the material stream.

In some embodiments, heat source described in the system is to handle and obtain through cooling in the heat exchanger A part of cryogenic high pressure gas mixing logistics stock to be processed.

In some embodiments, in the system in the heat exchanger, the liquid low temperature through gasifying, which condenses, to be situated between Matter carries out heat exchange with high temperature and pressure gas mixing logistics stock to be processed and condenses the liquid low temperature through gasifying Medium by after re-heat become purifying argon gas product, and the high temperature and pressure it is to be processed gas mixing logistics stock-traders' know-how cooling processing Become cryogenic high pressure gas mixing logistics stock to be processed afterwards.

In some embodiments, throttle valve described in the system is also in fluid communication with the reboiler, the heat source After carrying out heat exchange with the liquid argon of the purifying obtained through condensation in the reboiler, through the throttle valve throttling expansion And become a part of the material stream.

In some embodiments, the temperature of liquid low temperature cooling medium described in the system is -170 DEG C to -198 ℃。

In some embodiments, the temperature of material stream described in the system is -165 DEG C to -197 DEG C, and described The temperature of cryogenic condensation medium is at least 1-5 DEG C lower than the temperature of the material stream.

In some embodiments, the temperature of the liquid argon of the purifying obtained in the system through condensation is -160 DEG C To -196 DEG C, and the temperature of the liquid argon of the purifying is 0.5 DEG C to 5 DEG C lower than the temperature of the material stream.

In some embodiments, the temperature of heat source described in the system is -170 DEG C to -195 DEG C, and the heat source Temperature it is at least 1-5 DEG C higher than the temperature of the liquid argon of the purifying.

It in some embodiments, include adsorbent in absorbing unit described in the system, and the adsorbent includes Following is one or more: active carbon, activated alumina, modified silica-gel, carbon molecular sieve, natural zeolite, modified zeolite, sial base Molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, metal-organic framework material and their mixture.

In some embodiments, the system also includes at least one control unit, wherein described control unit and institute State the pretreatment unit, catalytic oxidation unit, the deacidification unit, the absorbing unit, first buffer cell, described Second buffer cell and the cryogenic rectification unit are operably connected, with adjust the temperature of the system, pressure, and/or The circulation style and/or flow of fluid in the system.

Those skilled in the art can from detailed description below in easily have insight into the other aspects of the disclosure and excellent Gesture.The illustrative embodiments of the disclosure only have been shown and described in detailed description below.As those skilled in the art will recognize Know, content of this disclosure enables those skilled in the art to be modified without de- disclosed specific embodiment Spirit and scope from invention involved by the application.Correspondingly, the description in the drawing and description of the application is only example Property, rather than be restrictive.

Detailed description of the invention

The specific features invented involved in the application are as shown in the appended claims.By reference in more detail below The illustrative embodiments and attached drawing of description better understood when the application involved the characteristics of inventing and advantage.To attached drawing letter Want specification as follows:

Fig. 1 shows the schematic diagram of an example of system provided herein.

Fig. 2 shows the experiment curv that argon concentration changes over time in monocrystalline silicon production.

Specific embodiment

Illustrate the embodiment of the present application by particular specific embodiment below, those skilled in the art can be by this Specification disclosure of that is easily realized by other advantages and effect of the present application.

In this application, " ppm " is often referred to parts per million, i.e., accounts for whole system with the quality of certain substance Quality part per million or account for whole system volume part per million come the concentration indicated, also referred to as parts per million concentration.Example Such as, when whole system is solution system, 1ppm can be equal to 1mg/L.In another example 1ppm can be waited when whole system is solid In 1 μ g/g.

In this application, " ppb " is often referred to parts per billion, i.e., accounts for whole system with the quality of certain substance 1,000,000,000 points of 1,000,000,000 points of the quality volumes for comparing or accounting for whole system than come the concentration that indicate.For example, when whole system is molten When liquid system, 1ppb can be equal to 1 μ g/L.In another example 1ppb can be equal to 1 μ g/Kg when whole system is solid.

In this application, " fluid " is often referred to fixed mass and the object without fixed shape, such as liquids and gases.

In this application, " cryogenic condensation medium " is often referred to that gas and/or liquid to be processed can be made to meet by heat exchange Cold and condensation substance.For example, the cryogenic condensation medium in the application can be liquid nitrogen, liquid argon and/or liquid CO 2 etc..

In this application, " adsorption treatment " is often referred to physical absorption and/or chemisorption performance using adsorbent, passes through The method that adsorbent realizes separation for the difference of the adsorption capacity of different component in mixture.It is not intended to be bound by theory, During the adsorption treatment, to realize that circulate operation can regenerate used adsorbent (as by adjusting pressure Power and/or temperature).For example, the adsorption treatment may include pressure-variable adsorption, temp.-changing adsorption and/or alternating temperature pressure-variable adsorption etc..

In this application, " condensation process " is interchangeably used with " condensation ", and typically refers to through cryogenic condensation medium With the heat exchange between gas and/or liquid to be processed, some or all of make in gas and/or liquid to be processed component The process condensed to the cold.

In this application, " liquid nitrogen " is often referred to the liquid form of nitrogen, and " liquid argon " is often referred to the liquid form of argon gas, " liquid Body carbon dioxide " is often referred to the liquid form of carbon dioxide.

In this application, " pressure-variable adsorption " is usually using adsorbent for different in mixture (such as admixture of gas) Characteristic that the difference of the adsorption capacity of component changes in pressure change and the method for realizing separation.For example, pressure-variable adsorption It may include the pressure-variable adsorption based on balancing effect, the pressure-variable adsorption based on kinetic effect and the transformation based on steric effect Absorption etc..Pressure-variable adsorption based on balancing effect is usually the difference for utilizing different component molecule equilibrium adsorption capacity on the sorbent It is separated.Pressure-variable adsorption based on kinetic effect be usually be to be diffused into adsorbent pores according to different component molecule Rate is different, appropriate to select the adsorbance of adsorption time control target components and non-target components to realize separation.Based on steric hindrance The pressure-variable adsorption of effect is usually that micropore in absorbent particles is utilized to realize to the difference of the steric effect of each group fractionated molecule point From.

In this application, " temp.-changing adsorption " is usually using adsorbent for different in mixture (such as admixture of gas) Characteristic that the difference of the adsorption capacity of component changes in temperature change and the method for realizing separation.

In this application, " pressure and temperature varying absorption " is usually using adsorbent in mixture (such as admixture of gas) Characteristic that the difference of the adsorption capacity of different component changes in pressure and temperature change and the method for realizing separation.

In this application, term " about " typically refers to change in the range of the following 0.5%-10% more than specified numerical value, Such as following 0.5% more than specified numerical value, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, it changes in the range of 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%.

In this application, " fluid communication " is often referred to that between two or more devices, the fluid in a device can be introduced In another device.

In this application, " compression " typically refers to increase the volume reduction of fluid and/or pressure by applying pressure Process.Compression can be realized by various means appropriate, for example, can be real by air blower, exhaust fan and/or compressor Now compress.

In this application, " catalysis oxidation " typically refers to the oxidation reaction carried out in the presence of a catalyst.

In this application, " deoxidation " typically refers to reduce the oxygen content in processed object (for example, admixture of gas) Or the process of the oxygen in the processed object of removal.

In this application, " rectification process " typically refers to make mixture obtain the distillation side of high-purity separation using reflux Method." cryogenic rectification " typically refers to the rectification process that (for example, -190 DEG C or lower) carry out at quite low temperatures.

In this application, it " has no substantial effect on " and typically refers to result, purpose, appearance or observable other aspects Substantive variation is not brought.

In this application, substantially free typically refer to content be not detected by conventional means or content not Characteristic or target needed for influencing.For example, substantially free can refer to content below about 5%, it is below about 4.5%, is below about 4%, it is below about 3.5%, is below about 3%, be below about 2.5%, be below about 2%, be below about 1.5%, is below about 1%, is below about 0.5%, it is below about 0.4%, is below about 0.3%, be below about 0.2%, be below about 0.1%, is below about 0.05% or lower.

In this application, " rectifying qualification buffer gas " typically refers to its component, state, physicochemical properties etc. and is adapted for The gas or gas composition of rectification process.For example, the oxygen content of rectifying qualification buffering gas can no more than about 40ppm, argon Content can be not less than 98%, and can be substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water and carbon Hydrogen compound.

In this application, " operating flexibility range " typically refers on or below the designated value or setting value in a certain range And the numberical range of operating effect is not influenced substantially.

In this application, " bulk processing " typically refers to the process that preliminary treatment is carried out to admixture of gas to be processed.

In this application, " precision processing " typically refers to that the admixture of gas through preliminary treatment is further processed, To remove impurity therein and/or increase the concentration of required component.

In this application, " deoxidation qualification buffer gas " typically refers to its component, state, physicochemical properties etc. and is adapted for The gas or gas composition of deoxidation treatment.For example, oxygen content in deoxidation qualification buffering gas can no more than about 40ppm, Argon content can be not less than 98%, and can be substantially free of mist of oil, dust or other particulate matters, carbon monoxide and hydrocarbon.

In this application, " reducibility gas " typically refer under suitable condition can or easily oxidized gas Or admixture of gas.For example, the reducibility gas may include carbon monoxide, hydrogen sulfide, methane or sulfur monoxide etc..

In this application, what " exhaust gas " typically referred to generate during the production (for example, monocrystalline silicon production) need to be by into one The gas or admixture of gas of step processing, discharge and/or recycling.

In this application, " environmental gas " typically refers to gas present in the external environment around system and/or device Or admixture of gas, such as air.

In this application, " Design cooling load flow " is typically referred to for specific device, system or equipment is default or calculates true Fixed Reasonable load flow, to guarantee that the device, system or equipment run well under the load flow.

In this application, " re-heat " be usually instigate target object, system or admixture of gas temperature reduce after again again The operation or process of secondary rising.

The method for being used to prepare liquid argon and/or argon gas product

On the one hand, this application provides a kind of methods of liquid argon for being used to prepare purifying and/or argon gas product.The method Can include: a) make admixture of gas to be processed be subjected to pretreatment with remove mist of oil, dust and other particulate matters therein to Obtain pretreated admixture of gas；Contact pretreated admixture of gas a) with catalytic oxidation unit, To make the reducibility gas in the admixture of gas by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；c) It contacts the admixture of gas through catalysis oxidation b) with deacidification unit, and is passed through proper proportion into the deacidification unit Hydrogen so that oxygen content therein be reduced to 2ppm or less (for example, about 0.1ppm hereinafter, about 0.5ppm hereinafter, about 1ppm with Under, about 1.5ppm hereinafter, about 2ppm hereinafter, about 5ppm or less), to obtain the admixture of gas of hydrogenated deoxidation；D) make c) The admixture of gas of the hydrogenated deoxidation contacted with absorbing unit, to remove the water in the admixture of gas, titanium dioxide Carbon and/or hydrocarbon, to obtain the admixture of gas to rectification process；E) gas to rectification process of measurement d) The flow of body mixture, and make the admixture of gas to rectification process by being buffered and gas is adjusted with rectifying qualification Flow is within the scope of the flow operating flexibility of rectification process；And f) pass through the admixture of gas to rectification process e) Cryogenic rectification processing is to remove nitrogen and hydrogen, to obtain the liquid argon and/or argon gas product of purifying.

In the method for the application, the hydrogen of proper proportion can be passed through into the deacidification unit so that wherein in c) Oxygen content be reduced to 0.1ppm or less (for example, can be about 0.1ppm hereinafter, about 0.05ppm hereinafter, about 0.04ppm hereinafter, About 0.03ppm hereinafter, about 0.02ppm hereinafter, about 0.01ppm or less).

Pretreatment may include for removing the mist of oil in admixture of gas to be processed, dust and the institute of other particulate matters There are adoptable means and method.In some embodiments, pretreatment can also include mixed for removing gas to be processed The means and method for closing water, carbon dioxide, and/or hydrocarbon in object etc., to obtain pretreated gas mixing Object.In the certain embodiments of the method for the application,

The pretreatment may include bulk processing and accurate processing, and the bulk processing can be in the advance of the accurate processing Row.

The bulk processing may include using selected from following one or more means: adsorbing mist of oil using asphalt felt, passes through Filter device filters dust, removes mist of oil and dust by water spray, or pass through rotating device separation removal mist of oil and dust, And/or generate the water comprising microbubble and by the admixture of gas spray water comprising microbubble to be processed come Remove oil mist removing.The diameter of the microbubble can be for example, about 30-100 μm, 40-100 μm, 50-100 μm, and 60-100 μm, 70- 100 μm, 80-100 μm, 90-100 μm, 95-100 μm.In some embodiments, the bulk processing may include utilizing above-mentioned one Kind or multiple means alternately dedusting oil mist removing, to persistently remove the mist of oil in the admixture of gas to be processed, powder Dirt and other particulate matters.

The accurate processing may include using following one or more means: membrane filter, ceramic filter, metal mistake Filter and/or active carbon adsorber.

In method described herein, impurity to be removed may include but not in the admixture of gas to be processed Be limited to, such as other particulate matters such as mist of oil, dust, silicon powder, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water and/ Or hydrocarbon.

In some embodiments, the admixture of gas to be processed is the exhaust gas that monocrystaline silicon stove or ingot furnace generate.

