CN101723338B - Method for extracting krypton-xenon from liquid oxygen - Google Patents
Method for extracting krypton-xenon from liquid oxygen Download PDFInfo
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- CN101723338B CN101723338B CN 200910198684 CN200910198684A CN101723338B CN 101723338 B CN101723338 B CN 101723338B CN 200910198684 CN200910198684 CN 200910198684 CN 200910198684 A CN200910198684 A CN 200910198684A CN 101723338 B CN101723338 B CN 101723338B
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Abstract
The invention relates to a method for extracting krypton-xenon from liquid oxygen. The method comprises the following steps of: introducing the liquid oxygen into a first stage rectification tower of a fractionating tower system for rectifying separation to obtain oxygen gas at the tower top and concentrated solution of krypton-xenon at the tower bottom, allowing the concentrated solution to pass through a methane eliminating system and a heat exchanger for cooling and then to enter a second stage rectification tower to obtain the oxygen gas at the tower top and the secondary concentrated solution of krypton-xenon at the tower bottom, delivering the secondary concentrated solution to a third stage rectification tower for rectifying separation to obtain the concentrate of krypton at the tower top and the concentrate of xenon at the tower bottom, delivering the concentrated solution of krypton to a fourth stage rectification tower for rectification to obtain purified krypton products, delivering the xenon containing concentrate to a fifth stage rectification tower for rectification to obtain a xenon containing stream, and finally delivering the xenon containing stream to a sixth stage rectification tower for rectification to obtain purified xenon products. Compared with the prior art, the method has the advantages of having high recovery of krypton and xenon and good economic benefits, improving operating safety of the device, simplifying operation, saving equipment investment cost and energy consumption, widening an application range, preventing the oxygen gas in the raw materials from being polluted and ensuring high purity of the oxygen gas in the raw materials.
Description
Technical field
The present invention relates to a kind of method of extracting rare gas, relate in particular to a kind of method of from liquid oxygen, extracting the krypton xenon.
Background technology
Krypton in the atmosphere and xenon content are about respectively 1.138 * 10
-6With 0.0857 * 10
-6After trace krypton and xenon enter the low-temperature fractionating tower of air separation plant with air, high boiling component krypton, xenon, hydrocarbon polymer (mainly being methane) and fluorochemical all accumulate in the liquid oxygen of lower pressure column, and the liquid oxygen of lower pressure column is sent into a krypton additional rectification column (being commonly called as a krypton tower).Can obtain the poor krypton-xenon concentrate that krypton xenon content is 0.2～0.3%Kr+Xe, wherein methane content is about 0.3～0.4%.
In known method, the extraction equipment of krypton xenon depends on must be with a krypton tower in the large-scale air separation plant, and the poor krypton-xenon concentrate of then a krypton tower being discharged is pressurized to 5.5MPa and makes its vaporization, enters the methane purification devices behind the 1.0MPa that reduces pressure again.The methane purification devices is by palladium catalyst, and under 480～500 ℃ temperature, oxygen and methane carry out behind the chemical reaction methane and is removed that (remaining methane content can be lower than 1 * 10
-6), then remove chemical reaction product-carbonic acid gas and water with molecular sieve adsorption.Along with the krypton xenon is concentrated step by step, methane content improves again thereupon, and therefore this chemical reaction removes methane and also will repeatedly carry out.
Trace Fluoride compound in the poor krypton-xenon concentrate belongs to high boiling component.In the sepn process of krypton xenon, will accumulate in pure krypton and the pure xenon.In known method, be to pass through respectively activated zr aluminium getter, under 700 ℃ of temperature, remove the foreign gas fluorochemical.
Several steps such as the purification of krypton xenon will be passed through deoxygenation, the separation of krypton xenon, krypton is refining, slightly xenon is purified, xenon is refining, each step is finished in rectifying tower.Normal liquid nitrogen, low temperature nitrogen, the normal temperature nitrogen etc. of adopting are as low-temperature receiver at present, go out the low-temperature receiver gas temperature of condenser/evaporator generally below-100 ℃, the direct re-heat press that makes the return trip empty through air temperature type vaporizer after the low wet that rectifying tower at different levels are discharged compiles, cold is directly lost to atmosphere.
