CN101723339B - Rectification method for extracting krypton-xenon from liquid oxygen - Google Patents
Rectification method for extracting krypton-xenon from liquid oxygen Download PDFInfo
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- CN101723339B CN101723339B CN2009102002316A CN200910200231A CN101723339B CN 101723339 B CN101723339 B CN 101723339B CN 2009102002316 A CN2009102002316 A CN 2009102002316A CN 200910200231 A CN200910200231 A CN 200910200231A CN 101723339 B CN101723339 B CN 101723339B
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Abstract
The invention relates to a rectification method for extracting krypton-xenon from liquid oxygen. The method comprises the following steps of: collecting extracted liquid oxygen by a storage tank and allowing the liquid oxygen to enter a fractionating tower system; and removing impurities by a rectifying tower and a nitrogen washing tower arranged in a fractionating tower system so as to extract the krypton-xenon with high purity. Compared with the prior art, the method has the advantages of high recovery of krypton and xenon, safe and reliable whole flow, good economic benefits, high device operation safety, low equipment investment cost and energy consumption, wide application range, and the realization of continuous and stable production operation.
Description
Technical field
The present invention relates to a kind of rare gas method of purification, especially relate to a kind of rectificating method that from liquid oxygen, extracts the krypton xenon.
Background technology
Krypton in the atmosphere and xenon content are about 1.138 * 10 respectively
-6With 0.0857 * 10
-6Behind trace krypton and the low-temperature fractionating tower of xenon with the air admission air separation plant; 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 have 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, gets into the methane purification devices behind the 1.0MPa that reduces pressure again.The methane purification devices is through 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), remove chemical reaction product-carbonic acid gas and water with molecular sieve adsorption then.Along with the krypton xenon concentrates step by step, methane content improves again thereupon, and therefore this chemical reaction removes methane and also will repeatedly carry out.The device that adopts chemical reaction method to remove methane moves dangerous and will lose a part of krypton and xenon, simultaneously because operational path is long, and equipment is many, reveals also increase thereupon of loss.Therefore the recovery of krypton and xenon is lower, and the micro-fluorochemical 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 activated zr aluminium getter respectively, 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 all accomplished in rectifying tower.Normal at present employing liquid nitrogen, low temperature nitrogen, normal temperature nitrogen etc. are as low-temperature receiver; The low-temperature receiver gas temperature that goes out condenser/evaporator is generally below-100 ℃; Directly through air temperature type vaporizer re-heat making the return trip empty press, cold directly scattered and disappeared to atmosphere after the low wet that rectifying tower at different levels are discharged compiled.
The known technology of producing pure krypton and pure xenon has following shortcoming: the recovery of (1) krypton and xenon is lower, generally is no more than 80%; (2) removing the required activated zr aluminium getter of fluorochemical is to belong to consuming goods and materials, needs periodic replacement; (3) cold does not reclaim, and energy consumption is high; (4) depend on and have a krypton tower, narrow in application range in the large-scale space division device.
Summary of the invention
The object of the invention is exactly that a kind of applied range, energy-conservation, the rectificating method that from liquid oxygen, extracts the krypton xenon that the product extraction yield is high are provided in order to overcome the defective that above-mentioned prior art exists.