In the method for the application, connect the pretreated admixture of gas with the catalytic oxidation unit Before touching, the oxygen concentration in the pretreated admixture of gas can measure.For example, when the measured oxygen concentration can be with It is at least 4% (v/v) (for example, at least about 4.5% (v/v), at least about 5% (v/v), at least about 6% (v/v), at least about 7% (v/v), at least about 8% (v/v), at least about 9% (v/v), at least about 10% (v/v) or higher) when, it can be by will be described At least part of pretreated admixture of gas discharges and is passed through deoxidation qualification buffering gas to allow its oxygen concentration be 4% (v/v) below (for example, be about 4% (v/v) hereinafter, about 3.5% (v/v) hereinafter, about 3% (v/v) hereinafter, about 2.5% (v/ V) hereinafter, about 2% (v/v) hereinafter, about 1.5% (v/v) hereinafter, about 1% (v/v) is below or lower).For example, when measured The oxygen concentration can be at least 2% (v/v) (for example, at least about 2.5% (v/v), at least about 3% (v/v), at least about 3.5% (v/v), at least about 4% (v/v), at least about 4.5% (v/v), at least about 5% (v/v), at least about 5.5% (v/v) or It is higher) when, it can be by the way that at least part of the pretreated admixture of gas to be discharged to and is passed through deoxidation qualification buffering Gas come allow its oxygen concentration be 2% (v/v) below (for example, being about 2% (v/v) hereinafter, about 1.5% (v/v) is hereinafter, about 1% (v/v) hereinafter, about 0.5% (v/v) is below or lower).For example, when the measured oxygen concentration is more than about 4% (v/v), The pretreated admixture of gas can be completely or partially emitted into exhaust gas storage tank or other suitable places, and made remaining The pretreated admixture of gas is mixed with deoxidation qualification buffering gas, for contacting with the catalytic oxidation unit. In some embodiments, when the measured oxygen concentration can be 4% (v/v), which can be mixed It closes object all to empty, and the deoxidation qualification buffering gas in storage tank is passed through the catalytic oxidation unit.

The hydrogen being passed through into the deacidification unit and the oxygen in the measured pretreated admixture of gas Molar ratio can be about 2.2:1 to about 3:1, for example, about 2.4:1 to about 3.2:1, about 2.5:1 are to about 3.1:1, about 2.6:1 is to about 3:1, about 2.7:1 are to about 3:1, about 2.8:1 to about 3:1, about 2.9:1 to about 3:1, or about 2.9:1 to about 3:1 etc..

In the method for the application, the catalysis oxidation can be by the reproducibility including hydrocarbon and carbon monoxide Gas is oxidized to water and carbon dioxide.When the molar fraction of oxygen in the pretreated admixture of gas is less than described in oxidation When the molar fraction of oxygen needed for pretreated gas, then oxygen is added, makes oxygen in the pretreated admixture of gas The molar fraction of gas can be 10-50% higher than the molar fraction of oxygen needed for the pretreated gas (for example, high 10- 50%, 12-50%, 15-50%, 15-45%, 20-45%, 25-45%, 25-40%, 25-35%, 25-30% or 28- 30%).

The catalytic oxidation unit may include catalyst, and the catalyst can be selected from the following group: Carulite catalyst, platinum Catalyst, palladium catalyst and any combination thereof.

In the method for the application, the deacidification unit may include catalyst, and the catalyst can be selected from the following group: Cu, platinum catalyst, palladium catalyst and any combination thereof.

In the method for the application, when the molar fraction of oxygen in the pretreated admixture of gas is greater than 2% (for example, being greater than 3%, being greater than 4%, be greater than 5%, be greater than 6%, be greater than 7%, be greater than 8%, be greater than 9%, be greater than 10% or big In 15%) or the pretreated admixture of gas carry out the temperature of the catalysis oxidation be more than 400 degrees Celsius when (for example, More than 410 degrees Celsius, 420 degrees Celsius, 430 degrees Celsius, 440 degrees Celsius, 450 degrees Celsius, 460 degrees Celsius, 470 degrees Celsius, 480 Degree Celsius, 490 degrees Celsius or 500 degrees Celsius), the catalytic oxidation unit may include segmentation reactor；And/or work as institute State the temperature that deacidification unit is reacted when being more than 400 degrees Celsius (for example, more than 410 degrees Celsius, 420 degrees Celsius, it is 430 Celsius Degree, 440 degrees Celsius, 450 degrees Celsius, 460 degrees Celsius, 470 degrees Celsius, 480 degrees Celsius, 490 degrees Celsius or 500 degrees Celsius), institute The deacidification unit stated may include segmentation reactor.

The catalysis oxidation can about 50 DEG C to about 400 DEG C at a temperature of carry out.For example, the catalysis oxidation can be about 60 DEG C at a temperature of about 350 DEG C, at a temperature of about 70 DEG C to about 330 DEG C, at a temperature of about 80 DEG C to about 320 DEG C, about 90 DEG C extremely At a temperature of about 310 DEG C, at a temperature of about 100 DEG C to about 300 DEG C, at a temperature of about 110 DEG C to about 290 DEG C, about 120 DEG C to about At a temperature of 280 DEG C, at a temperature of about 130 DEG C to about 270 DEG C, at a temperature of about 140 DEG C to about 260 DEG C, about 150 DEG C to about It is equal at a temperature of about 160 DEG C to about 240 DEG C to carry out at a temperature of 250 DEG C.

In method described herein, the hydrogen being passed through can come from the hydrogen being in fluid communication with the deacidification unit Storage tank.In some embodiments, the hydrogen being passed through comes from hydrogen generator, and the hydrogen generator can be by, for example, point Solution, methanol decomposition method or steam methane reforming (Steam Methane Reforming, SMR) etc. generate hydrogen.

In the certain embodiments of herein described method, the absorbing unit may include pressure-swing absorption apparatus, alternating temperature Adsorbent equipment and/or alternating temperature pressure-swing absorption apparatus.It may include adsorbent in the absorbing unit.The adsorbent can: 1) be State large amount of adsorption, separation are high and desorb easy adsorbent；2) there is enough wear-resistant strengths and compression strength；And/or 3) there is chemical inertness to all gases or admixture of gas to be separated.For example, the adsorbent may include following one kind Or it is a variety of: active carbon, carbon molecular sieve, natural zeolite, modified zeolite, sial based molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, Metal-organic framework material and their mixture.

In the certain embodiments of herein described method, at least two absorbing units can be used, and described at least When one of two absorbing units are adsorbed, another absorbing unit therein is regenerated, so that described at least two inhale Coupon member is alternately adsorbed and is regenerated, and is then realized and is persistently carried out adsorption treatment to the admixture of gas.Described at least two A absorbing unit can include pressure-swing absorption apparatus, temperature swing absorption unit and/or alternating temperature pressure-swing absorption apparatus each independently.

In method described herein, rectifying qualification buffering gas can be adapted for rectification process gas or Gas composition.For example, in the rectifying qualification buffering gas oxygen content can be 0.1ppm or less (for example, be 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less), argon content not less than 98% (for example, be not less than 97%, 96%, 95%, 94%, 93%, 92%, 91%, 90%, 88%, 86%, 85%, 80%), and substantially free of mist of oil, dust or other particulate matters, one Carbonoxide, carbon dioxide, water and hydrocarbon.

In this application, for example, the partial size for referring to oil droplet in the rectifying qualification buffering gas substantially free of mist of oil It can be about 0.1 μm or less (for example, being 0.08 μm or less, 0.06 μm or less, 0.04 μm or less, 0.02 μm or less, 0.15 μm or less Or 0.01 μm or less).In this application, for example, described refer to the rectifying qualification buffering gas without dust or other particulate matters The partial size of middle dust or other particulate matters can be about 0.1 μm or less (for example, for 0.08 μm or less, 0.06 μm or less, 0.04 μm with Under, 0.02 μm or less, 0.15 μm or less or 0.01 μm or less).In this application, for example, it is described substantially free of carbon monoxide Refer to the content of carbon monoxide in rectifying qualification buffering gas can be about 0.1ppm or less (for example, for 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).In this application, for example, described refer to the rectifying substantially free of carbon dioxide Qualification buffering gas in carbon dioxide content can be 0.1ppm or less (for example, be 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).In some embodiments, the dew point temperature that the rectifying qualification buffering gas is referred to substantially free of water Degree is about -50 DEG C or less (for example, about -90 DEG C or less, -80 DEG C or less, -70 DEG C or less, -60 DEG C or less, -55 DEG C or less or -50 DEG C or less).In this application, for example, described refer to non-first in the deoxidation qualification buffering gas substantially free of hydrocarbon The content of alkane total hydrocarbon be about 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm with Under, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).

In method described herein, deoxidation qualification buffering gas can be adapted for deoxidation treatment gas or Gas composition.For example, oxygen content in deoxidation qualification buffering gas can for 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less, 0.01ppm or less or 0.1ppm or less), argon content can be (not low for example, be not less than 99% not less than 98% In 99.5%, it is not less than 99.9%, is not less than 99.99% or higher).In addition, the deoxidation qualification buffering gas can substantially not Containing mist of oil, dust or other particulate matters, carbon monoxide and hydrocarbon

In this application, for example, the partial size for referring to oil droplet in the deoxidation qualification buffering gas substantially free of mist of oil It can be about 0.1 μm or less (for example, about 0.08 μm or less, 0.06 μm or less, 0.04 μm or less, 0.02 μm or less, 0.15 μm or less Or 0.01 μm or less).In this application, for example, described refer to the deoxidation qualification buffering gas without dust or other particulate matters The partial size of middle dust or other particulate matters can be about 0.1 μm or less (for example, about 0.08 μm or less, 0.06 μm or less, 0.04 μm with Under, 0.02 μm or less, 0.15 μm or less or 0.01 μm or less).In this application, for example, it is described substantially free of carbon monoxide Refer to the content of carbon monoxide in deoxidation qualification buffering gas can be about 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).In this application, for example, described refer to the deoxidation substantially free of carbon dioxide The content of carbon dioxide can be 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm in qualification buffering gas Below, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm with Under).In some embodiments, the dew-point temperature that the deoxidation qualification buffering gas is referred to substantially free of water is about -40 DEG C or less (for example, about -90 DEG C or less, -80 DEG C or less, -70 DEG C or less, -60 DEG C or less, -50 DEG C or less or -40 DEG C or less). In this application, for example, described refer to non-methane total hydrocarbons in the deoxidation qualification buffering gas substantially free of hydrocarbon Content be about 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).

In method described herein, the flow operating flexibility range of the rectification process can be the rectification process The 60% to 120% of Design cooling load flow is the Design cooling load for example, being the 75% to 115% of the Design cooling load flow The 80% to 110% of flow, be the Design cooling load flow 85% to 105%, be the Design cooling load flow 90% to 100%, it is the 95% to 105% of the Design cooling load flow, is the 99% to 102% of the Design cooling load flow.

In method described herein, the liquid argon and/or argon gas product of the purifying may include liquid argon, argon gas and/or The mixture of liquid argon and argon gas.

In method described herein, it is useless that the admixture of gas to be processed is that monocrystaline silicon stove or ingot furnace generate Gas, and method described herein may also include, and before making the exhaust gas be subjected to pretreatment, control the monocrystaline silicon stove or casting The discharge opportunity of exhaust gas in ingot furnace, so that the content of argon gas is maintained in the admixture of gas to be pre-treated 80% (v/v) is (for example, at least 85% (v/v), at least 90% (v/v), at least 95% (v/v), at least 98% (v/v), at least 99% (v/v), at least 99.5% (v/v), at least 99.9% (v/v), at least 99.99% (v/v) or higher).In certain implementations In mode, the admixture of gas to be pre-treated can be the exhaust gas from two or more monocrystaline silicon stoves or ingot furnace, And when any of the two or more monocrystaline silicon stoves or ingot furnace need to be in fluid communication with environmental gas, it can stop Exhaust gas is discharged into the admixture of gas to be pre-treated from the monocrystaline silicon stove or ingot furnace.For example, any when needing to open The opening (for example, when the product for needing to take out in furnace or when needing that raw material is added into furnace) of monocrystaline silicon stove or ingot furnace and make When air in environment is entered in furnace, it can disconnect and fluidly connect (example between the monocrystaline silicon stove or ingot furnace and pretreatment unit Such as, by closing the control valve that the monocrystaline silicon stove or ingot furnace and the pretreatment unit is in fluid communication), so that it is guaranteed that institute Air is stated not with blend gas mix to be pre-treated, then ensures containing for argon gas in the admixture of gas to be pre-treated Amount remains at least 80% (v/v) (for example, at least 85% (v/v), at least 90% (v/v), at least 95% (v/v), at least 98% (v/v), at least 99% (v/v), at least 99.5% (v/v), at least 99.9% (v/v), at least 99.99% (v/v) or higher).

In method described herein, the content of argon can be at least about in the liquid argon and/or argon gas product of the purifying 96%.For example, the content of argon can be at least about 97%, at least about 98% in the liquid argon and/or argon gas product of the purifying, at least About 99%, at least about 99.9%, at least about 99.99%, at least about 99.999% or higher.

In method described herein, the mode of the hydrogen and the hydrogen being passed through are passed through in Xiang Suoshu deacidification unit Amount have no substantial effect on it is described b) in catalytic oxidation efficiency.For example, can include catalyst into the deacidification unit The intermediate position of filler device is passed through suitable hydrogen, so that be passed through hydrogen be avoided to send out before the catalytic oxidation with oxygen Raw reaction.

In method described herein, the cryogenic rectification processing can include: i) gas to rectification process is mixed At least part for closing object becomes material stream；Ii the material stream and liquid low temperature cooling medium i)) is made to carry out hot friendship It changes, so that at least part of the liquid low temperature cooling medium is made to be gasified, and at least part in the material stream Argon gas is condensed into liquid argon；And iii) make ii) in through condensation obtain the purifying liquid argon and heat source carry out heat exchange, from And the liquid argon of the purifying is made to gasify as the argon gas product of purifying.The liquid low temperature cooling medium can be liquid nitrogen or liquid argon.

In some embodiments, the liquid low temperature cooling medium is liquid argon.For example, ii) described in liquid low temperature Cooling medium is liquid argon.In another example ii) described in liquid low temperature cooling medium liquid argon be to through condensation obtain the purifying Liquid argon carry out the low pressure liquid argon that obtains after throttling expansion.In another example the ii of the method) in the liquid through gasifying it is low Warm cooling medium becomes the argon gas product of purifying after re-heat.

In this application, the ii of the method) described in liquid low temperature cooling medium pressure than the cryogenic rectification In processing under operating pressure the material stream dew-point temperature reduce 1-7 DEG C (for example, reduce by 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C) when corresponding liquid argon pressure.For example, the pressure of the liquid low temperature cooling medium can be handled for the cryogenic rectification When the dew-point temperature of the material stream reduces 2-3 DEG C under middle operating pressure (for example, 2 DEG C are reduced, and 2.5 DEG C, 2.8 DEG C, 3 DEG C, 3.2 DEG C, 3.5 DEG C) corresponding liquid argon pressure.For example, the pressure of the liquid low temperature cooling medium can be 0.02-0.2Mpa (example Such as, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.10Mpa, 0.12Mpa, 0.14Mpa, 0.16Mpa, 0.18Mpa or 0.2Mpa)。

In this application, ii) in carry out heat exchange with the liquid low temperature cooling medium the material stream press Power be 0.1-1.0MPa (for example, 0.001Mpa, 0.01Mpa, 0.1Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa, 0.9Mpa, 1.0Mpa, 1.5Mpa, 2.0Mpa), and its pressure is situated between than the cryogenic condensation The high 0.02-0.1Mpa of the pressure of matter (for example, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).