Prior art making pure krypton and pure xenon have following shortcoming:
(1) removing the required activated zr aluminium getter of fluorochemical is to belong to consuming goods and materials, needs periodic replacement;
(2) need to repeatedly use chemical method to remove methane;
(3) cold does not reclaim, and energy consumption is high;
(4) depend in the large-scale space division device with a krypton tower, range of application is narrow.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of product purity is high, simple to operate, the method for extraction krypton xenon from liquid oxygen of applied range.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method of extracting the krypton xenon from liquid oxygen is characterized in that the method may further comprise the steps:
(1) liquid oxygen is passed in the first step rectifying tower in the fractionating column system, the rectifying tower pressure-controlled is at 0.1～0.4MPa, preferred 0.3MPa, stage number is 4～20, and preferred 10, the tower temperature control is made as-160～-180 ℃, carry out rectifying separation, obtain oxygen at cat head, obtain krypton xenon concentrated solution at the bottom of the tower;
(2) the krypton xenon concentrated solution that step (1) tower reactor is obtained is sent ice chest, through removing the methane system, the methane molar content in the krypton-xenon concentrate is down to 1 * 10
-6Then mol uses molecular screener adsorbing system to remove water and carbonic acid gas in the krypton-xenon concentrate;
(3) krypton-xenon concentrate that step (2) is obtained is sent ice chest to, through sending in the two-stage rectification tower after the interchanger cooling, the rectifying tower pressure-controlled is at 0.1～0.7MPa, preferred 0.6MPa, stage number is 10～50, and preferred 25, the tower temperature control is made as-110～-160 ℃, obtain oxygen at cat head, obtain krypton xenon secondary concentration liquid at the bottom of the tower;
(4) the krypton xenon secondary concentration liquid that step (3) tower reactor is obtained is sent in the third stage rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.7MPa, preferred 0.5MPa, stage number is 4～40, preferred 18, the tower temperature control is made as-70～-140 ℃, carries out rectifying separation, cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower;
(5) the krypton concentrated solution that step (4) cat head is obtained is sent in the fourth stage rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.6MPa, preferred 0.45MPa, stage number is 4～30, preferred 15, the tower temperature control is made as-120～-140 ℃, carries out rectifying separation, and cat head obtains molar content and is not less than 99.999% pure krypton product;
(6) xenon concentrate that contains that step (4) tower reactor is obtained is sent in the level V rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.4MPa, preferred 0.3MPa, stage number is 10～90, preferred 60, the tower temperature control is made as-80～-110 ℃, carries out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid;
(7) the xenon fluid that contains that step (6) cat head is obtained is sent in the 6th grade of rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.4MPa, preferred 0.25MPa, stage number is 4～20, preferred 10, the tower temperature control is made as-80～-110 ℃, carries out rectifying separation, obtains molar content and be not less than 99.999% pure xenon product at the bottom of tower.
Be provided with reboiler at the bottom of the tower of described first step rectifying tower, cat head is provided with condenser/evaporator, and nitrogen is introduced fractionating column system, and through passing in the tower bottom reboiler of first step rectifying tower after the main heat exchanger cooling, as thermal source, nitrogen is cooled to liquid nitrogen.
Use as low-temperature receiver in the condenser/evaporator of described liquid nitrogen extraction part introducing first step rectifying tower and second stage rectifying tower cat head.
The cat head of described third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower and the 6th grade of rectifying tower is provided with condenser/evaporator, and described condenser/evaporator adopts low temperature nitrogen and the mixed gas of normal temperature nitrogen.
The nitrogen that the condenser/evaporator of described rectifying tower cat head is discharged converges the rear main heat exchanger that all returns, and carries out the cold recovery utilization.
Described rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower all wrap in the ice chest that is filled with thermal insulation material.
Described thermal insulation material comprises super glass wool or pearlstone.
Compared with prior art, the present invention has the following advantages:
(1) rate of recovery of the krypton in the liquid oxygen and xenon is high, can reach more than 95% respectively;
(2) the present invention arranges a krypton tower in native system, carries out the once concentration of krypton xenon, removes methane by chemical method, by step by step rectifying, removes all the low boiling component (O in the dense krypton xenon unstripped gas again
2, N
2, Ar) and high boiling component hydrocarbon polymer (CH
4, C
2H
4, C
2H
6, C
3H
8) and fluorochemical (CF
4, C
2F
6, SF
6) finally obtain purity and be higher than 99.999% pure krypton and pure xenon product, wherein various impurity individual event content all are lower than the high-purity krypton technical indicator of GB/T5829-2006 and the high-purity xenon technical indicator of GB/T5828-2006;
(3) this technical process good in economic efficiency, improved the device operational safety performance, simple to operate, saved facility investment expense and energy consumption;
(4) applied range, this device only needs a small amount of nitrogen namely to can be whole fractionating column system provides low-temperature receiver to replenish, the user be provided with fill krypton-xenon liquid body vacuum jacketed flask and liquid nitrogen cryogenics storage tank after, apparatus of the present invention can break away from air separation plant, independent operating, also can use by supporting existing air separation plant, realize the continuous and stable production operation;
(5) oxygen in this device raw material can be not contaminated, by can directly providing the user to use after the main heat exchanger re-heat.This device has reclaimed the cold of liquid oxygen and has produced liquid nitrogen product.