The object of the invention can be realized through following technical scheme:
A kind of rectificating method that from liquid oxygen, extracts the krypton xenon; It is characterized in that this method is collected the back with the liquid oxygen that extracts through storage tank and got into fractionating column system, removes the impurity in the liquid oxygen through the rectifying tower and the nitrogen wash column that are provided with in the fractionating column system; Extract the krypton xenon, specifically may further comprise the steps:
(1) liquid oxygen is fed in the first step rectifying tower in the fractionating column system, carry out rectifying separation, obtain oxygen at cat head; Obtain krypton xenon liquid concentrator at the bottom of the tower, working pressure is 0.11MPa～0.4MPa in the first step rectifying Tata, preferred 0.21MPa; 3～20 of stage number, preferred 15;
(2) the krypton xenon liquid concentrator that step (1) tower still is obtained is sent into nitrogen wash column, and cat head top feeds liquid nitrogen as solvent, and the tower still feeds rising tolerance in the nitrogen control tower; After krypton xenon liquid concentrator absorbed in the absorption tower, the nitrogen that obtains, oxygen mixture were derived by cat head, and the krypton xenon liquid concentrator that obtains is derived by the tower still; Working pressure is 0.4～0.8MPa in the nitrogen wash column; Preferred 0.6MPa, stage number is 20～40, preferred 28;
(3) krypton-xenon concentrate that step (2) tower still is obtained is sent in the rectifying tower of the second stage, obtains nitrogen at cat head, and the tower still obtains krypton xenon secondary concentration liquid; Second stage rectifying tower working pressure is 0.4～0.8MPa; Preferred 0.55MPa, stage number is 5～22, preferred 18;
(4) the krypton xenon secondary concentration thing that step (3) tower still is obtained is sent in the third stage rectifying tower, obtains nitrogen and methane at cat head, and the tower still obtains three liquid concentrators of krypton xenon; Third stage rectifying tower working pressure is 0.4～0.8MPa; Preferred 0.5MPa, stage number is 25～60, preferred 40;
(5) three liquid concentrators of krypton xenon that step (5) tower still obtained are sent in the fourth stage rectifying tower, carry out rectifying separation, and cat head obtains the krypton enriched material; Obtain xenon concentrate at the bottom of the tower, fourth stage rectifying tower working pressure is 0.1～0.6MPa, preferred 0.4MPa; Stage number is 5～26, preferred 15;
(6) the krypton liquid concentrator that step (5) cat head is obtained is sent in the level V rectifying tower, carries out rectifying separation, and cat head obtains molar content and is not less than 99.999% pure krypton product; Level V rectifying tower working pressure is 0.2～0.7MPa; Preferred 0.34MPa, stage number is 7～23, preferred 12;
(7) xenon concentrate that contains that step (5) tower still is obtained is sent into the 6th grade of rectifying tower, carries out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid; The 6th grade of rectifying tower working pressure is 0.1～0.7MPa; Preferred 0.43MPa, stage number is 50～100, preferred 88;
(8) the xenon fluid that contains that step (7) cat head is obtained is sent in the 7th grade of rectifying tower, carries out rectifying separation, at the bottom of tower, obtains molar content and is not less than 99.999% pure xenon product; The 7th grade of rectifying tower working pressure is 0.1～0.7MPa; Preferred 0.38MPa, stage number is 5～30, preferred 27.
Be provided with reboiler at the bottom of the described first step rectifying Tata; Cat head is provided with condenser/evaporator, and nitrogen feeds in the tower bottom reboiler of first step rectifying tower after introducing the cooling of separation column process main heat exchanger; Use as thermal source; Nitrogen further is cooled to liquid nitrogen, with liquid nitrogen throttling step-down, extracts a part of liquid nitrogen and introduces in the condenser/evaporator of first step rectifying tower cat head as low-temperature receiver; Part liquid nitrogen directly gets into nitrogen wash column, gets in the nitrogen wash column after the low temperature nitrogen re-heat of first step rectifying tower condenser/evaporator outlet.
Be provided with reboiler at the bottom of the tower of described second stage rectifying tower, cat head is provided with condenser/evaporator, after nitrogen is lowered the temperature through main heat exchanger; A part feeds in the tower bottom reboiler of second stage rectifying tower, uses as thermal source, and another part nitrogen is cooled to liquid nitrogen; After the throttling step-down; Extract a part of liquid nitrogen and introduce in the condenser/evaporator of second stage rectifying tower cat head as low-temperature receiver, a part is introduced and is removed in the condenser/evaporator of methane tower as low-temperature receiver, and remaining liquid nitrogen compiles the back and discharges as product.
The low-temperature receiver of described third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower, the 6th grade of rectifying tower and the 7th grade of rectifying tower is selected low temperature nitrogen and the mixed gas of normal temperature nitrogen for use, avoids sink temperature to hang down excessively and causes the krypton xenon to solidify.
Return main heat exchanger after the nitrogen that the condenser/evaporator of described rectifying tower cats head at different levels is discharged converges, carry out the cold recovery utilization.
Described rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower 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) recovery of krypton and xenon is high, can reach more than 95% respectively;
(2) a krypton tower is set in fractionating column system; Carry out the once concentration of krypton xenon; Remove the oxygen in the raw material through nitrogen wash column is set, nitrogen-rejection column is set removes the nitrogen that a step is introduced, setting removes the methane tower and removes the most of methane in the raw material; Through rectifying step by step, remove all the low boiling component (O in the dense krypton xenon virgin 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 high-purity krypton technical indicator of GB/T5829-2006 and the high-purity xenon technical indicator of GB/T5828-2006, and whole flow process is safe and reliable;
(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 small amount of nitrogen promptly to can be whole fractionating column system provides low-temperature receiver to replenish; The user be provided with fill krypton-xenon liquid body Dewar bottle and liquid nitrogen cryogenics storage tank after; Can break away from air-separating plant; Independent operating; Also can use by supporting existing air separation plant, realize the continuous and stable production operation;
(5) the oxygen recycling as much as possible in this device raw material through can directly providing the user to use after the main heat exchanger re-heat, also has a certain amount of liquid nitrogen in the sub product.