In this application, the iii of the method) described in heat source be by the gas to rectification process e) At least part of mixture carries out pressurization and heating treatment and obtains, and the pressure of the heat source can be at the cryogenic rectification In reason under operating pressure the material stream dew-point temperature increase 1-7 DEG C (for example, increase 0.5 DEG C, 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C, 8 DEG C, 9 DEG C, 10 DEG C, 12 DEG C) when corresponding argon pressure, and the pressure of the heat source is than the low temperature cold Solidifying medium the high 0.02-0.1Mpa of pressure (for example, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa)。

For example, the pressure of the heat source of the method can be the material under operating pressure in cryogenic rectification processing The dew-point temperature for flowing stock increases 2-3 DEG C (for example, increasing 0.5 DEG C, 0.8 DEG C, 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 2.8 DEG C or 3 DEG C) When corresponding argon pressure, and the pressure of the heat source is than the high 0.02-0.1Mpa (example of pressure of the cryogenic condensation medium Such as, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).In another example the pressure of the heat source can For 0.15-0.7MPa (for example, 0.15Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa), And the pressure of the heat source than the cryogenic condensation medium the high 0.02-0.1Mpa of pressure (for example, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).

In method described herein, the admixture of gas to rectification process can be handled as follows and be obtained The material stream: ia) make the admixture of gas to rectification process e) wait locating as high temperature and pressure through compressor compresses The gas mixing logistics stock of reason；Ib) make ia) high temperature and pressure gas mixing logistics stock to be processed in heat exchanger through dropping Temperature handles and becomes cryogenic high pressure gas mixing logistics stock to be processed；And ic) make ib) the cryogenic high pressure it is to be processed At least part of gas mixing logistics stock becomes the material stream after throttling expansion.For example, the heat source can be ib) A part of the cryogenic high pressure of middle acquisition gas mixing logistics stock to be processed.

In method described herein, the admixture of gas to rectification process can be compressed first and be allowed to Gas mixing logistics stock to be processed as high temperature and pressure.It then, can be in heat exchanger to the to be processed of the high temperature and pressure Gas mixing logistics stock carry out cooling processing, and obtain the gas mixing logistics stock to be processed of cryogenic high pressure.Later, it can incite somebody to action A part of cryogenic high pressure gas mixing logistics stock to be processed can be used as the heat source, and the cryogenic high pressure is to be processed The material stream that another part of gas mixing logistics stock further decreases after throttling expansion as temperature and pressure.

For example, can be by keeping the liquid low temperature cooling medium through gasifying and high temperature and pressure gas to be processed mixed Close logistics stock carry out heat exchange in the heat exchanger and make the liquid low temperature cooling medium through gasifying by re-heat after become The argon gas product of purifying, and the gas mixing logistics stock-traders' know-how cooling for keeping the high temperature and pressure to be processed handles and becomes low temperature height Press gas mixing logistics stock to be processed.In method described herein, the heat source can be with described through the pure of condensation acquisition After the liquid argon of change carried out heat exchange, a part of the material stream is expanded into through throttling.

In method described herein, the temperature of the liquid low temperature cooling medium can be -170 DEG C to -198 DEG C (for example, being -170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, -195 DEG C or -198 DEG C).For example, the material stream Temperature can be -165 DEG C to -197 DEG C (for example, be -165 DEG C, -170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, - 195 DEG C or -197 DEG C), and the temperature at least 1-5 DEG C of (example low than the temperature of the material stream of the cryogenic condensation medium Such as, low at least 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C).For example, through described in condensation acquisition The temperature of the liquid argon of purifying can for -160 DEG C to -196 DEG C (for example, about -200 DEG C hereinafter, about -190 DEG C hereinafter, about -180 DEG C Hereinafter, about -170 DEG C hereinafter, about -160 DEG C hereinafter, about -150 DEG C hereinafter, about -140 DEG C hereinafter, about -130 DEG C or less), and The temperature of the liquid argon of the purifying it is about 0.5 DEG C to about 5 DEG C low than the temperature of the material stream (for example, low 0.5 DEG C, 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C).For example, the temperature of the heat source can for -170 DEG C to - 195 DEG C (for example, being -170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, -193 DEG C or -195 DEG C), and the heat source Temperature than at least 1-5 DEG C of the temperature height of the liquid argon of the purifying (for example, high at least 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C).

Positive displacement compressor (such as piston compressor or screw compressor) and/or speed mode can be used in the compression Compressor (for example, centrifugal compressor).

It is allowed to obtain in general, centrifugal compressor transfers energy to the gas continuously flowed in pipeline mainly by high speed blade Great speed, while improving pressure, have unit power unit light-weight, small in size, land occupation is few, without air valve, piston, For the quick-wear parts such as piston ring, it can be achieved that oil free compression, smooth running is reliable, and Equipment Foundations are light, and gas supply pulsating nature is small, maintenance cost Low advantage.

In general, one of screw compressor category displacement type Clothoid type compressor, due to not occurring remaining in clearance volume The reflation process of residual air body, with the gap of very little between rotor and casing, between each other without sliding friction, within Efficiency and mechanical efficiency are relatively high.Since it is without air inlet-exhaust valve device, few easy workout part, maintenance management is convenient, long service life.

In general, piston compressor is traditional positive displacement compressor, and it is most widely used at present, there is broad work pressure Power range, variable working condition adaptability are stronger.

In the application, the method may also include that the hydrogen for g) recycling and/or purifying and be removed in f).For example, can pass through Cryogenic rectification, flash distillation, and/or absorption are to recycle and/or purify the hydrogen.

The cryogenic rectification may include under the conditions of the temperature of deep cooling (for example, at least partly temperature at or below- At 110 DEG C, for instance in or lower than -120 DEG C, at or below -130 DEG C, at or below -140 DEG C, at or below -150 DEG C, at or below -160 DEG C, at or below -170 DEG C, at or below -180 DEG C, at or below -190 DEG C, and/or At or below -200 DEG C, or lower) method that carries out rectifying.Flash distillation may include making to be heated to the substance close to its boiling point (for example, gas-liquid mixture etc.) abruptly enters negative pressure space, to realize the separation of lighter component and heavy constituent.Absorption may include Pressure-variable adsorption, temp.-changing adsorption or pressure and temperature varying absorption.Pressure-variable adsorption is typically referred to using adsorbent for mixture (such as gas Mixture) in different component adsorption capacity the difference characteristic to change in pressure change and the method for realizing separation. Temp.-changing adsorption typically refers to the difference using adsorbent for the adsorption capacity of different component in mixture (such as admixture of gas) The different characteristic to change in temperature change and the method for realizing separation.

It is used to prepare the liquid argon of purifying and/or the system of argon gas product

On the other hand, this application provides the systems of a kind of liquid argon for being used to prepare purifying and/or argon gas product.Institute State system can include: pretreatment unit, with gas mixing fluid communication to be processed and remove mist of oil therein, dust and Other particulate matters are to obtain pretreated admixture of gas；Catalytic oxidation unit connects with the pretreatment unit fluid Logical, the catalytic oxidation unit makes the reducibility gas in the pretreated admixture of gas by catalysis oxidation, to obtain Admixture of gas through catalysis oxidation；Deacidification unit is in fluid communication with the catalytic oxidation unit, in Xiang Suoshu deacidification unit After being passed through the hydrogen of proper proportion, the deacidification unit is reduced to the oxygen content in the admixture of gas through catalysis oxidation 2ppm (for example, about 0.1ppm hereinafter, about 0.5ppm hereinafter, about 1ppm hereinafter, about 1.5ppm hereinafter, about 2ppm hereinafter, about 5ppm Below) hereinafter, to obtain the admixture of gas of hydrogenated deoxidation；Absorbing unit is in fluid communication, institute with the deacidification unit Stating absorbing unit includes water, the carbon dioxide and/or hydrocarbon in admixture of gas of the adsorbent to remove the hydrogenated deoxidation Compound, to obtain the admixture of gas to rectification process；First buffer cell, it is mixed with the gas to rectification process It closes fluid communication and includes the flow rate-measuring device for measuring the flow of the admixture of gas to rectification process, it is described Gas is buffered comprising rectifying qualification in first buffer cell, the rectifying qualification buffering gas is used to adjust for described to rectification process The flow of admixture of gas, and make the flow within the scope of flow operating flexibility of rectification process；And cryogenic rectification unit, It is in fluid communication with the absorbing unit and first buffer cell, described in the admixture of gas of rectification process to remove Nitrogen and hydrogen, to obtain the liquid argon and/or argon gas product of purifying.

System described herein may also include hydrogen retrieval unit, and the hydrogen retrieval unit can be with the cryogenic rectification unit It is in fluid communication and is used to recycle and/or purify the hydrogen being removed in the cryogenic rectification unit.For example, the hydrogen retrieval list Member may include selected from following device: cryogenic rectification device, flash distillation plant, and/or adsorbent equipment.

In system described herein, the pretreatment unit may include bulk processing device and accurate processing unit.Institute Stating bulk processing device and the accurate processing unit can be in fluid communication.The bulk processing device may include selected from following one kind or It is a variety of: asphalt felt, dust filtering device, water spray system, and/or the rotating device for removing mist of oil and dust simultaneously.Example Such as, the water spray system can produce the water comprising microbubble and by spraying the packet to the admixture of gas to be processed Water containing microbubble is made a return journey oil mist removing.The diameter of the microbubble can be for example, about 30-100mm, 40-100mm, 50- 100mm, 60-100mm, 70-100mm, 80-100mm, 90-100mm, 95-100mm.

In some embodiments, may include above-mentioned one or more devices in the bulk processing device, it is described a kind of or A variety of devices can alternately dedusting oil removing, thus persistently remove the oil in the admixture of gas to be processed, dust and its Its particulate matter.

For example, the bulk processing device may include carrying out oil removing by gas-liquid separation device.The gas-liquid device can be one Cover combined type knockout drum.Following step separation oil removing: first step oil removing, rotation can be used in the combined type knockout drum Wind separator is removed compared with larger oil droplet.The drop carried secretly in the air-flow of certain speed is tangentially entered under separator by gas phase import Portion, by the density contrast of gas and oil, oil droplet is thrown toward inner tank wall, is guided to bottom along wall surface, and air-flow rises, through collision water conservancy diversion gear Plate carries out collision separation, enters back into next stage separation.Second step oil removing is separated using the further gas and oil of two layers of spiral board.Third Oil removing is walked, is separated using the latter step gas and oil of vortex-flow and defrosting device (ZL200710018412.8).Air-flow forms eddy flow, drop after entering It is thrown to wall surface and is gathered into liquid film and flows down, the certain angle of blade lean is conducive to oil droplet and converges and flow to tower wall, multiple S Type channel increases air flow contacts time and collision separation probability.Gas phase after separation is discharged by top of the tank gaseous phase outlet N2. Sump oil after second level and the separation of three-level gas and oil converges to being discharged together.

The precision processing unit may include one of the following or a variety of: membrane filter, ceramic filter, metal filtration Device and/or active carbon adsorber.

In system described herein, impurity to be removed in the admixture of gas to be processed can include: oil, powder Other particulate matters such as dirt, silicon powder, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water and/or hydrocarbon.Example Such as, the exhaust gas that the admixture of gas to be processed can generate for monocrystaline silicon stove or ingot furnace.

System described herein may also include air inlet adjustment valve, and the air inlet adjustment valve controls the monocrystaline silicon stove or casting Fluid communication between ingot furnace and the pretreatment unit, so that argon gas contains in the admixture of gas to be pre-treated Amount is maintained at 80% (for example, at least 85% (v/v), at least 90% (v/v), at least 95% (v/v), at least 98% (v/ V), at least 99% (v/v), at least 99.5% (v/v), at least 99.9% (v/v), at least 99.99% (v/v) or higher).Example Such as, the system may include two or more described air inlet adjustment valves, wherein each air inlet adjustment valve can independently control one Fluid communication between a individual monocrystaline silicon stove or ingot furnace and the pretreatment unit, and work as any one described monocrystalline silicon When furnace or ingot furnace need to be in fluid communication with environmental gas, corresponding air inlet adjustment valve block the monocrystaline silicon stove or ingot furnace with it is described Fluid communication between pretreatment unit.In some embodiments, the admixture of gas to be pre-treated is from two Or more monocrystaline silicon stove or ingot furnace exhaust gas, and when any in the two or more monocrystaline silicon stoves or ingot furnace It is a when need to be in fluid communication with environmental gas, can by close the air inlet adjustment valve stop from the monocrystaline silicon stove or ingot furnace to Exhaust gas is discharged in the admixture of gas to be pre-treated.For example, when the opening for needing to open any monocrystaline silicon stove or ingot furnace (for example, when the product for needing to take out in furnace or when needing that raw material is added into furnace) and enters the air in environment in furnace When, the monocrystalline silicon can be disconnected by adjusting the air inlet adjustment valve while opening the monocrystaline silicon stove or ingot furnace is open Fluidly connecting between furnace or ingot furnace and pretreatment unit, so that it is guaranteed that the air not with admixture of gas to be pre-treated Mixing, then ensures that the content of argon gas in the admixture of gas to be pre-treated remains at least 80% (v/v) (for example, extremely Few 85% (v/v), at least 90% (v/v), at least 95% (v/v), at least 98% (v/v), at least 99% (v/v), at least 99.5% (v/v), at least 99.9% (v/v), at least 99.99% (v/v) or higher).

System described herein may also include oxygenation measurement unit, and the oxygenation measurement unit can be with the pretreatment unit stream Body is connected to and can measure the oxygen concentration in the pretreated admixture of gas.