Description of drawings
Fig. 1 is the process flow sheet among the embodiment 1;
Fig. 2 is the process flow sheet among the embodiment 2.
1 is first step rectifying tower among the figure, 2 is second stage rectifying tower, 3 is third stage rectifying tower, 4 is fourth stage rectifying tower, 5 is the level V rectifying tower, 6 is the 6th grade of rectifying tower, 7 is condenser/evaporator, 8 is condenser/evaporator, 9 is condenser/evaporator, 10 is condenser/evaporator, 11 is condenser/evaporator, 12 is condenser/evaporator, 13 is electric reboiler, 14 is electric heater, 15 is electric heater, 16 is electric heater, 17 is electric heater, 18 is electric heater, 19 is head tank, 20 is liquid oxygen pump, 21 is vaporizer, 22 is regenerator, 23 is electric heater, 24 is the methane contact oven, 25 is water cooler, 26 is molecular sieve adsorber, 27 is main heat exchanger, 28 is main heat exchanger, 29 is ice chest.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of krypton xenon lamp method of extracting from liquid oxygen, its technical process comprises a fractionating column system as shown in Figure 1, includes: main heat exchanger 27,28, six grades of rectifying tower, first step rectifying tower 1 bottom liquid gives off ice chest, enters the methane system that removes.Enter in the second stage rectifying tower 2 through the enriched material after the removing methane system.Rectifying tower 2 top ejectas in the second stage are oxygen, through discharging ice chest after the main heat exchanger re-heat.Rectifying tower 2 bottoms in the second stage are connected in the third stage rectifying tower 3.Third stage rectifying tower 3 tops are connected in the fourth stage rectifying tower 4, and third stage rectifying tower 3 bottoms are connected in the level V rectifying tower 5.Level V rectifying tower 5 tops are connected in the 6th grade of rectifying tower 6.Rectifying tower at different levels top is equipped with a condenser/evaporator, and first step rectifier bottoms is provided with reboiler, and all the other rectifier bottoms are equipped with an electric heater.First step rectifying tower 1 bottom makes electricity consumption reboiler 13, electric heater 14 is used in rectifying tower 2 bottoms in the second stage, electric heater 15 is used in third stage rectifying tower 3 bottoms, electric heater 16 is used in fourth stage rectifying tower 4 bottoms, level V rectifying tower 5 bottoms use 17, the six grades of rectifying tower 6 bottoms of electric heater to use electric heater 18.Reboiler 13 thermals source of first step rectifying tower 1 bottom are selected low temperature nitrogen, and low temperature nitrogen derives from by main heat exchanger 27,28 cooled normal temperature nitrogen.First step rectifying tower 1 top be provided with condenser/evaporator 7, low-temperature receiver adopts liquid nitrogen.Second stage rectifying tower 2 tops be provided with condenser/evaporator 8, low-temperature receiver adopts liquid nitrogen 26.The condenser/evaporator 9,10,11 of other rectifying tower cats head, 12 entrance low-temperature receiver are according to a certain percentage mixed gas of normal temperature nitrogen and low temperature nitrogen, enter in the main heat exchanger 27 after the cryogenic gas of condenser/evaporator outlet converges.
Raw material in the head tank 19 enters in the first step rectifying tower 1, and first step rectifying tower 1 top condenser/evaporator adopts liquid-nitrogen boiling, and control liquid nitrogen pressure is about 0.55MPa, makes the interior rising vapor condensation of tower become phegma, thereby sets up the rectifying operating mode.The condenser/evaporator of other rectifying tower adopts low temperature nitrogen, temperature is about-180 ℃, make low-temperature receiver with normal temperature nitrogen mixture body, temperature control is greatly about-110～-150 ℃, under this temperature, can avoid the krypton xenon crystallization in the steam in the tower, can form again the phegma of the needs of rectifying operating mode in the tower simultaneously.
This device also comprises one and removes the methane system: at first poor krypton-xenon concentrate is pressurized to 5.5MPa by liquid oxygen pump 20, then pass into gasifier 21 and make its vaporization, reduce pressure again behind the 1.0MPa successively by regenerator 22, enter except methane contact oven 24 behind the electric heater 23.Palladium catalyst is housed except methane contact oven 24, under 480～500 ℃ temperature, oxygen and methane carry out behind the chemical reaction methane and are removed that (remaining methane molar content can be lower than 1 * 10
-6), then through after entering water cooler 25 further coolings after regenerator 22 coolings, gas enters molecular sieve adsorber 26, is used for removing chemical reaction product---carbonic acid gas and water.Enter fractionating column system through the poor krypton xenon thing behind the removing methane, through being introduced in the two-stage rectification tower 2 after main heat exchanger 27,28 coolings.