Description of drawings
Fig. 1 is a schema of the present invention.
1 is first step rectifying tower among the figure; 2 is nitrogen wash column; 3 is second stage rectifying tower; 4 is third stage rectifying tower; 5 is fourth stage rectifying tower; 6 is the level V rectifying tower; 7 is the 6th grade of rectifying tower; 8 is the 7th grade of rectifying tower; 9 is condenser/evaporator; 10 is condenser/evaporator; 11 is condenser/evaporator; 12 is condenser/evaporator; 13 is condenser/evaporator; 14 is condenser/evaporator; 15 is condenser/evaporator; 16 is electric reboiler; 17 is electric reboiler; 18 is electric heater; 19 is electric heater; 20 is electric heater; 21 is electric heater; 22 is electric heater; 23 is main heat exchanger; 24 is main heat exchanger; 25 is liquid oxygen pump.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
A kind of rectificating method that from liquid oxygen, extracts the krypton xenon, its flow process is as shown in Figure 1, and this method is collected the back with the liquid oxygen that extracts through storage tank and is got into fractionating column system, removes impurity through the rectifying tower and the nitrogen wash column that are provided with in the fractionating column system.Fractionating column system comprises 23,24, seven grades of rectifying tower of main heat exchanger and a nitrogen wash column 2, and liquid stock gets in the first step rectifying tower 1; Working pressure is 0.21MPa in the tower, and stage number is 15, after separating; The top of tower ejecta is an oxygen, through discharging ice chest after main heat exchanger 23 re-heats.The bottom liquid of first step rectifying tower 1 gets in the nitrogen wash column 2 through liquid oxygen pump 25 pressurization backs.Working pressure is 0.6MPa in the nitrogen wash column 2; Stage number is 28; Discharge after nitrogen wash column 2 top expellant gas parts are advanced main heat exchanger 23 re-heats, all the other low-temperature receivers as condenser/evaporator 9, condenser/evaporator 10, condenser/evaporator 11, condenser/evaporator 12, condenser/evaporator 13, condenser/evaporator 14 and condenser/evaporator 15 use.Nitrogen wash column 2 bottoms are connected in the second stage rectifying tower 3, and the working pressure of second stage rectifying tower 3 is 0.55MPa, and stage number is 18.Rectifying tower 3 bottoms in the second stage are connected in the third stage rectifying tower 4, and the working pressure of third stage rectifying tower 4 is 0.5MPa, and stage number is 40.Third stage rectifying tower 4 bottoms are connected in the fourth stage rectifying tower 5, and the working pressure of fourth stage rectifying tower 5 is 0.4MPa, and stage number is 15; Fourth stage rectifying tower 5 tops are connected in the level V rectifying tower 6, the working pressure 0.34MPa of level V rectifying tower 6, and stage number is 12; Fourth stage rectifying tower 5 bottoms are connected in the 6th grade of rectifying tower 7; The working pressure of the 6th grade of rectifying tower 7 is 0.43MPa, and stage number is 88, and the 6th grade of rectifying tower 7 tops are connected in the 7th grade of rectifying tower 8; The working pressure of the 7th grade of rectifying tower 8 is 0.38MPa, and stage number is 27.First step rectifying tower 1 bottom makes electricity consumption reboiler 16; Rectifying tower 3 bottoms in the second stage make electricity consumption reboiler 17; Electric heater 18 is used in third stage rectifying tower 4 bottoms, and electric heater 19 is used in fourth stage rectifying tower 5 bottoms, and electric heater 20 is used in level V rectifying tower 6 bottoms; The 6th grade of rectifying tower 7 bottoms use 21, the seven grades of rectifying tower 8 bottoms of electric heater to use electric heater 22.Reboiler 16 thermals source of first step rectifying tower 1 bottom are selected low temperature nitrogen for use, and low temperature nitrogen derives from by main heat exchanger 23 and main heat exchanger 24 cooled normal temperature nitrogen.First step rectifying tower 1 top be provided with condenser/evaporator 9, low-temperature receiver adopts liquid nitrogen.Reboiler 17 thermals source of second stage rectifying tower 3 bottoms are selected low temperature nitrogen for use, and low temperature nitrogen derives from by main heat exchanger 23 and main heat exchanger 24 cooled normal temperature nitrogen.Second stage rectifying tower 3 tops be provided with condenser/evaporator 10, low-temperature receiver adopts liquid nitrogen.Liquid nitrogen pressure is 0.1～0.15MPa, makes the interior rising vapor condensation of tower become phegma, sets up the rectifying operating mode.The inlet low-temperature receiver of the condenser/evaporator 11 of other rectifying tower cats head, condenser/evaporator 12, condenser/evaporator 13, condenser/evaporator 14, condenser/evaporator 15 is normal temperature nitrogen and the mixed according to a certain percentage gas of low temperature nitrogen; After converging, the cryogenic gas of condenser/evaporator outlet gets in the main heat exchanger 23; The temperature of low temperature nitrogen is-180 ℃; Make low-temperature receiver with normal temperature nitrogen mixture body; Temperature is controlled at-110～-150 ℃, under this temperature, can avoid the krypton xenon crystallization in the steam in the tower, can form the phegma of the needs of rectifying operating mode in the tower simultaneously again.