System described herein may also include the second buffer cell, and second buffer cell may include that deoxidation qualification is slow Qi of chong channel ascending adversely and with the pretreated gas mixing fluid communication.For example, when the oxygen concentration measured is more than about 4% (v/ V) (for example, at least about 4.5% (v/v), at least about 5% (v/v), at least about 6% (v/v), at least about 7% (v/v), at least About 8% (v/v), at least about 9% (v/v), at least about 10% (v/v) or higher) when, it can be by the pretreated gas mixing At least part of object discharges and is passed through deoxidation into the pretreated admixture of gas from second buffer cell Qualification buffers gas to make oxygen concentration therein no more than about 4% (v/v) (for example, being about 4% (v/v) hereinafter, about 3.5% (v/v) Hereinafter, about 3% (v/v) hereinafter, about 2.5% (v/v) hereinafter, about 2% (v/v) hereinafter, about 1.5% (v/v) hereinafter, about 1% (v/ V) below or lower).For example, when the oxygen concentration that measure more than about 2% (v/v) (for example, at least about 2.5% (v/v), At least about 3% (v/v), at least about 3.5% (v/v), at least about 4% (v/v), at least about 4.5% (v/v), at least about 5% (v/ V), at least about 5.5% (v/v) or higher) when, at least part of the pretreated admixture of gas can be discharged simultaneously Deoxidation qualification buffering gas is passed through into the pretreated admixture of gas from second buffer cell to make oxygen therein Concentration no more than about 2% (v/v) (for example, be about 2% (v/v) hereinafter, about 1.5% (v/v) hereinafter, about 1% (v/v) hereinafter, about 0.5% (v/v) is below or lower).

In system described herein, the catalytic oxidation unit can by include hydrocarbon and carbon monoxide also Originality gas is oxidized to water and carbon dioxide.The catalytic oxidation unit may include catalyst, and the catalyst can be selected from down Group: Carulite catalyst, platinum catalyst, palladium catalyst and any combination thereof.For example, the catalytic oxidation unit may include One or more catalytic oxidation reaction devices are (for example, one or more packed towers, wherein each packed tower may include one or more A catalysis oxidation bed), wherein each reaction unit can independently include one or more catalyst.The catalysis oxygen Change can about 50 DEG C to about 400 DEG C at a temperature of carry out.For example, the catalysis oxidation can be in about 60 DEG C to about 350 DEG C of temperature Under, at a temperature of about 70 DEG C to about 330 DEG C, at a temperature of about 80 DEG C to about 320 DEG C, at a temperature of about 90 DEG C to about 310 DEG C, about At a temperature of 100 DEG C to about 300 DEG C, at a temperature of about 110 DEG C to about 290 DEG C, at a temperature of about 120 DEG C to about 280 DEG C, about At a temperature of 130 DEG C to about 270 DEG C, at a temperature of about 140 DEG C to about 260 DEG C, at a temperature of about 150 DEG C to about 250 DEG C, about It is carried out at a temperature of 160 DEG C to about 240 DEG C.

In system described herein, after being passed through the hydrogen of proper proportion in the deacidification unit, the deacidification unit Make the oxygen content in the admixture of gas through catalysis oxidation be reduced to 0.1ppm or less (for example, can be about 0.1ppm with Under, about 0.05ppm hereinafter, about 0.04ppm hereinafter, about 0.03ppm hereinafter, about 0.02ppm hereinafter, about 0.01ppm or less).

The deacidification unit may include catalyst, and the catalyst can be selected from the following group: Cu, platinum catalyst, palladium catalyst, And any combination thereof.The deacidification unit may include one or more reaction units (for example, one or more packed tower, wherein Each packed tower may include one or more deoxidation beds), wherein each reaction unit can be independently comprising one or more The catalyst.

In system described herein, the hydrogen that is passed through in Xiang Suoshu deacidification unit with it is measured described preprocessed Admixture of gas in the molar ratio of oxygen can be about 2.2:1 to about 3:1, for example, about 2.4:1 is to about 3.2:1, about 2.5:1 To about 3.1:1, about 2.6:1 to about 3:1, about 2.7:1 to about 3:1, about 2.8:1 to about 3:1, about 2.9:1 to about 3:1, Huo Zheyue 2.9:1 to about 3:1 etc..

In system described herein, the hydrogen being passed through can come from the hydrogen being in fluid communication with the deacidification unit Storage tank.In some embodiments, the system comprises hydrogen generators for generating the hydrogen being passed through into the deacidification unit Gas.The hydrogen generator can be by, for example, a solution, methanol decomposition method or steam methane reforming (Steam Methane Reforming, SMR) etc. generate hydrogen.

In system described herein, the content of argon can be at least about in the liquid argon and/or argon gas product of the purifying 96%.For example, the content of argon can be at least about 97%, at least about 98% in the liquid argon and/or argon gas product of the purifying, at least About 99%, at least about 99.9%, at least about 99.99%, at least about 99.999% or higher.

In system described herein, the mode of the hydrogen and the hydrogen being passed through are passed through in Xiang Suoshu deacidification unit Amount has no substantial effect on the efficiency of the catalytic oxidation.For example, can include the filler of catalyst into the deacidification unit The intermediate position of device is passed through suitable hydrogen, so that it is anti-to avoid be passed through hydrogen from occurring before the catalytic oxidation with oxygen It answers.

It may include adsorbent in the absorbing unit in system described herein.The adsorbent can: 1) for dynamic Large amount of adsorption, separation are high and desorb easy adsorbent；2) there is enough wear-resistant strengths and compression strength；And/or 3) There is chemical inertness to all gases or admixture of gas to be separated.For example, the adsorbent may include following one kind or It is a variety of: active carbon, carbon molecular sieve, natural zeolite, modified zeolite, sial based molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, gold Belong to organic framework materials and their mixture.

It may include at least two absorbing units in system described herein, and when one of described at least two absorbing unit When being adsorbed, another absorbing unit therein is regenerated, so that at least two absorbing unit is alternately inhaled Attached and regeneration, then realizes that the admixture of gas to the hydrogenated deoxidation persistently carries out adsorption treatment.Described at least two inhale Coupon member can include pressure-swing absorption apparatus, temperature swing absorption unit and/or alternating temperature pressure-swing absorption apparatus each independently.

In system described herein, rectifying qualification buffering gas can be adapted for rectification process gas or Gas composition.For example, in the rectifying qualification buffering gas oxygen content can for 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less), argon content not less than 98% (for example, be not less than 97%, 96%, 95%, 94%, 93%, 92%, 91%, 90%, 88%, 86%, 85%, 80%), and substantially free of mist of oil, dust or other particulate matters, one Carbonoxide, carbon dioxide, water and hydrocarbon.

In this application, for example, the partial size for referring to oil droplet in the rectifying qualification buffering gas substantially free of mist of oil It can be about 0.1 μm or less (for example, about 0.08 μm or less, 0.06 μm or less, 0.04 μm or less, 0.02 μm or less, 0.15 μm or less Or 0.01 μm or less).In this application, for example, described refer to the rectifying qualification buffering gas without dust or other particulate matters The partial size of middle dust or other particulate matters can be about 0.1 μm or less (for example, about 0.08 μm or less, 0.06 μm or less, 0.04 μm with Under, 0.02 μm or less, 0.15 μm or less or 0.01 μm or less).In this application, for example, it is described substantially free of carbon monoxide Refer to the content of carbon monoxide in rectifying qualification buffering gas can be about 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).In this application, for example, described refer to the rectifying substantially free of carbon dioxide The content of carbon dioxide can be 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm in qualification buffering gas Below, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm with Under).In some embodiments, the dew-point temperature that the rectifying qualification buffering gas is referred to substantially free of water is about -50 DEG C or less (for example, about -90 DEG C or less, -80 DEG C or less, -70 DEG C or less, -60 DEG C or less, -55 DEG C or less or -50 DEG C or less). In this application, for example, described refer to non-methane total hydrocarbons in the deoxidation qualification buffering gas substantially free of hydrocarbon Content be about 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less or 0.01ppm or less).

In system described herein, deoxidation qualification buffering gas can be adapted for deoxidation treatment gas or Gas composition.For example, oxygen content in deoxidation qualification buffering gas can for 0.1ppm or less (for example, 0.09ppm or less, 0.08ppm or less, 0.07ppm or less, 0.06ppm or less, 0.05ppm or less, 0.04ppm or less, 0.03ppm or less, 0.02ppm or less, 0.01ppm or less or 0.1ppm or less), argon content can be (not low for example, be not less than 99% not less than 98% In 99.5%, it is not less than 99.9%, is not less than 99.99% or higher).In addition, the deoxidation qualification buffering gas can substantially not Containing mist of oil, dust or other particulate matters, carbon monoxide and hydrocarbon

In system described herein, the flow operating flexibility range that the cryogenic rectification unit carries out rectification process can Think the 60% to 120% of the cryogenic rectification unit Design cooling load flow, for example, for the Design cooling load flow 70% to 120%, it is the 75% to 115% of the Design cooling load flow, is the 80% to 110% of the Design cooling load flow, is described The 85% to 105% of Design cooling load flow is the 90% to 100% of the Design cooling load flow, is the Design cooling load flow 95% to 105%, be the Design cooling load flow 99% to 102%.

In system described herein, the cryogenic rectification unit may include one or more following components: compressor, Throttle valve, heat exchanger, rectifying column, condenser/evaporator, and/or reboiler.

For example, the cryogenic rectification unit may include one or more rectifying columns, each rectifying column is equipped with condensation reflux device And reboiler, wherein the condensation reflux device is located at the rectifying column upper end, the reboiler is located at the rectifying column lower end；Institute Stating cryogenic rectification unit makes at least part of the admixture of gas to rectification process become material stream；The material stream Stock carries out heat exchange, the material stream to be gasified with the reboiler；The material stream of the gasification and the condensing reflux Device carries out heat exchange, obtains the argon gas product of purifying in the rectifying column bottom end；At least one in the material stream of the gasification Part is condensed into phegma after the condensation reflux device heat exchange；Liquid low temperature of the phegma as the rectification process Cooling medium.

In this application, the liquid low temperature cooling medium in the condenser can be with the warm in the reboiler Source is mutually indepedent.For example, the liquid low temperature cooling medium in the condenser can be with the heat source in the reboiler Between by being connected to selected from following process: compression, throttling expansion and/or heat exchange.

In system described herein, the liquid low temperature cooling medium can be liquid nitrogen or liquid argon.In certain embodiment party In formula, the liquid low temperature cooling medium is liquid argon.For example, the liquid argon of the liquid low temperature cooling medium can be to obtain to through condensation The liquid argon of the purifying obtained carries out the low pressure liquid argon obtained after throttling expansion.

In system described herein, the liquid low temperature cooling medium through gasifying can become purifying after re-heat Argon gas product.

In system described herein, the pressure of the liquid low temperature cooling medium can be in cryogenic rectification processing Under operating pressure the material stream dew-point temperature reduce 1-7 DEG C (for example, reduce by 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C, 7 DEG C)) when corresponding liquid argon pressure.For example, the pressure of the liquid low temperature cooling medium can be to grasp in cryogenic rectification processing When making the dew-point temperature of the material stream under pressure reduces 2-3 DEG C (for example, 2 DEG C are reduced, and 2.5 DEG C, 2.8 DEG C, 3 DEG C, 3.2 DEG C, 3.5 DEG C) corresponding liquid argon pressure.For example, the pressure of the liquid low temperature cooling medium can be 0.02-0.2Mpa (for example, being 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.10Mpa, 0.12Mpa, 0.14Mpa, 0.16Mpa, 0.18Mpa or 0.2Mpa)。

In system described herein, what the liquid low temperature cooling medium carried out the material stream of heat exchange can Pressure be 0.1-1.0MPa (for example, 0.1Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa, 0.9Mpa, 1.0Mpa, 1.5Mpa, 1.9Mpa), and the high 0.02- of pressure of cryogenic condensation medium described in its pressure ratio 0.1Mpa (for example, 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).

In system described herein, the heat source be by the admixture of gas to rectification process at least A part carries out pressurization and heating treatment and obtains, and the pressure of the heat source can be operating pressure in cryogenic rectification processing Under the dew-point temperature of the material stream increase 1-7 DEG C of (for example, increase 1 DEG C, 2 DEG C, 3 DEG C, 4 DEG C, 5 DEG C, 6 DEG C or 7 DEG C) phase The pressure for the argon answered, and the pressure of the heat source than the high 0.02-0.1Mpa of pressure of the cryogenic condensation medium (for example, high 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).

For example, the pressure of the heat source of the system can be the material under operating pressure in cryogenic rectification processing Flow stock dew-point temperature increase 2-3 DEG C (for example, increase 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 2.8 DEG C, 3 DEG C, 3.2 DEG C, 3.5 DEG C, 4 DEG C, 5 DEG C) when corresponding argon pressure, and the pressure of the heat source is than the high 0.02- of pressure of the cryogenic condensation medium 0.1Mpa (for example, high 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).In another example the heat The pressure in source can be 0.15-0.7MPa (for example, be 0.15Mpa, 0.2Mpa, 0.3Mpa, 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa), and the pressure of the heat source than the cryogenic condensation medium the high 0.02-0.1Mpa of pressure (for example, High 0.02Mpa, 0.04Mpa, 0.06Mpa, 0.08Mpa, 0.09Mpa or 0.10Mpa).

In system described herein, the cryogenic rectification unit may also include one or more compressors, heat exchanger And throttle valve, the compressor is connected to the heat exchanger fluid and the heat exchanger and the throttle valve are in fluid communication, described Admixture of gas to rectification process becomes high temperature and pressure gas mixing logistics stock to be processed through the compressor compresses, and High temperature and pressure gas mixing logistics stock to be processed handles through cooling in the heat exchanger and becomes cryogenic high pressure and wait locating The gas mixing logistics stock of reason；And at least part of cryogenic high pressure gas mixing logistics stock to be processed flows through the section Stream valve becomes the material stream after being throttled expansion.For example, can make the admixture of gas to rectification process through pressing first Contracting machine compresses and becomes the gas mixing logistics stock to be processed of high temperature and pressure.It then, can be high to the high temperature in heat exchanger The gas mixing logistics stock to be processed of pressure carries out cooling processing, and obtains the gas mixing logistics to be processed of cryogenic high pressure Stock.Later, a part of cryogenic high pressure gas mixing logistics stock to be processed can be used as to the heat source, and by the low temperature Another part of high pressure gas mixing logistics stock to be processed further drops after throttle valve throttling expansion as temperature and pressure The low material stream.