The present invention utilizes hydrocarbon polymer (C
nH
m), fluorochemical (CF
4, C
2F
6, SF
6), krypton, xenon boiling point separately is different, separates successively impurities, under the prerequisite that keeps high extraction (being not less than 95%), production purity is higher than 99.999% pure krypton and pure xenon product.
Liquid oxygen is passed in the one-level rectifying tower 1, obtain one-level krypton xenon concentrated solution at the bottom of the tower, wherein methane content is no more than 5000 * 10
-6Krypton xenon concentrated solution is drawn separation column deliver to and again introduce in the fractionating column system after removing the methane system, the methane content of this moment is 1 * 10
-6About.Introduce in the two-stage rectification tower 2 through krypton xenon concentrated solution after main heat exchanger 27,28 coolings, at the bottom of tower, obtain secondary krypton xenon concentrated solution, the krypton xenon content about 99.9% of this moment.Secondary krypton xenon concentrated solution is introduced three grades of rectifying tower 3 krypton xenons to be separated through the krypton xenon.To contain the krypton enriched material and send in the fourth stage rectifying tower 4, and obtain the pure krypton of product fluid at cat head, wherein the molar content of Kr is not less than 99.999%, CH
4Molar content be no more than 0.3 * 10
-6, CF
4Discharge at the bottom of the tower to collect and recycle.
To contain xenon concentrate and send in the level V rectifying tower 5, and obtain containing the xenon fluid at cat head, wherein the molar content of Xe is not less than 99.99%, CF
4Molar content be not higher than 100 * 10
-6, impurity C
2H
4Molar content be no more than 1 * 10
-6, C
2F
6, SF
6, CH
4, C
3H
8, N
2O, C
2H
6Cryogenic pipelines 41 is discharged and is collected at the bottom of the tower.
To contain the xenon fluid and send in the 6th grade of rectifying tower 6, and obtain the liquid pure xenon at the bottom of tower, wherein the molar content of Xe is not less than 99.999%, impurity C
2H
4Molar content be no more than 1 * 10
-6, and contain CF in the xenon fluid 40
4Will be at cat head along with fluid is discharged from collection along cryogenic pipelines.
The low wet that all condenser/evaporators are discharged converges the rear main heat exchanger that all returns, and carries out cold recovery.
All rectifying tower, cryogenic pipelines and valve all wrap in the ice chest 29 that is filled with thermal insulation material such as super glass wool, pearlstone etc.
Embodiment 2
A kind of method of from liquid oxygen, extracting the krypton xenon, its technical process as shown in Figure 2, be that with embodiment 1 difference this flow process has been cancelled gasifier, the krypton xenon concentrated solution after liquid oxygen pump 20 pressurizations is sent into re-heat in the main heat exchanger 27,28, then pass in the regenerator 22, all the other are identical with embodiment 1: comprise a fractionating column system, include: main heat exchanger 27,28, six grades of rectifying tower, first step rectifying tower 1 bottom liquid gives off ice chest, enters the methane system that removes.Enter in the second stage rectifying tower 2 through the enriched material after the removing methane system.Rectifying tower 2 top ejectas in the second stage are oxygen, through discharging ice chest after the main heat exchanger re-heat.Rectifying tower 2 bottoms in the second stage are connected in the third stage rectifying tower 3.Third stage rectifying tower 3 tops are connected in the fourth stage rectifying tower 4, and third stage rectifying tower 3 bottoms are connected in the level V rectifying tower 5.Level V rectifying tower 5 tops are connected in the 6th grade of rectifying tower 6.Rectifying tower at different levels top is equipped with a condenser/evaporator, and first step rectifier bottoms is provided with reboiler, and all the other rectifier bottoms are equipped with an electric heater.First step rectifying tower 1 bottom makes electricity consumption reboiler 13, electric heater 14 is used in rectifying tower 2 bottoms in the second stage, electric heater 15 is used in third stage rectifying tower 3 bottoms, electric heater 16 is used in fourth stage rectifying tower 4 bottoms, level V rectifying tower 5 bottoms use 17, the six grades of rectifying tower 6 bottoms of electric heater to use electric heater 18.Reboiler 13 thermals source of first step rectifying tower 1 bottom are selected low temperature nitrogen, and low temperature nitrogen derives from by main heat exchanger 27,28 cooled normal temperature nitrogen.First step rectifying tower 1 top be provided with condenser/evaporator 7, low-temperature receiver adopts liquid nitrogen.Second stage rectifying tower 2 tops be provided with condenser/evaporator 8, low-temperature receiver adopts liquid nitrogen 26.The condenser/evaporator 9,10,11 of other rectifying tower cats head, 12 entrance low-temperature receiver are according to a certain percentage mixed gas of normal temperature nitrogen and low temperature nitrogen, enter in the main heat exchanger 27 after the cryogenic gas of condenser/evaporator outlet converges.