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 impurities successively, 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 fed in the first step rectifying tower 1, obtain one-level krypton xenon liquid concentrator at the bottom of the tower, wherein methane content is no more than 5000 * 10
-6Nitrogen wash column 2 middle and upper parts are introduced in a krypton xenon liquid concentrator pressurization back; Cat head top feeds liquid nitrogen as solvent; The middle and upper part of tower feeds nitrogen, and the tower still feeds rising tolerance in the nitrogen control tower, after one time krypton xenon liquid concentrator absorbs in nitrogen wash column; The krypton xenon liquid concentrator that obtains is derived by the tower still, and the nitrogen that obtains, oxygen mixture are derived by cat head.Wherein, liquid nitrogen comes from the condenser/evaporator of one-level rectifying tower, and nitrogen comes from through the nitrogen after main heat exchanger 24 re-heats and the outlet nitrogen of one-level rectifying tower condenser/evaporator.Krypton xenon liquid concentrator is sent in the second stage rectifying tower 3, and most of nitrogen is discharged from from cat head, obtains secondary krypton xenon liquid concentrator at the bottom of the tower.Secondary krypton xenon liquid concentrator is sent in the third stage rectifying tower 4, and most of methane is discharged from from cat head, obtains krypton xenon liquid concentrator at the bottom of the tower three times, and krypton xenon content is about 99.9%.Three krypton xenon liquid concentrators are introduced in the fourth stage rectifying tower, and the krypton xenon separates through the krypton xenon, will contain the krypton enriched material and send in the level V rectifying tower 6, obtains the pure krypton of product fluid at cat head, and 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 6th grade of rectifying tower 7, 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 56 is discharged and is collected at the bottom of the tower.To contain the xenon fluid and send in the 7th grade of rectifying tower 8, and at the bottom of tower, obtain the liquid pure xenon, 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 the CF in the xenon fluid
4Will be at cat head along with fluid is discharged from collection along cryogenic pipelines.All return main heat exchanger after the low wet that all condenser/evaporators are discharged converges, carry out cold recovery.Rectifying tower, cryogenic pipelines and valve all wrap in the ice chest that is filled with thermal insulation material such as super glass wool, pearlstone etc.