In system described herein, the heat source can be the institute for handling and obtaining through cooling in the heat exchanger State a part of cryogenic high pressure gas mixing logistics stock to be processed.

In system described herein, in the heat exchanger, the liquid low temperature cooling medium through gasifying can be with High temperature and pressure gas mixing logistics stock to be processed carries out heat exchange and makes the liquid low temperature cooling medium through gasifying By after re-heat become purifying argon gas product, and the high temperature and pressure it is to be processed gas mixing logistics stock-traders' know-how cooling processing after at For the gas mixing logistics stock that the cryogenic high pressure is to be processed.

In system described herein, the throttle valve can also be in fluid communication with the reboiler, and the heat source is in institute It stated after carrying out heat exchange with the liquid argon of the purifying obtained through condensation in reboiler, is formed through the throttle valve throttling expansion For a part of the material stream.

In system described herein, the temperature of the liquid low temperature cooling medium can be -170 DEG C to -198 DEG C (for example, being -170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, -195 DEG C or -198 DEG C).The temperature of the material stream It can be -165 DEG C to -197 DEG C (for example, being -165 DEG C, -170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, -195 DEG C Or -197 DEG C), and the temperature of the cryogenic condensation medium it is at least 1-5 DEG C low than the temperature of the material stream (for example, down to It is 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C few).The liquid argon of the purifying obtained through condensation Temperature can be -160 DEG C to -196 DEG C (for example, be about -200 DEG C hereinafter, about -190 DEG C hereinafter, about -180 DEG C hereinafter, about -170 DEG C hereinafter, about -160 DEG C hereinafter, about -150 DEG C hereinafter, about -140 DEG C hereinafter, about -130 DEG C or less), and the purifying The temperature of liquid argon it is about 0.5 DEG C to about 5 DEG C low than the temperature of the material stream (for example, low 0.5 DEG C, 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C).The temperature of the heat source can be -170 DEG C to -195 DEG C (for example, for - 170 DEG C, -175 DEG C, -180 DEG C, -185 DEG C, -190 DEG C, -193 DEG C or -195 DEG C), and the temperature of the heat source is pure than described At least 1-5 DEG C of the temperature height of the liquid argon of change is (for example, high at least 1 DEG C, 1.5 DEG C, 2 DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C Or 5 DEG C).

The compressor can be below one or more: positive displacement compressor (such as piston compressor or screw rod Formula compressor) and/or speed mode compressor (for example, centrifugal compressor).

System described herein may also include at least one control unit.Described control unit can be single with the pretreatment First, the described catalytic oxidation unit, the deacidification unit, the absorbing unit, first buffer cell, second buffering are single The first and described cryogenic rectification unit is operably connected, in the temperature, pressure, and/or the system to adjust the system The circulation style and/or flow of fluid.

Fig. 1 shows an example of system provided herein.Firstly, passing through admixture of gas 113 to be processed Pretreatment unit 101 pre-processes, to remove oil, dust and other particulate matters therein to obtain pretreated gas mixing Object 114.Pretreated admixture of gas 114 can be passed through in absorbing unit 102, further to remove water therein, dioxy Change carbon, hydrocarbon etc., obtains pretreated admixture of gas 115.Then, it is detected by oxygenation measurement unit 103 described Oxygen concentration in pretreated admixture of gas 115, when the oxygen concentration measured is more than about 4% (v/v), by the warp At least part of pretreated admixture of gas 115 discharges and as stream stock 127 from the second buffer cell 112 to the warp Deoxidation qualification buffering gas 124 is passed through in pretreated admixture of gas 116 to make oxygen concentration therein no more than about 4% (v/v). Make the catalysis oxidation in the pretreated admixture of gas 116 and catalysis oxidation and hydrogenation deoxidation unit 104 of oxygen content qualification Part contacts, to make the reducibility gas in the admixture of gas by catalysis oxidation, to obtain the gas through catalysis oxidation Mixture.Then, make the admixture of gas through catalysis oxidation and adding in the catalysis oxidation and hydrogenation deoxidation unit 104 The contact of hydrogen deoxygenated moiety, and be passed through into the hydrogenation deoxidation part from hydrogen generating unit 109 proper proportion hydrogen 126 so that Oxygen content therein is reduced to no more than about 40ppm, to obtain the admixture of gas 117 of hydrogenated deoxidation.Described second is slow The gas rushed in unit 112 may be from through catalysis oxidation and hydrogenation deoxidation treated stream stock 125.Then, make described hydrogenated The admixture of gas 117 of deoxidation is contacted with absorbing unit 105, with remove the water in the admixture of gas, carbon dioxide and/or Hydrocarbon, to obtain the admixture of gas 120 to rectification process.The measurement admixture of gas to rectification process 120 flow, and by rectifying qualification from the first buffer cell 111 buffer make and gas 119 is adjusted it is described to rectifying The flow of the admixture of gas 120 of processing is within the scope of the flow operating flexibility of rectification process.First buffer cell 111 In buffer gas can partly from through the absorbing unit 105 treated stream stock 118.Later, make it is described to rectifying at The admixture of gas 120 of reason through cryogenic rectification unit 106 handle to remove hydrogen and nitrogen, thus obtain purifying liquid argon and/ Or argon gas product 121, and be stored into products pot 107.Meanwhile the hydrogen 122 that need to be removed can be handled through hydrogen retrieval unit 108 And it recycles.Liquid argon storage tank 110 and the cryogenic rectification unit 106 are in fluid communication, to be supplied as the liquid argon of cold source thereto 123。

Fig. 2 shows the experiment curv that argon concentration changes over time in monocrystalline silicon production.As seen from Figure 2, not It is to be processed when opening monocrystaline silicon stove or ingot furnace and it is in fluid communication with environmental gas in the case that control valve is set Admixture of gas in argon gas changes of contents it is violent, this will seriously affect argon gas recycling ability.

The application further relates to following specific embodiment:

1, a kind of method of liquid argon for being used to prepare purifying and/or argon gas product, which comprises

A) make admixture of gas to be processed be subjected to pretreatment with remove mist of oil, dust and other particulate matters therein to Obtain pretreated admixture of gas；

Contact pretreated admixture of gas a) with catalytic oxidation unit, to make the gas mixing Reducibility gas in object is by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；

It contacts the admixture of gas through catalysis oxidation b) with deacidification unit, and leads into the deacidification unit Enter the hydrogen of proper proportion so that oxygen content therein is reduced to 2ppm hereinafter, to obtain the gas mixing of hydrogenated deoxidation Object；

Contact the admixture of gas of hydrogenated deoxidation c) with absorbing unit, to remove the admixture of gas In water, carbon dioxide and/or hydrocarbon, to obtain admixture of gas to rectification process；

E) flow of the admixture of gas to rectification process of measurement d), and carried out by buffering gas with rectifying qualification It adjusts and makes the flow of the admixture of gas to rectification process within the scope of the flow operating flexibility of rectification process；And

Handle the admixture of gas to rectification process e) to remove nitrogen and hydrogen through cryogenic rectification, thus Obtain the liquid argon and/or argon gas product of purifying.

2, the method according to embodiment 1, wherein being passed through the hydrogen of proper proportion in Xiang Suoshu deacidification unit in c) Gas is so that oxygen content therein is reduced to 0.1ppm or less.

3, the method according to any one of embodiment 1-2, further include: it g) recycles and/or purifies in f) and gone The hydrogen removed.

4, the method according to any one of embodiment 1-3, wherein pretreatment a) includes bulk processing and essence Close processing.

5, the method according to embodiment 4, wherein the bulk processing includes using selected from following one or more: Mist of oil is adsorbed using asphalt felt, dust is filtered by filter device, mist of oil and dust are removed by water spray, pass through rotating device Separation removal mist of oil and dust, and/or generate the water comprising microbubble and by spraying to the admixture of gas to be processed The water comprising microbubble is made a return journey oil mist removing.

6, the method according to any one of embodiment 4-5, wherein the accurate processing includes using following one Kind is a variety of: membrane filter, ceramic filter, metallic filter and/or active carbon adsorber.

7, the method according to any one of embodiment 3-6, wherein by cryogenic rectification, flash distillation, and/or absorption come Recycle and/or purify the hydrogen.

8, the method according to any one of embodiment 1-7, wherein making the pretreated gas in b) Before mixture is contacted with the catalytic oxidation unit, the oxygen concentration in the pretreated admixture of gas is measured；With/ Or,

Before contacting the pretreated admixture of gas with the catalytic oxidation unit, measures the warp and located in advance Oxygen concentration in the admixture of gas of reason；And/or

Before contacting the pretreated admixture of gas with the catalytic oxidation unit, removes the warp and located in advance Water and carbon dioxide in the admixture of gas of reason.

9, the method according to embodiment 8, wherein passing through when the measured oxygen concentration is more than 4% (v/v) At least part of the pretreated admixture of gas is discharged and is passed through deoxidation qualification buffering gas to make its oxygen concentration No more than about 4% (v/v).

10, the method according to embodiment 8, wherein leading to when the measured oxygen concentration is more than 2% (v/v) It crosses and at least part of the pretreated admixture of gas is discharged to and is passed through deoxidation qualification buffering gas to keep its oxygen dense Spend no more than about 2% (v/v).

11, the method according to any one of embodiment 8-10, wherein being passed through in Xiang Suoshu deacidification unit in c) Hydrogen and the measured pretreated admixture of gas in the molar ratio of oxygen be about 2.2:1 to about 3:1.

12, the method according to any one of embodiment 1-11, wherein the catalysis oxidation will include carbon in b) The reducibility gas of hydrogen compound and carbon monoxide is oxidized to water and carbon dioxide.

13, the method according to any one of embodiment 1-12, wherein in b), when the pretreated gas When the molar fraction of oxygen needed for the molar fraction of oxygen is less than the oxidation pretreated gas in mixture, then oxygen is added Gas makes the molar fraction of oxygen in the pretreated admixture of gas rubbing than oxygen needed for the pretreated gas You are the high 10-50% of score.

14, the method according to any one of embodiment 1-13, wherein b) described in catalytic oxidation unit include Catalyst, and the catalyst is selected from the group: Carulite catalyst, platinum catalyst, palladium catalyst and any combination thereof.

15, the method according to any one of embodiment 1-14, wherein c) described in deacidification unit include catalysis Agent, and the catalyst is selected from the group: Cu, platinum catalyst, palladium catalyst and any combination thereof.

16, the method according to any one of embodiment 1-15, wherein in the admixture of gas to be processed to The impurity of removal includes: other particulate matters such as oil, dust, silicon powder, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water And/or hydrocarbon；And/or

The admixture of gas to be processed is the exhaust gas that monocrystaline silicon stove or ingot furnace generate.

17, the method according to any one of embodiment 1-16, wherein when the pretreated admixture of gas The molar fraction of middle oxygen, which is greater than 2% or described pretreated admixture of gas and carries out the temperature of the catalysis oxidation, is more than At 400 degrees Celsius, the catalytic oxidation unit includes segmentation reactor；And/or

When the temperature that the deacidification unit is reacted is more than 400 degrees Celsius, the deacidification unit includes that segmentation is anti- Answer device.

18, the method according to embodiment 17 further includes, and before a), controls the monocrystaline silicon stove or ingot casting The discharge opportunity of exhaust gas in furnace, so that the content of argon gas is maintained in the admixture of gas to be pre-treated 80%.

19, the method according to embodiment 18, wherein the admixture of gas to be pre-treated be from two or The exhaust gas of more monocrystaline silicon stoves or ingot furnace, and when any of the two or more monocrystaline silicon stoves or ingot furnace When need to be in fluid communication with environmental gas, stopping is arranged from the monocrystaline silicon stove or ingot furnace into the admixture of gas to be pre-treated Put tail gas.

20, according to the described in any item methods of embodiment 1-19, wherein in the liquid argon of the purifying and/or argon gas product The content of argon is at least about 99%.

21, according to the described in any item methods of embodiment 1-20, wherein in the liquid argon of the purifying and/or argon gas product The content of argon is at least about 99.999%.

22, the method according to any one of embodiment 1-21, it is wherein d) middle using at least two absorbing units, and When one of described at least two absorbing unit is adsorbed, another absorbing unit therein is regenerated, thus described At least two absorbing units are alternately adsorbed and are regenerated, and are then realized and are persistently carried out adsorption treatment to the admixture of gas.

23, the method according to any one of embodiment 1-22, wherein oxygen content in rectifying qualification buffering gas For 0.1ppm hereinafter, argon content is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, dioxy Change carbon, water and hydrocarbon.

24, the method according to embodiment 23, wherein described refer to that the rectifying qualification is slow substantially free of mist of oil The partial size of oil droplet is 0.1 μm or less in qi of chong channel ascending adversely.

25, the method according to embodiment 23 or 24, wherein described be substantially free of dust or other particulate matters Refer to that the partial size of dust or other particulate matters is 0.1 μm or less in the rectifying qualification buffering gas.

26, the method according to any one of embodiment 23-25, wherein described refer to substantially free of carbon monoxide The content of carbon monoxide is 0.1ppm or less in the rectifying qualification buffering gas.

27, the method according to any one of embodiment 23-26, wherein described refer to substantially free of carbon dioxide The content of carbon dioxide is 0.1ppm or less in the rectifying qualification buffering gas.

28, the method according to any one of embodiment 23-27, wherein described refer to the essence substantially free of water The dew-point temperature for evaporating qualified buffering gas is -50 DEG C or less.

29, the method according to any one of embodiment 23-28, wherein described be substantially free of hydrocarbon The total content for referring to non-methane total hydrocarbons in the rectifying qualification buffering gas is 0.1ppm or less.

30, the method according to embodiment 9 or 10, wherein oxygen content is 0.1ppm in deoxygenation lattice buffering gas Hereinafter, argon content is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, carbon dioxide, water And hydrocarbon.

31, the method according to embodiment 30, wherein described refer to that the deoxidation qualification is slow substantially free of mist of oil The partial size of oil droplet is 0.1 μm or less in qi of chong channel ascending adversely.

32, the method according to embodiment 30 or 31, wherein described be substantially free of dust or other particulate matters Refer to that the partial size of dust or other particulate matters is 0.1 μm or less in the deoxidation qualification buffering gas.