Raw material in the head tank 19 enters in the first step rectifying tower 1, and first step rectifying tower 1 top condenser/evaporator adopts liquid-nitrogen boiling, and control liquid nitrogen pressure is about 0.55MPa, makes the interior rising vapor condensation of tower become phegma, thereby sets up the rectifying operating mode.The condenser/evaporator of other rectifying tower adopts low temperature nitrogen, temperature is about-180 ℃, make low-temperature receiver with normal temperature nitrogen mixture body, temperature control is greatly about-110～-150 ℃, under this temperature, can avoid the krypton xenon crystallization in the steam in the tower, can form again the phegma of the needs of rectifying operating mode in the tower simultaneously.
This device also comprises one and removes the methane system: at first poor krypton-xenon concentrate is pressurized to 5.5MPa by liquid oxygen pump 20, directly pass into re-heat in the main heat exchanger 27,28, reduce pressure again behind the 1.0MPa by regenerator 22, enter except methane contact oven 24 behind the electric heater 23.Palladium catalyst is housed except methane contact oven 24, under 480～500 ℃ temperature, oxygen and methane carry out behind the chemical reaction methane and are removed that (remaining methane molar content can be lower than 1 * 10
-6), then through after entering water cooler 25 further coolings after regenerator 22 coolings, gas enters molecular sieve adsorber 26, is used for removing chemical reaction product---carbonic acid gas and water.Enter fractionating column system through the poor krypton xenon thing behind the removing methane, through being introduced in the two-stage rectification tower 2 after main heat exchanger 27,28 coolings.
The present invention utilizes hydrocarbon polymer (C
nH
m), fluorochemical (CF
4, C
2F
6, SF
6), krypton, xenon boiling point separately is different, separates successively impurities, under the prerequisite that keeps high extraction (being not less than 95%), production purity is higher than 99.999% pure krypton and pure xenon product.
Liquid oxygen is passed in the one-level rectifying tower 1, obtain one-level krypton xenon concentrated solution at the bottom of the tower, wherein methane content is no more than 5000 * 10
-6Krypton xenon concentrated solution is drawn separation column deliver to and again introduce in the fractionating column system after removing the methane system, the methane content of this moment is 1 * 10
-6About.Introduce in the two-stage rectification tower 2 through krypton xenon concentrated solution after main heat exchanger 27,28 coolings, at the bottom of tower, obtain secondary krypton xenon concentrated solution, the krypton xenon content about 99.9% of this moment.Secondary krypton xenon concentrated solution is introduced three grades of rectifying tower 3 krypton xenons to be separated through the krypton xenon.To contain the krypton enriched material and send in the fourth stage rectifying tower 4, and obtain the pure krypton of product fluid at cat head, wherein the molar content of Kr is not less than 99.999%, CH
4Molar content be no more than 0.3 * 10
-6, CF
4Discharge at the bottom of the tower to collect and recycle.
To contain xenon concentrate and send in the level V rectifying tower 5, and obtain containing the xenon fluid at cat head, wherein the molar content of Xe is not less than 99.99%, CF
4Molar content be not higher than 100 * 10
-6, impurity C
2H
4Molar content be no more than 1 * 10
-6, C
2F
6, SF
6, CH
4, C
3H
8, N
2O, C
2H
6Cryogenic pipelines 41 is discharged and is collected at the bottom of the tower.
To contain the xenon fluid and send in the 6th grade of rectifying tower 6, and obtain the liquid pure xenon at the bottom of tower, wherein the molar content of Xe is not less than 99.999%, impurity C
2H
4Molar content be no more than 1 * 10
-6, and contain CF in the xenon fluid 40
4Will be at cat head along with fluid is discharged from collection along cryogenic pipelines.
The low wet that all condenser/evaporators are discharged converges the rear main heat exchanger that all returns, and carries out cold recovery.
All rectifying tower, cryogenic pipelines and valve all wrap in the ice chest 29 that is filled with thermal insulation material such as super glass wool, pearlstone etc.