33, the method according to any one of embodiment 30-32, wherein described refer to substantially free of carbon monoxide The content of carbon monoxide is 0.1ppm or less in the deoxidation qualification buffering gas.

34, the method according to any one of embodiment 30-33, wherein described refer to substantially free of carbon dioxide The content of carbon dioxide is 0.1ppm or less in the deoxidation qualification buffering gas.

35, the method according to any one of embodiment 30-34, wherein described refer to the essence substantially free of water The dew-point temperature for evaporating qualified buffering gas is -40 DEG C or less.

36, the method according to any one of embodiment 30-35, wherein described be substantially free of hydrocarbon The total content for referring to non-methane total hydrocarbons in the rectifying qualification buffering gas is 0.1ppm or less.

37, the method according to any one of embodiment 1-36, wherein the flow operating flexibility of the rectification process Range is the 60% to 120% of the Design cooling load flow of the rectification process.

38, the method according to any one of embodiment 1-37, wherein in f), the cryogenic rectification processing packet It includes:

I) making at least part of the admixture of gas to rectification process e) becomes material stream；

Ii the material stream and heat source i)) is made to carry out heat exchange, the material stream to be gasified；And

Iii) make ii) the gasification material stream and liquid low temperature cooling medium carry out heat exchange, obtain purifying Argon gas product；Also, at least part in the material stream of gasification ii) is condensed into phegma, the phegma Liquid low temperature cooling medium as the rectification process.

39, the method according to embodiment 38, wherein ii) described in liquid low temperature cooling medium be liquid nitrogen or liquid Change air or liquid argon.

40, the method according to embodiment 39, wherein ii) described in liquid low temperature cooling medium be liquid argon.

41, the method according to embodiment 40, wherein as ii) described in the liquid argon of liquid low temperature cooling medium be To the low pressure liquid argon obtained after the liquid argon throttling expansion of the purifying obtained through condensation.

42, the method according to embodiment 41, wherein ii) in the liquid low temperature cooling medium warp through gasifying Become the argon gas product of purifying after re-heat.

43, the method according to any one of embodiment 40-42, wherein ii) described in liquid low temperature cooling medium Pressure be that the dew-point temperature of the material stream under operating pressure in cryogenic rectification processing reduces corresponding liquid at 1-7 DEG C Argon pressure.

44, the method according to embodiment 43, wherein the pressure of the liquid low temperature cooling medium is the low temperature The dew-point temperature of the material stream reduces corresponding liquid argon pressure at 2-3 DEG C under operating pressure in rectification process.

45, the method according to any one of embodiment 40-44, wherein the pressure of the liquid low temperature cooling medium 0.02-0.2MPa。

46, the method according to any one of embodiment 40-45, wherein ii) in condense and be situated between with the liquid low temperature Matter carries out the pressure of the material stream of heat exchange as 0.1-1.0MPa, and the pressure of cryogenic condensation medium described in its pressure ratio High 0.02-0.1MPa.

47, the method according to any one of embodiment 40-46, wherein iii) described in heat source be by e) The admixture of gas to rectification process at least part carry out pressurization and heating treatment and obtain, the heat source Pressure is that the dew-point temperature of the material stream under operating pressure in cryogenic rectification processing increases corresponding argon at 1-7 DEG C Pressure, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

48, the method according to embodiment 47, wherein the pressure of the heat source is to grasp in cryogenic rectification processing Make the pressure of corresponding argon when the dew-point temperature of the material stream under pressure increases 2-3 DEG C, described in the pressure ratio of the heat source The high 0.02-0.1MPa of the pressure of cryogenic condensation medium.

49, the method according to any one of embodiment 40-48, wherein the pressure of the heat source is 0.7- 0.15MPa, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

50, the method according to any one of embodiment 40-49, wherein in i), to e) described to rectifying at The admixture of gas of reason, which is handled as follows, obtains the material stream:

Ia the admixture of gas to rectification process e)) is made to become high temperature and pressure gas to be processed through compressor compresses Body mixture flow stock；

Ib) make ia) high temperature and pressure gas mixing logistics stock to be processed handled in heat exchanger through cooling For the gas mixing logistics stock that cryogenic high pressure is to be processed；And

Ic) make ib) cryogenic high pressure gas mixing logistics stock to be processed at least part after throttling expansion As the material stream.

51, the method according to embodiment 50, wherein iii) described in heat source be ib) in the low temperature that obtains A part of high pressure gas mixing logistics stock to be processed.

52, the method according to embodiment 50, wherein by make the liquid low temperature cooling medium through gasifying with High temperature and pressure gas mixing logistics stock to be processed carries out heat exchange in the heat exchanger and makes the liquid through gasifying State cryogenic condensation medium is become the argon gas product of purifying, and the gas mixing logistics for keeping the high temperature and pressure to be processed after re-heat Stock-traders' know-how cooling handles and becomes cryogenic high pressure gas mixing logistics stock to be processed.

53, the method according to any one of embodiment 47-52, wherein the heat source is with described through condensing acquisition After the liquid argon of purifying carried out heat exchange, a part of the material stream is expanded into through throttling.

54, the method according to any one of embodiment 38-53, wherein the temperature of the liquid low temperature cooling medium It is -170 DEG C to -198 DEG C.

55, the method according to any one of embodiment 38-54, wherein i) described in material stream temperature be- 165 DEG C to -197 DEG C, and the temperature of the cryogenic condensation medium is at least 1-5 DEG C lower than the temperature of the material stream.

56, the method according to any one of embodiment 38-55, wherein the liquid argon of the purifying obtained through condensation Temperature be -160 DEG C to -196 DEG C, and the temperature of the liquid argon of the purifying it is lower than the temperature of the material stream about 0.5 DEG C extremely About 5 DEG C.

57, the method according to any one of embodiment 38-56, wherein the temperature of the heat source be -170 DEG C to - 195 DEG C, and the temperature of the heat source is at least 1-5 DEG C higher than the temperature of the liquid argon of the purifying.

58, the method according to any one of embodiment 1-57, wherein include adsorbent in the absorbing unit, and The adsorbent includes following one or more: active carbon, activated alumina, modified silica-gel, carbon molecular sieve, natural zeolite, Modified zeolite, sial based molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, metal-organic framework material and their mixing Object.

59, the system of a kind of liquid argon for being used to prepare purifying and/or argon gas product, the system comprises:

Pretreatment unit, and gas mixing fluid communication to be processed and removes mist of oil therein, dust and other Particulate matter is to obtain pretreated admixture of gas；

Catalytic oxidation unit is in fluid communication with the pretreatment unit, and the catalytic oxidation unit locates the warp in advance Reducibility gas in the admixture of gas of reason is by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；

Deacidification unit is in fluid communication with the catalytic oxidation unit, is passed through proper proportion in Xiang Suoshu deacidification unit After hydrogen, the deacidification unit so that the oxygen content in the admixture of gas through catalysis oxidation is reduced to about 2ppm hereinafter, from And obtain the admixture of gas of hydrogenated deoxidation；

Absorbing unit is in fluid communication with the deacidification unit, and the absorbing unit includes adsorbent to remove the warp Water, carbon dioxide and/or hydrocarbon in the admixture of gas of hydrogenation deoxidation, to obtain mixed to the gas of rectification process Close object；

First buffer cell, with the gas mixing fluid communication to rectification process and include described for measuring The flow rate-measuring device of the flow of admixture of gas to rectification process is buffered comprising rectifying qualification in first buffer cell Gas, the rectifying qualification buffering gas is used to adjust for the flow of the admixture of gas to rectification process, and the flow is made to exist Within the scope of the flow operating flexibility of rectification process；And

Cryogenic rectification unit is in fluid communication with the absorbing unit and first buffer cell, with remove it is described to Nitrogen and hydrogen in the admixture of gas of rectification process, to obtain the liquid argon and/or argon gas product of purifying.

60, the system according to embodiment 59, wherein the deacidification unit keeps the gas through catalysis oxidation mixed It closes the oxygen content in object and is reduced to about 0.1ppm hereinafter, to obtain the admixture of gas of hydrogenated deoxidation.

61, the system according to embodiment 59 or 60 further includes hydrogen retrieval unit, the hydrogen retrieval unit and institute Cryogenic rectification unit is stated to be in fluid communication and be used to recycle the hydrogen being removed in the cryogenic rectification unit.

62, the system according to any one of embodiment 59-61 further includes deoxidation preparatory unit, respectively with The catalytic oxidation unit and the deacidification unit are in fluid communication, and the deoxidation preparatory unit includes that removal is described through catalysis oxidation Admixture of gas in water, carbon dioxide and/or hydrocarbon, to obtain the gas mixing that handles to deacidification unit Object.

63, the system according to any one of embodiment 59-62, wherein the pretreatment unit includes bulk processing dress It sets and accurate processing unit.

64, the system according to embodiment 63, wherein the bulk processing device includes selected from following one kind or more Kind: asphalt felt, dust filtering device, water spray system and/or the rotating device for removing mist of oil and dust simultaneously.

65, the system according to embodiment 64, wherein the water spray system generates the water comprising microbubble and leads to It crosses and makes a return journey oil mist removing to the admixture of gas spray water comprising microbubble to be processed.

66, the system according to any one of embodiment 63-65, wherein the precision processing unit includes in following It is one or more: membrane filter, ceramic filter, metallic filter and/or active carbon adsorber.

67, the system according to any one of embodiment 61-66, wherein the hydrogen retrieval unit includes selected from following Device: cryogenic rectification device, flash distillation plant, and/or adsorbent equipment.

68, the system according to any one of embodiment 59-67 further includes oxygenation measurement unit, the oxygenation measurement Unit and the pretreatment unit are in fluid communication and can measure the oxygen concentration in the pretreated admixture of gas；And/or

The system also includes impurity measurement unit, the impurity measurement unit and the pretreatment unit are in fluid communication simultaneously It can measure the impurity concentration in the pretreated admixture of gas.

69, the system according to embodiment 68 further includes the second buffer cell, and second buffer cell includes Deoxidation qualification buffer gas and with the pretreated gas mixing fluid communication, when the oxygen concentration measured is more than 4% (v/v) when, at least part of the pretreated admixture of gas is discharged and from second buffer cell to institute It states and is passed through deoxidation qualification buffering gas in pretreated admixture of gas to make oxygen concentration therein be no more than 4% (v/v).

70, the system according to embodiment 69, wherein when the oxygen concentration measured is more than 2% (v/v), by institute At least part for stating pretreated admixture of gas discharges and from second buffer cell to described pretreated Deoxidation qualification buffering gas is passed through in admixture of gas to make oxygen concentration therein be no more than 2% (v/v).

71, the system according to embodiment 69 or 70, wherein the hydrogen being passed through into the deacidification unit with surveyed The molar ratio of the oxygen in the pretreated admixture of gas obtained is about 2.2:1 to about 3:1.

72, the system according to any one of embodiment 59-71, wherein the catalytic oxidation unit will include hydrocarbon The reducibility gas of compound and carbon monoxide is oxidized to water and carbon dioxide.

73, the system according to any one of embodiment 59-72, wherein the catalytic oxidation unit includes catalysis Agent, and the catalyst is selected from the group: Carulite catalyst, platinum catalyst, palladium catalyst and any combination thereof.

74, the system according to any one of embodiment 59-73, wherein the deacidification unit includes catalyst, and The catalyst is selected from the group: Cu, platinum catalyst, palladium catalyst and any combination thereof.

75, the system according to any one of embodiment 59-74, wherein when the pretreated admixture of gas The molar fraction of middle oxygen, which is greater than 2% or described pretreated admixture of gas and carries out the temperature of the catalysis oxidation, is more than At 400 degrees Celsius, the catalytic oxidation unit includes segmentation reactor；And/or

76, the system according to any one of embodiment 59-75, wherein in the admixture of gas to be processed to The impurity of removal include: oil, dust, other particulate matters, silicon vapor, oxygen, nitrogen, carbon monoxide, carbon dioxide, water and/or Hydrocarbon.

77, the system according to any one of embodiment 59-76, wherein the admixture of gas to be processed is single The exhaust gas that crystal silicon furnace or ingot furnace generate.

78, the system according to embodiment 77 further includes air inlet adjustment valve, described in the air inlet adjustment valve control Fluid communication between monocrystaline silicon stove or ingot furnace and the pretreatment unit, so that the gas mixing to be pre-treated The content of argon gas is maintained at 80% in object.

79, the system according to embodiment 78 comprising two or more described air inlet adjustment valves, wherein each Air inlet adjustment valve independently controls an individual fluid communication between monocrystaline silicon stove or ingot furnace and the pretreatment unit, And when any one described monocrystaline silicon stove or ingot furnace need to be in fluid communication with environmental gas, corresponding air inlet adjustment valve blocks should Fluid communication between monocrystaline silicon stove or ingot furnace and the pretreatment unit.

80, the system according to any one of embodiment 59-79, wherein the liquid argon of the purifying and/or argon gas produce The content of argon is at least about 99% in product.

81, the system according to embodiment 80, wherein in the liquid argon of the purifying and/or argon gas product argon content It is at least about 99.999%.

82, the system according to any one of embodiment 59-81 comprising at least two absorbing units, and work as institute When stating one of at least two absorbing units and being adsorbed, another absorbing unit therein is regenerated, thus it is described at least Two absorbing units are alternately adsorbed and are regenerated, and then realize that the admixture of gas to the hydrogenated deoxidation is persistently inhaled Attached processing.

83, the system according to any one of embodiment 59-82, wherein oxygen content in rectifying qualification buffering gas For 0.1ppm hereinafter, argon content is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, dioxy Change carbon, water and hydrocarbon.

84, the system according to embodiment 83, wherein described refer to that the rectifying qualification is slow substantially free of mist of oil The partial size of oil droplet is 0.1 μm or less in qi of chong channel ascending adversely.

85, the system according to embodiment 83, wherein described refer to institute substantially free of dust or other particulate matters Stating the partial size of dust or other particulate matters in rectifying qualification buffering gas is 0.1 μm or less.

86, the system according to embodiment 83, wherein described refer to that the rectifying is closed substantially free of carbon monoxide The content that lattice buffer carbon monoxide in gas is 0.1ppm or less.

87, the system according to embodiment 83, wherein described refer to that the rectifying is closed substantially free of carbon dioxide The content that lattice buffer carbon dioxide in gas is 0.1ppm or less.