Embodiment 3
A kind of method of from liquid oxygen, extracting the krypton xenon, the method may further comprise the steps:
(1) liquid oxygen is passed in the first step rectifying tower in the fractionating column system, the rectifying tower pressure-controlled is at 0.1MPa, stage number is 4, preferred 10, the tower temperature control is made as-160, carry out rectifying separation, obtain oxygen at cat head, obtain krypton xenon concentrated solution at the bottom of the tower, be provided with reboiler and condenser/evaporator at the bottom of the tower of first step rectifying tower, nitrogen is introduced fractionating column system, through passing in the tower bottom reboiler of first step rectifying tower after the main heat exchanger cooling, as thermal source, nitrogen is cooled to liquid nitrogen, uses as low-temperature receiver in the condenser/evaporator of extraction part liquid nitrogen introducing first step rectifying tower and second stage rectifying tower cat head;
(2) the krypton xenon concentrated solution that step (1) tower reactor is obtained is sent ice chest, through removing the methane system, the methane molar content in the krypton-xenon concentrate is down to 1 * 10
-6Then mol uses molecular screener adsorbing system to remove water and carbonic acid gas in the krypton-xenon concentrate;
(3) krypton-xenon concentrate that step (2) is obtained is sent ice chest to, and through sending in the two-stage rectification tower after the interchanger cooling, the rectifying tower pressure-controlled is at 0.1MPa, stage number is 10, the tower temperature control is made as-110 ℃, obtains oxygen at cat head, and tower reactor obtains krypton xenon secondary concentration liquid;
(4) the krypton xenon secondary concentration liquid that step (3) tower reactor is obtained is sent in the third stage rectifying tower, and the rectifying tower pressure-controlled is at 0.1MPa, and stage number is 4, and the tower temperature control is made as-70 ℃, carries out rectifying separation, and cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower;
(5) the krypton concentrated solution that step (4) cat head is obtained is sent in the fourth stage rectifying tower, and the rectifying tower pressure-controlled is at 0.1MPa, and stage number is 4, and the tower temperature control is made as-120 ℃, carries out rectifying separation, and cat head obtains molar content and is not less than 99.999% pure krypton product;
(6) xenon concentrate that contains that step (4) tower reactor is obtained is sent in the level V rectifying tower, the rectifying tower pressure-controlled is at 0.1MPa, and stage number is 10, and the tower temperature control is made as-80 ℃, carry out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid;
(7) the xenon fluid that contains that step (6) cat head is obtained is sent in the 6th grade of rectifying tower, the rectifying tower pressure-controlled is at 0.1MPa, and stage number is 4, and the tower temperature control is made as-80 ℃, carry out rectifying separation, at the bottom of tower, obtain molar content and be not less than 99.999% pure xenon product.
The condenser/evaporator of third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower and the 6th grade of rectifying tower adopts low temperature nitrogen and the mixed gas of normal temperature nitrogen, the nitrogen that the condenser/evaporator of rectifying tower cat head is discharged converges the rear main heat exchanger that all returns, carry out the cold recovery utilization, rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower all wrap in the ice chest that is filled with thermal insulation material.
Embodiment 4
A kind of method of extracting the krypton xenon from liquid oxygen is characterized in that the method may further comprise the steps:
(1) liquid oxygen is passed in the first step rectifying tower in the fractionating column system, the rectifying tower pressure-controlled is at 0.4MPa, stage number is 20, the tower temperature control is made as-180 ℃, carry out rectifying separation, obtain oxygen at cat head, obtain krypton xenon concentrated solution at the bottom of the tower, be provided with reboiler and condenser/evaporator at the bottom of the tower of first step rectifying tower, nitrogen is introduced fractionating column system, through passing in the tower bottom reboiler of first step rectifying tower, as thermal source after the main heat exchanger cooling, nitrogen is cooled to liquid nitrogen, uses as low-temperature receiver in the condenser/evaporator of extraction part liquid nitrogen introducing first step rectifying tower and second stage rectifying tower cat head;
(2) the krypton xenon concentrated solution that step (1) tower reactor is obtained is sent ice chest, through removing the methane system, the methane molar content in the krypton-xenon concentrate is down to 1 * 10
-6Then mol uses molecular screener adsorbing system to remove water and carbonic acid gas in the krypton-xenon concentrate;
(3) krypton-xenon concentrate that step (2) is obtained is sent ice chest to, and through sending in the two-stage rectification tower after the interchanger cooling, the rectifying tower pressure-controlled is at 0.7MPa, stage number is 50, the tower temperature control is made as-160 ℃, obtains oxygen at cat head, and tower reactor obtains krypton xenon secondary concentration liquid;
(4) the krypton xenon secondary concentration liquid that step (3) tower reactor is obtained is sent in the third stage rectifying tower, and the rectifying tower pressure-controlled is at 0.7MPa, and stage number is 40, the tower temperature control is made as-140 ℃, carry out rectifying separation, cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower;
(5) the krypton concentrated solution that step (4) cat head is obtained is sent in the fourth stage rectifying tower, the rectifying tower pressure-controlled is at 0.6MPa, and stage number is 30, and the tower temperature control is made as-140 ℃, carry out rectifying separation, cat head obtains molar content and is not less than 99.999% pure krypton product;
(6) xenon concentrate that contains that step (4) tower reactor is obtained is sent in the level V rectifying tower, the rectifying tower pressure-controlled is at 0.4MPa, and stage number is 90, and the tower temperature control is made as-110 ℃, carry out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid;
(7) the xenon fluid that contains that step (6) cat head is obtained is sent in the 6th grade of rectifying tower, the rectifying tower pressure-controlled is at 0.4MPa, and stage number is 20, and the tower temperature control is made as-110 ℃, carry out rectifying separation, at the bottom of tower, obtain molar content and be not less than 99.999% pure xenon product.