88, the system according to embodiment 83, wherein described refer to the rectifying qualification buffering substantially free of water The dew-point temperature of gas is -50 DEG C or less.

89, the system according to embodiment 83, wherein described refer to the rectifying substantially free of hydrocarbon The total content of non-methane total hydrocarbons is 0.1ppm or less in qualification buffering gas.

90, the system according to embodiment 69 or 70, wherein oxygen content is in deoxygenation lattice buffering gas 0.1ppm is hereinafter, argon content is not less than 98%, and substantially free of mist of oil, dust or other particulate matters, carbon monoxide, titanium dioxide Carbon, water and hydrocarbon.

91, the system according to embodiment 90, wherein described refer to that the deoxidation qualification is slow substantially free of mist of oil The partial size of oil droplet is 0.1 μm or less in qi of chong channel ascending adversely.

92, the system according to embodiment 90, wherein described refer to institute substantially free of dust or other particulate matters Stating the partial size of dust or other particulate matters in deoxidation qualification buffering gas is 0.1 μm or less.

93, the system according to embodiment 90, wherein described refer to the deoxygenation substantially free of carbon monoxide The content that lattice buffer carbon monoxide in gas is 0.1ppm or less.

94, the system according to embodiment 90, wherein described refer to the deoxygenation substantially free of carbon dioxide The content that lattice buffer carbon dioxide in gas is 0.1ppm or less.

95, the system according to embodiment 90, wherein described refer to the deoxidation qualification buffering substantially free of water The dew-point temperature of gas is -40 DEG C or less.

96, the system according to embodiment 90, wherein described refer to the deoxidation substantially free of hydrocarbon The total content of non-methane total hydrocarbons is 0.1ppm or less in qualification buffering gas.

97, the system according to any one of embodiment 59-96, wherein the cryogenic rectification unit carries out at rectifying The flow operating flexibility range of reason is the 60% to 120% of the cryogenic rectification unit Design cooling load flow.

98, the system according to any one of embodiment 59-97, wherein the cryogenic rectification unit include one or Multiple following components: compressor, throttle valve, heat exchanger, rectifying column, condenser, evaporator and/or reboiler.

99, the system according to embodiment 98, wherein the cryogenic rectification unit includes one or more rectifying columns, Each rectifying column is equipped with condensation reflux device and reboiler, wherein the condensation reflux device is located at the rectifying column upper end, it is described again Boiling device is located at the rectifying column lower end；

The cryogenic rectification unit makes at least part of the admixture of gas to rectification process become material stream；

The material stream and the reboiler carry out heat exchange, the material stream to be gasified；The material of the gasification It flows stock and the condensation reflux device carries out heat exchange, obtain the argon gas product of purifying in the rectifying column bottom end；The gasification At least part in material stream is condensed into phegma after the condensation reflux device heat exchange；Described in the phegma is used as The liquid low temperature cooling medium of rectification process.

100, the system according to embodiment 99, wherein the liquid low temperature cooling medium in the condenser with The heat source in the reboiler is mutually indepedent.

101, the system according to embodiment 99, wherein the liquid low temperature cooling medium in the condenser with By being connected to selected from following process between the heat source in the reboiler: compression, throttling expansion and/or heat exchange.

102, the system according to any one of embodiment 99-101, wherein the liquid low temperature cooling medium is liquid Nitrogen, liquefied air or liquid argon.

103, the system according to embodiment 102, wherein the liquid low temperature cooling medium is liquid argon.

104, the system according to embodiment 103, wherein the liquid argon of the liquid low temperature cooling medium is to through cold The liquid argon of the solidifying purifying obtained carries out the low pressure liquid argon obtained after throttling expansion.

105, the system stated according to embodiment 103 or 104, wherein the liquid low temperature cooling medium through gasifying is through multiple Become the argon gas product of purifying after heat.

106, the method according to any one of embodiment 99-105, wherein the pressure of the liquid low temperature cooling medium Power is that the dew-point temperature of the material stream under operating pressure in the cryogenic rectification unit reduces corresponding liquid argon pressure at 1-7 DEG C Power.

107, the method according to embodiment 106, wherein the pressure of the liquid low temperature cooling medium is described low The dew-point temperature of the material stream reduces corresponding liquid argon pressure at 2-3 DEG C under operating pressure in warm rectification cell.

108, the method according to any one of embodiment 99-107, wherein the pressure of the liquid low temperature cooling medium Power 0.01-0.2MPa.

109, the method according to any one of embodiment 99-108, wherein with the liquid low temperature cooling medium into The pressure of the material stream of row heat exchange is 0.1-1.0MPa, and cryogenic condensation medium described in the pressure ratio of the heat source The high 0.02-0.1MPa of pressure.

110, the method according to any one of embodiment 99-109, wherein the heat source is by described low It is pressurizeed and is cooled down at least part of the admixture of gas to rectification process in warm rectification cell and handled and obtain , the pressure of the heat source is that the dew-point temperature of the material stream under operating pressure in the cryogenic rectification unit increases 1-7 DEG C when corresponding argon pressure, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

111, the method according to embodiment 110, wherein the pressure of the heat source is in cryogenic rectification processing The dew-point temperature of the material stream increases the pressure of corresponding argon at 2-3 DEG C, and the pressure ratio of the heat source under operating pressure The high 0.02-0.1MPa of pressure of the cryogenic condensation medium.

112, the method according to any one of embodiment 99-111, wherein the pressure of the heat source is 0.15- 0.7MPa, and the high 0.02-0.1MPa of pressure of cryogenic condensation medium described in the pressure ratio of the heat source.

113, the system according to any one of embodiment 99-112, wherein the cryogenic rectification unit further includes one A or multiple compressors, heat exchanger and throttle valve, the compressor is connected to the heat exchanger fluid and the heat exchanger and institute Throttle valve fluid communication is stated, the admixture of gas to rectification process becomes high temperature and pressure and wait locating through the compressor compresses The gas mixing logistics stock of reason, and high temperature and pressure gas mixing logistics stock to be processed in the heat exchanger through cooling at It manages and becomes cryogenic high pressure gas mixing logistics stock to be processed；And cryogenic high pressure gas mixing logistics stock to be processed At least part, which flows through after the throttle valve is throttled expansion, becomes the material stream.

114, the system according to embodiment 113, wherein the heat source is to handle in the heat exchanger through cooling And a part of the cryogenic high pressure gas mixing logistics stock to be processed obtained.

115, the system according to embodiment 113 or 114, wherein in the heat exchanger, the liquid through gasifying State cryogenic condensation medium and high temperature and pressure gas mixing logistics stock to be processed carry out heat exchange and make described gasified Liquid low temperature cooling medium is become the argon gas product of purifying, and the gas mixing logistics that the high temperature and pressure is to be processed after re-heat Become cryogenic high pressure gas mixing logistics stock to be processed after stock-traders' know-how cooling processing.

116, the system according to any one of embodiment 113-116, wherein the throttle valve is also boiled with described again Device is in fluid communication, after the heat source carried out heat exchange with the liquid argon of the purifying obtained through condensation in the reboiler, Become a part of the material stream through the throttle valve throttling expansion.

117, the system according to any one of embodiment 99-116, wherein the temperature of the liquid low temperature cooling medium Degree is -170 DEG C to -198 DEG C.

118, the system according to any one of embodiment 99-117, wherein the temperature of the material stream is -165 DEG C to -197 DEG C, and the temperature of the cryogenic condensation medium is at least 1-5 DEG C lower than the temperature of the material stream.

119, the system according to any one of embodiment 99-118, wherein the liquid of the purifying obtained through condensation The temperature of argon is -160 DEG C to -196 DEG C, and the temperature of the liquid argon of the purifying is about 0.5 DEG C lower than the temperature of the material stream To about 5 DEG C.

120, the system according to any one of embodiment 99-119, wherein the temperature of the heat source is -170 DEG C To -195 DEG C, and the temperature of the heat source is at least 1-5 DEG C higher than the temperature of the liquid argon of the purifying.

121, the system according to any one of embodiment 59-120, wherein including absorption in the absorbing unit Agent, and the adsorbent includes following one or more: active carbon, activated alumina, modified silica-gel, carbon molecular sieve, natural Zeolite, modified zeolite, sial based molecular sieve, mesopore molecular sieve, titanium-based molecular sieve, metal-organic framework material and they Mixture.

122, the system according to any one of embodiment 59-121 further includes at least one control unit, Described in control unit and the pretreatment unit, the catalytic oxidation unit, the deacidification unit, the absorbing unit, institute It states the first buffer cell, second buffer cell and the cryogenic rectification unit to be operably connected, to adjust the system The circulation style and/or flow of fluid in the temperature of system, pressure, and/or the system.

It is not intended to be limited by any theory, following embodiments is used for the purpose of illustrating the work of the present processes and system Make mode, rather than the range of limitation the present application.

Embodiment

The system and method that embodiment 1 is used to recycle the argon product in monocrystalline silicon production tail gas

1, equipment and scheme

The system and method for carrying out argon gas recycling with about 240Nm3/h are provided in the present embodiment.It is adopted in the method It include compressor band, Precooling unit, oil removing system, deoxidization by adding hydrogen system, molecule in the system with Deep Cooling Method separation principle Sieve purification system and the rectifying column for carrying out single tower distillation nitrogen.

In addition, the analytical unit and control unit include mating the system also includes analytical unit and control unit Software for calculation, for system and method carry out process optimization analysis and operation control.

Specifically, the system specifically includes that compressibility, accurate oil removing system, chilldown system, final stage high-precision oil removing System oil strainer, deoxidization by adding hydrogen system, molecular sieve adsorption and purification system, fractionating column cold box system, liquid standby and input system System and instrument electric-control system etc..

● admixture of gas compression to be processed

Firstly, making admixture of gas to be processed enter compressor suction port, through final stage after compressing it to required pressure Cooler is cooled to 40 degrees Celsius or less.

● pre-cooling

Chilldown system in the present embodiment includes Freon-Evaporator, refrigeration compressor, condenser, evaporator, water separation Device and control system.So that the pre-cooled unit of admixture of gas to be processed is cooled to 5~8 DEG C, is then separated through separator Free water makes the admixture of gas enter oil removing unit later, carries out oil removal treatment to it.

The refrigeration compressor uses energy saver, and hot gas bypass line is arranged, when pressure of inspiration(Pi) is lower than 0.3Mpa It works, using the refrigeration compressor of international top-brand, reliable for operation, power saving, service life are long, high cooling efficiency.Thoroughly avoid full envelope It closes compressor and is easy disadvantage brought by burning machine.Again can avoid semi-hermetic refrigeration compressor axle envelope at be easy oil leak leakage freon, The high disadvantage of maintenance rate.It sets refrigeration compressor to there is self-discharging function, sufficiently achieves energy-saving effect.

It avoids temperature sensing package come temperature control using platinum resistance thermometer sensor, and secondary control instrument in the chilldown system of the present embodiment and is easy The disadvantage that leakage and temperature controller thermometric are not allowed.

In addition, the chilldown system of the present embodiment, which is equipped with multiple-protection system, ensures refrigeration system stable operation:

1) traffic protection system: the Precooling unit when admixture of gas is lower than 1/3 load flow or other preset flows When Precooling unit can be automatically stopped the operating of refrigerator, being higher than that 1/2 load Precooling unit is inactive can automatic alarm, it is ensured that refrigeration Compressor protects the stable operation of molecular sieve purifier without liquid；

2) refrigerator temps protect electronic module: when compression ratio is excessively high or absorption causes delivery temperature inclined when the temperature is excessively high Height, refrigeration machine can automatically cut off the power protection refrigerator；

3) low-voltage protection device；

4) high pressure protector；

5) condensed water of special construction empties device, prevents evaporator icing frozen block.

● high-precision oil removing pretreatment

Make the oil removing cell processing in the preprocessed unit of compressed admixture of gas.The oil removing unit includes Accurate filter and end high-precision oil strainer.By three groups of accurate filters, make in pretreated admixture of gas The partial size of mist of oil drops to 0.1 μm or less.The oil removing unit may include water spray system, and the water spray system generation includes The water of microbubble simultaneously passes through oil mist removing of making a return journey to the water for described in the admixture of gas spray to be processed including microbubble, energy Enough efficiently remove most of mist of oil in the admixture of gas.

Wherein, the final stage high-precision oil strainer is using under cryogenic conditions, and the increased principle of adsorbance, final stage is in high precision Oil strainer can remove the mist of oil penetrated with depth.

● deoxidization by adding hydrogen system

In the present embodiment, deoxidization by adding hydrogen system includes reacting furnace and cooler.In order to remove the oxygen in raw material argon gas Component needs to be passed through hydrogen before reacting furnace, so that oxygen content is dropped to 1ppm under the action of catalyst.The reaction process is put Heat makes admixture of gas to be processed cool down using aftercooler.

● sieve purification system

In the present embodiment, absorbing unit may include sieve purification system, may include molecular sieve adsorber, electric heating Device, switch valve and control system.The absorber of the sieve purification system may include at least two molecular sieve adsorbers, It being capable of moisture, carbon dioxide and some hydrocarbons in adsorbed gas mixture.At least two molecular sieve adsorbers In a job when, other molecular sieve adsorbers are reproduced.

The sieve purification system may also include purifier and automatically switch valve, use air-cylinder type switch valve, and Ensure purifier stable operation using 25 three-way electromagnetic valves, valve leakage phenomenon will not occur.

The sieve purification system may also include electric heating tube, use unique rodlike design, it is ensured that and failure rate is low, Convenient disassembly.It single can extract, be replaced when electrothermal tube failure；Core ensures that regeneration gas is uniform using baffle arrangement Electric heating pipe surface is flowed through, makes electrothermal tube that hot-spot phenomenon not occur.

The sieve purification system may also include electric heater control element, use regeneration gas flow and electric heater Start-stop chain control, fully ensure that regeneration gas electric heater long-term safety operation, electric heater control element use two groups Electric heater can stop one group of electric heater when temperature is higher than set temperature value, when temperature is lower than setting value, restart This group of electric heater reaches energy-efficient requirement.

● fractionating column cold box system

The fractionating column cold box system may include ice chest, main heat exchanger, rectifying column, condenser/evaporator, valve and pipeline Deng.Admixture of gas to rectifying can enter main heat exchanger and exchange heat, and through throttling expansion and be admitted to after being further cooled by Rectifying column middle and upper part participates in rectifying.Liquid argon is obtained in tower bottom, exhaust gas is discharged from tower top.

Converge feeding condenser/evaporator with the liquid argon of external complement after tower bottom liquid argon warp knuckle stream, condenser/evaporator is evaporated Argon gas enter main heat exchanger re-heat to room temperature, cooling box pressure can be directly fed to user, be not necessarily to argon gas product compressor, drop In low product compression process, the risk of secondary pollution.

Equipment cold box interior part uses all aluminium alloy structure, and ice chest inner and outer surfaces take anti-corrosion measure, keeps ice chest whole It is more beautiful, it is durable.Rectifying column is made of special process, fully ensures that the flatness of column plate production, it is ensured that operating condition is steady It is fixed, to obtain the high extraction of product.

For critical component-cryogenic globe valve, throttle valve in fractionating column, spy is using high-intensitive rustproof aluminum alloy valve body structure, stream Body inlet-outlet valve body is welding structure, changes traditional flange form connection, has been inherently eliminated that may be present in fractionating column Leak source, the operation for enabling fractionating column steady in a long-term are fully protected.

The low-temp angular stop valve of custom-made uses stainless steel connecting plate, can avoid because valve rod is sweated, frosting is to valve It is corroded caused by connecting plate.

Improved rectifying column support, vavle shelf etc. are all made of stainless steel material production and special insulation support construction, with Loss of refrigeration capacity is reduced, avoids running cold phenomenon generation.

Using three-dimensional parabolic equation, it is ensured that ice chest interior conduit moves towards reasonable, appropriate stress compensation.

● liquid standby and input system

When liquid back-up system is to guarantee unit something unexpected happened, gas supply is unlikely to interrupt at once.Liquid standby system The capacity of system is designed according to field condition and gas-supply ensuring demand.Meanwhile in order to reduce device operating cost, this process Using the cooling capacity of supplement liquid argon as the cold source of rectifying column.The liquid argon of injection ice chest will be drawn from back-up system.

● instrument electric control system

System in the present embodiment uses advanced DCS Computer Control Technology, realize middle control, by machine, one on the spot The control of change, can effective monitoring the whole series reclaimer production process.Complete control system reliable, performance with advanced design Price than it is high the features such as.

2, specific embodiment

The composition of admixture of gas to be processed is as shown in table 1:

Project	Numerical value
		Gas mixture flow to be processed	240Nm³/h
Ar	> 95%
		N₂	< 4%
O₂	< 1%
		CO₂	≤400ppm
C₂H₂	≤0.5ppm
		H₂	<0.7ppm
CO	≤0.5ppm
		N₂O	<0.3ppm
SO_X	<0.2ppm
		CnHm (removes C₂H₂) outside	≤8ppm
Dustiness	<30mg/m³

The composition of the admixture of gas to be processed of table 1

Atmospheric conditions are as shown in table 2:

Project	Numerical value
		Atmospheric pressure	0.1013MPa(A)
Environment temperature	32℃
		Opposite highest humidity	95%
Atmosphere oxygen content	20.95%
		Extreme maximum temperature	42℃
Extreme minimum temperature	-20℃
		Earthquake intensity	7 Maxwell degree
Wind speed	10 grades or more
		Winter cardinal wind	Northwester
Summer cardinal wind	South wind
		Day maximum rainfall	250mm

2 atmospheric conditions of table

The system and method that embodiment 2 is used to recycle the argon product in monocrystalline silicon production tail gas

1. design scheme and basic condition

The flow of admixture of gas to be processed: 2400Nm³/h

Major impurity component in admixture of gas to be processed: dust, hydrocarbon, CO, N₂、O₂Deng each impurity composition Content is about 2-6%.

The pressure of gas mixture inlet to be processed: 2.5kg/cm²

Purified argon product purity: 99.999%, wherein O₂Impurity content be less than 1ppm, technical indicator is specifically shown in Table 3。

The constituent analysis of the purified argon product of table 3

* without metering water content in argon gas

The above-mentioned metering of * is volume fraction

2. capital equipment

The capital equipment that this system is related to is referring to table 4.

4 master device process equipment list of table

In conjunction with various types of compact function consumption, stability, features etc. and the present embodiment process characteristic, in the present embodiment Gas mixture compressor to be processed is recommended to select helical-lobe compressor.

Since the quality of performance of the adsorbent by the purity for directly affecting product and rate of recovery index and is that device is continuously grown Phase stable operation and the guarantee of service using life, thus be the key technology in pressure swing adsorption gas separation device.

Pressure-swing absorption apparatus should follow following principle in adsorbent type selecting:

(1) selection dynamic adsorbance is big, separation is high and the easy adsorbent of desorption；

(2) require selection different for different admixture of gas compositions to be processed and different product quality indicators The adsorbent of type；Or

It (3) is the service life for guaranteeing adsorbent, selected adsorbent must have enough wear-resistant strengths and resistance to compression Intensity has chemical inertness to all gas mediums to be separated.

As the PSA sequencing valve of key equipment, high-performance sequencing valve is selected, with small in size, movement is fast, sealing performance Feature good, the service life is long simultaneously has switching speed separately adjustable and closes pooling feature, reaches No. 1,000,000 switch No leakage (quotient Business guarantees horizontal) advanced level, can better ensure that the long-term running reliability of device, and there is antistatic and spark to design, Further ensure the safety of system.

The anti-fluctuation ability of the method and system of the present embodiment is strong: using high efficiency packing, impurity removal depth is high, adsorption capacity Increase with admixture of gas impurity to be processed and greatly improve, antigen material fluctuation ability is strong, can repeatedly regenerate, Reusability is filled out Expect long service life.

The method and system advanced design, anti-unexpected ability of the present embodiment are strong: according to filler feature, using advanced technologies, Cooperate unique design reaction gas and control program, short time power-off, cutting off the water supply does not influence to produce gas；Configuration optimization through many years, Single electric appliance, instrument element fault condition do not influence normal gas producing, and most of element can realize uninterrupted production gas on-line maintenance.

The method and system of the present embodiment is constructed in implementation process using clean, safe and reliable: clean using famous brand name Net pipe fitting, valve, Full-automatic rail welding, helium ion leak test, cleaning construction, strict guarantee product quality；All elements accord with Close concerned countries security regulations.

The method and system reliable performance of the present embodiment: main element, instrument are all made of import famous brand name, and performance can It leans on.

Cool source part recycles in the method and system of the present embodiment, and cooling capacity is fully used.

3. costs and benefits

It is every to save 0.33 yuan (according to argon gas 1 yuan/kilogram of market price in 2016, reuse cost 0.67 using one kilogram of argon gas Member/kilogram calculating).It is calculated by 1000 monocrystaline silicon stoves, deducts amortization charge, 8,310,000 yuan can be saved every year.The economic effect of project Benefit, social benefit are bigger.There are many crystal growing furnace that solar silicon wafers use at present, and it is meaningful to do this work.

Embodiment 3 carries out oil removing using the bulk processing device for including gas-liquid separation device

Gas-liquid separation device is a set of combined type knockout drum.Oil removing: first step oil removing is separated using following step, Using cyclone separator, remove compared with larger oil droplet.The drop carried secretly in the air-flow of certain speed is tangentially entered by gas phase import and is divided From device lower part, by the density contrast of gas and oil, oil droplet is thrown toward inner tank wall, is guided to bottom along wall surface, air-flow rises, through colliding Flow apron carries out collision separation, enters back into next stage separation.Second step oil removing utilizes the further gas and oil of two layers of spiral board point From.Third step oil removing is separated using vortex-flow and defrosting device further progress gas and oil.Air-flow forms eddy flow after entering, and drop is thrown to Wall surface and be gathered into liquid film flow down, the certain angle of blade lean is conducive to oil droplet and converges and flow to tower wall, multiple S types channel Increase air flow contacts time and collision separation probability.Gas phase after separation is discharged by top of the tank gaseous phase outlet.Second level and three Sump oil after grade gas and oil separation converges to being discharged together.

Aforementioned detailed description is to be not intended to limit scope of the appended claims to explain and provide with example way. A variety of variations of illustrated embodiments set forth herein at present are it will be apparent that and retaining for those of ordinary skills In the range of the attached claims and its equivalent program.

Claims

1. a kind of method of liquid argon for being used to prepare purifying and/or argon gas product, which comprises

A) admixture of gas to be processed is made to be subjected to pretreatment to remove mist of oil, dust and other particulate matters therein to obtain Pretreated admixture of gas；

Contact pretreated admixture of gas a) with catalytic oxidation unit, to make in the admixture of gas Reducibility gas by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；

It contacts the admixture of gas through catalysis oxidation b) with deacidification unit, and is passed through into the deacidification unit suitable When the hydrogen of ratio is so that oxygen content therein is reduced to 2ppm hereinafter, to obtain the admixture of gas of hydrogenated deoxidation；

Contact the admixture of gas of hydrogenated deoxidation c) with absorbing unit, to remove in the admixture of gas Water, carbon dioxide and/or hydrocarbon, to obtain the admixture of gas to rectification process；

E) flow of the admixture of gas to rectification process of measurement d), and be adjusted by buffering gas with rectifying qualification And make the flow of the admixture of gas to rectification process within the scope of the flow operating flexibility of rectification process；And

Handle the admixture of gas to rectification process e) to remove nitrogen and hydrogen through cryogenic rectification, to obtain The liquid argon and/or argon gas product of purifying.

2. according to the method described in claim 1, its further include: g) recycle and/or purify the hydrogen that is removed in f).

3. according to the method described in claim 1, wherein in f), the cryogenic rectification processing includes:

Iii) make ii) the gasification material stream and liquid low temperature cooling medium carry out heat exchange, obtain the argon gas of purifying Product；Also, at least part in the material stream of gasification ii) is condensed into phegma, the phegma conduct The liquid low temperature cooling medium of the rectification process.

4. according to the method described in claim 1, wherein ii) described in heat source be by described to rectification process to e) At least part of admixture of gas carry out pressurization heating or heat temperature raising processing and obtain, the pressure of the heat source is described The dew-point temperature of the material stream increases the pressure of corresponding argon at 1-7 DEG C under operating pressure in cryogenic rectification processing, described The high 0.02-0.1MPa of the pressure of cryogenic condensation medium described in the pressure ratio of heat source.

5. according to the method described in claim 1, being carried out wherein in i) to the admixture of gas to rectification process e) Following processing obtains the material stream:

Ia) make the admixture of gas to rectification process e) mixed through the compressor compresses gas to be processed as high temperature and pressure Close logistics stock；

Ib) make ia) high temperature and pressure gas mixing logistics stock to be processed handle and become low through cooling in heat exchanger Warm high pressure gas mixing logistics stock to be processed；And

Ic) make ib) at least part of cryogenic high pressure gas mixing logistics stock to be processed become after throttling expansion The material stream.

6. the system of a kind of liquid argon for being used to prepare purifying and/or argon gas product, the system comprises:

Pretreatment unit, and gas mixing fluid communication to be processed and removes mist of oil, dust and other particles therein Object is to obtain pretreated admixture of gas；

Catalytic oxidation unit is in fluid communication with the pretreatment unit, and the catalytic oxidation unit makes described pretreated Reducibility gas in admixture of gas is by catalysis oxidation, to obtain the admixture of gas through catalysis oxidation；

Deacidification unit is in fluid communication with the catalytic oxidation unit, and the hydrogen of proper proportion is passed through in Xiang Suoshu deacidification unit Afterwards, the deacidification unit makes the oxygen content in the admixture of gas through catalysis oxidation be reduced to about 2ppm hereinafter, to obtain Obtain the admixture of gas of hydrogenated deoxidation；

Absorbing unit is in fluid communication with the deacidification unit, and the absorbing unit includes that adsorbent is described hydrogenated to remove Water, carbon dioxide and/or hydrocarbon in the admixture of gas of deoxidation, to obtain the gas mixing to rectification process Object；

First buffer cell, with the gas mixing fluid communication to rectification process and include described to essence for measuring The flow rate-measuring device of the flow of the admixture of gas of processing is evaporated, includes that rectifying qualification buffers gas in first buffer cell, The rectifying qualification buffering gas is used to adjust for the flow of the admixture of gas to rectification process, and makes the flow in rectifying Within the scope of the flow operating flexibility of processing；And

Cryogenic rectification unit is in fluid communication with the absorbing unit and first buffer cell, described to rectifying to remove Nitrogen and hydrogen in the admixture of gas of processing, to obtain the liquid argon and/or argon gas product of purifying.

7. system according to claim 6, the system also includes hydrogen retrieval unit, the hydrogen retrieval unit with it is described low Warm rectification cell is in fluid communication and is used to recycle the hydrogen being removed in the cryogenic rectification unit；And/or

The system also includes deoxidation preparatory units, connect respectively with the catalytic oxidation unit and the deacidification unit fluid Logical, the deoxidation preparatory unit includes to remove water in the admixture of gas through catalysis oxidation, carbon dioxide and/or hydrocarbon Compound, to obtain the admixture of gas handled to deacidification unit.

8. system according to claim 6, wherein the pretreatment unit includes bulk processing device and accurate processing unit.

9. system according to claim 6, the system also includes oxygenation measurement unit, the oxygenation measurement unit with it is described pre- Processing unit is in fluid communication and can measure the oxygen concentration in the pretreated admixture of gas；And/or

The system also includes impurity measurement unit, the impurity measurement unit is in fluid communication with the pretreatment unit and can survey Measure the impurity concentration in the pretreated admixture of gas.

10. system according to claim 6, wherein the cryogenic rectification unit includes one or more rectifying columns, each Rectifying column is equipped with condensation reflux device and reboiler, wherein the condensation reflux device is located at the rectifying column upper end, the reboiler Positioned at the rectifying column lower end；

The material stream and the reboiler carry out heat exchange, the material stream to be gasified；The material stream of the gasification Heat exchange is carried out with the condensation reflux device, obtains the argon gas product of purifying in the rectifying column bottom end；The material of the gasification At least part in stream stock is condensed into phegma after the condensation reflux device heat exchange；The phegma is as the rectifying The liquid low temperature cooling medium of processing.