The condenser/evaporator of third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower and the 6th grade of rectifying tower adopts low temperature nitrogen and the mixed gas of normal temperature nitrogen, the nitrogen that the condenser/evaporator of rectifying tower cat head is discharged converges the rear main heat exchanger that all returns, carry out the cold recovery utilization, rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower all wrap in the ice chest that is filled with thermal insulation material.
Embodiment 5
A kind of method of extracting the krypton xenon from liquid oxygen is characterized in that the method may further comprise the steps:
(1) liquid oxygen is passed in the first step rectifying tower in the fractionating column system, the rectifying tower pressure-controlled is at 0.3MPa, and stage number is 10, and the tower temperature control is made as-170 ℃, carries out rectifying separation, obtains oxygen at cat head, obtains krypton xenon concentrated solution at the bottom of the tower;
(2) the krypton xenon concentrated solution that step (1) tower reactor is obtained is sent ice chest, through removing the methane system, the methane molar content in the krypton-xenon concentrate is down to 1 * 10
-6Then mol uses molecular screener adsorbing system to remove water and carbonic acid gas in the krypton-xenon concentrate;
(3) krypton-xenon concentrate that step (2) is obtained is sent ice chest to, and through sending in the two-stage rectification tower after the interchanger cooling, the rectifying tower pressure-controlled is at 0.6MPa, stage number is 25, the tower temperature control is made as-150 ℃, obtains oxygen at cat head, and tower reactor obtains krypton xenon secondary concentration liquid;
(4) the krypton xenon secondary concentration liquid that step (3) tower reactor is obtained is sent in the third stage rectifying tower, and the rectifying tower pressure-controlled is at 0.5MPa, and stage number is 18, the tower temperature control is made as-100 ℃, carry out rectifying separation, cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower;
(5) the krypton concentrated solution that step (4) cat head is obtained is sent in the fourth stage rectifying tower, the rectifying tower pressure-controlled is at 0.45MPa, and stage number is 15, and the tower temperature control is made as-130 ℃, carry out rectifying separation, cat head obtains molar content and is not less than 99.999% pure krypton product;
(6) xenon concentrate that contains that step (4) tower reactor is obtained is sent in the level V rectifying tower, the rectifying tower pressure-controlled is at 0.3MPa, and stage number is 60, and the tower temperature control is made as-100 ℃, carry out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid;
(7) the xenon fluid that contains that step (6) cat head is obtained is sent in the 6th grade of rectifying tower, the rectifying tower pressure-controlled is at 0.25MPa, and stage number is 10, and the tower temperature control is made as-100 ℃, carry out rectifying separation, at the bottom of tower, obtain molar content and be not less than 99.999% pure xenon product.
The condenser/evaporator of third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower and the 6th grade of rectifying tower adopts low temperature nitrogen and the mixed gas of normal temperature nitrogen, the nitrogen that the condenser/evaporator of rectifying tower cat head is discharged converges the rear main heat exchanger that all returns, carry out the cold recovery utilization, rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower all wrap in the ice chest that is filled with thermal insulation material.
Claims (7)
1. method of extracting the krypton xenon from liquid oxygen is characterized in that the method may further comprise the steps:
(1) liquid oxygen is passed in the first step rectifying tower in the fractionating column system, the rectifying tower pressure-controlled is at 0.1～0.4MPa, and stage number is 4～20, and the tower temperature control is made as-160～-180 ℃, carries out rectifying separation, obtains oxygen at cat head, obtains krypton xenon concentrated solution at the bottom of the tower;
(2) the krypton xenon concentrated solution that step (1) tower reactor is obtained is sent ice chest, through removing the methane system, the methane molar content in the krypton-xenon concentrate is down to 1 * 10
-6Then mol uses molecular screener adsorbing system to remove water and carbonic acid gas in the krypton-xenon concentrate;
(3) krypton-xenon concentrate that step (2) is obtained is sent ice chest to, through sending in the two-stage rectification tower after the interchanger cooling, the rectifying tower pressure-controlled is at 0.1～0.7MPa, stage number is 10～50, the tower temperature control is made as-110～-160 ℃, obtain oxygen at cat head, obtain krypton xenon secondary concentration liquid at the bottom of the tower;
(4) the krypton xenon secondary concentration liquid that step (3) tower reactor is obtained is sent in the third stage rectifying tower, and the rectifying tower pressure-controlled is at 0.1～0.7MPa, and stage number is 4～40, the tower temperature control is made as-70～-140 ℃, carry out rectifying separation, cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower;
(5) the krypton concentrated solution that step (4) cat head is obtained is sent in the fourth stage rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.6MPa, and stage number is 4～30, and the tower temperature control is made as-120～-140 ℃, carry out rectifying separation, cat head obtains molar content and is not less than 99.999% pure krypton product;
(6) xenon concentrate that contains that step (4) tower reactor is obtained is sent in the level V rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.4MPa, and stage number is 10～90, and the tower temperature control is made as-80～-110 ℃, carry out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid;
(7) the xenon fluid that contains that step (6) cat head is obtained is sent in the 6th grade of rectifying tower, the rectifying tower pressure-controlled is at 0.1～0.4MPa, and stage number is 4～20, and the tower temperature control is made as-80～-110 ℃, carry out rectifying separation, at the bottom of tower, obtain molar content and be not less than 99.999% pure xenon product.
2. a kind of method of from liquid oxygen, extracting the krypton xenon according to claim 1, it is characterized in that, be provided with reboiler at the bottom of the tower of described first step rectifying tower, cat head is provided with condenser/evaporator, nitrogen is introduced fractionating column system, through passing in the tower bottom reboiler of first step rectifying tower after the main heat exchanger cooling, as thermal source, nitrogen is cooled to liquid nitrogen.
3. a kind of method of extracting the krypton xenon from liquid oxygen according to claim 2 is characterized in that, uses as low-temperature receiver in the condenser/evaporator of described liquid nitrogen extraction part introducing first step rectifying tower and second stage rectifying tower cat head.
4. a kind of method of from liquid oxygen, extracting the krypton xenon according to claim 1, it is characterized in that, the cat head of described third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower and the 6th grade of rectifying tower is provided with condenser/evaporator, and described condenser/evaporator adopts low temperature nitrogen and the mixed gas of normal temperature nitrogen.
5. according to claim 2 or 4 described a kind of methods of from liquid oxygen, extracting the krypton xenon, it is characterized in that the nitrogen that the condenser/evaporator of rectifying tower cat head is discharged converges the rear main heat exchanger that all returns, and carries out
Cold recovery is utilized.
6. a kind of method of from liquid oxygen, extracting the krypton xenon according to claim 1, its spy
Levy and be that the cryogenic pipelines between described rectifying tower, the connection rectifying tower and valve all wrap in and be filled with thermal insulation material
Ice chest in.
7. a kind of method of extracting the krypton xenon from liquid oxygen according to claim 6 is characterized in that described thermal insulation material comprises super glass wool or pearlstone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795607B (en) * | 2011-05-25 | 2014-09-10 | 俄罗斯深冷机械制造股份公司 | Xenon-krypton mixture extraction equipment and technology |
| CN102538393A (en) * | 2011-07-26 | 2012-07-04 | 上海启元空分技术发展股份有限公司 | Method for separating concentrated krypton-xenon containing CO2 and methane |
| CN102583280A (en) * | 2012-01-29 | 2012-07-18 | 济南鲍德气体有限公司 | Device and method for purifying high-purity xenon and krypton |
| CN103743195B (en) * | 2014-01-24 | 2016-05-18 | 俄罗斯深冷机械制造股份公司 | A kind of Apparatus and method for that extracts crude krypton xenon from liquid oxygen |
| CN109292743A (en) * | 2018-11-09 | 2019-02-01 | 瀚沫能源科技（上海）有限公司 | The device and method thereof of concentrated krypton-xenon concentrate in a kind of liquid oxygen |
| CN109279587A (en) * | 2018-11-09 | 2019-01-29 | 瀚沫能源科技（上海）有限公司 | The device and method thereof of concentrated krypton-xenon concentrate in a kind of liquid oxygen |
| CN113144655B (en) * | 2021-04-28 | 2022-06-21 | 安徽金轩科技有限公司 | Jiale musk rectification unit and rectification process thereof |
| CN113465292B (en) * | 2021-07-05 | 2023-02-21 | 乔治洛德方法研究和开发液化空气有限公司 | Method for increasing yield of krypton/xenon in air rectification device |
| CN114440554B (en) * | 2022-01-26 | 2024-05-07 | 中科富海(杭州)气体工程科技有限公司 | Device and method for producing high-purity oxygen |
| CN116119629A (en) * | 2023-01-07 | 2023-05-16 | 首钢京唐钢铁联合有限责任公司 | Heating regulation and control method for extracting and enriching krypton-xenon gas |
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