Embodiment 2
A kind of rectificating method that from liquid oxygen, extracts the krypton xenon, this method is collected the back with the liquid oxygen that extracts through storage tank and is got into fractionating column system, removes impurity through the rectifying tower and the nitrogen wash column that are provided with in the fractionating column system.Fractionating column system comprises main heat exchanger, and seven grades of rectifying tower and a nitrogen wash column, liquid stock get in the first step rectifying tower; Working pressure is 3 for the 0.11MPa stage number in the tower; After separating, the top of tower ejecta is an oxygen, through discharging ice chest after the main heat exchanger re-heat.First step rectifier bottoms liquid gets in the nitrogen wash column through liquid oxygen pump pressurization back.Working pressure is 0.4MPa in the nitrogen wash column, and stage number is 20, discharges after a nitrogen wash column top expellant gas part is advanced the main heat exchanger re-heat, and all the other low-temperature receivers as condenser/evaporator use.The nitrogen wash column bottom is connected in the rectifying tower of the second stage, and second stage rectifying tower working pressure is 0.4MPa, and stage number is 5.Second stage rectifier bottoms is connected in the third stage rectifying tower, and third stage rectifying tower working pressure is 0.4MPa, and stage number is 25.Third stage rectifier bottoms is connected in the fourth stage rectifying tower, and fourth stage rectifying tower working pressure is 0.1MPa, and stage number is 5; Fourth stage rectifying tower top is connected in the level V rectifying tower, and level V rectifying tower working pressure is 0.2MPa, and stage number is 12; Fourth stage rectifier bottoms is connected in the 6th grade of rectifying tower; The 6th grade of rectifying tower working pressure is 0.1MPa, and stage number is 50, and the 6th grade of rectifying tower top is connected in the 7th grade of rectifying tower; The 7th grade of rectifying tower working pressure is 0.1MPa, and stage number is 5.First step rectifying tower and second stage rectifier bottoms make the electricity consumption reboiler, and the third stage, the fourth stage, level V, the 6th grade, the 7th grade rectifier bottoms are used electric heater.The reboiler thermal source of first step rectifier bottoms is selected low temperature nitrogen for use, and low temperature nitrogen derives from by the cooled normal temperature nitrogen of main heat exchanger.First step rectifying tower top be provided with condenser/evaporator, low-temperature receiver adopts liquid nitrogen.The reboiler thermal source of second stage rectifier bottoms is selected low temperature nitrogen for use, and low temperature nitrogen derives from by the cooled normal temperature nitrogen of main heat exchanger.Rectifying tower top, the second stage be provided with condenser/evaporator, low-temperature receiver adopts liquid nitrogen.Liquid nitrogen pressure is 0.1～0.15MPa, makes the interior rising vapor condensation of tower become phegma, sets up the rectifying operating mode.The inlet low-temperature receiver of the condenser/evaporator of other rectifying tower cats head is normal temperature nitrogen and the mixed according to a certain percentage gas of low temperature nitrogen; After converging, the cryogenic gas of condenser/evaporator outlet gets in the main heat exchanger; The temperature of low temperature nitrogen is that-180 ℃ and normal temperature nitrogen mixture body are made low-temperature receiver, and temperature is controlled at-110～-150 ℃; Under this temperature, can avoid the krypton xenon crystallization in the steam in the tower, can form the phegma of the needs of rectifying operating mode in the tower simultaneously again.
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 impurities successively, 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 fed in the first step rectifying tower 1, obtain one-level krypton xenon liquid concentrator at the bottom of the tower, wherein methane content is no more than 5000 * 10
-6Nitrogen wash column 2 middle and upper parts are introduced in a krypton xenon liquid concentrator pressurization back; Cat head top feeds liquid nitrogen as solvent; The middle and upper part of tower feeds nitrogen, and the tower still feeds rising tolerance in the nitrogen control tower, after one time krypton xenon liquid concentrator absorbs in nitrogen wash column; The krypton xenon liquid concentrator that obtains is derived by the tower still, and the nitrogen that obtains, oxygen mixture are derived by cat head.Wherein, liquid nitrogen comes from the condenser/evaporator of one-level rectifying tower, and nitrogen comes from through the nitrogen after the main heat exchanger re-heat and the outlet nitrogen of one-level rectifying tower condenser/evaporator.Krypton xenon liquid concentrator is sent in the rectifying tower of the second stage, and most of nitrogen is discharged from from cat head, obtains secondary krypton xenon liquid concentrator at the bottom of the tower.Secondary krypton xenon liquid concentrator is sent in the third stage rectifying tower, and most of methane is discharged from from cat head, obtains krypton xenon liquid concentrator at the bottom of the tower three times, and krypton xenon content is about 99.9%.Three krypton xenon liquid concentrators are introduced in the fourth stage rectifying tower, and the krypton xenon separates through the krypton xenon, will contain the krypton enriched material and send in the level V rectifying tower, obtains the pure krypton of product fluid at cat head, and 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 6th grade of rectifying tower, 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 is discharged and is collected at the bottom of the tower.To contain the xenon fluid and send in the 7th grade of rectifying tower, and at the bottom of tower, obtain the liquid pure xenon, 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 the CF in the xenon fluid
4Will be at cat head along with fluid is discharged from collection along cryogenic pipelines.All return main heat exchanger after the low wet that all condenser/evaporators are discharged converges, carry out cold recovery.Rectifying tower, cryogenic pipelines and valve all wrap in the ice chest that is filled with thermal insulation material such as super glass wool, pearlstone etc.
Embodiment 3
A kind of rectificating method that from liquid oxygen, extracts the krypton xenon, this method is collected the back with the liquid oxygen that extracts through storage tank and is got into fractionating column system, removes impurity through the rectifying tower and the nitrogen wash column that are provided with in the fractionating column system.Fractionating column system comprises main heat exchanger, and seven grades of rectifying tower and a nitrogen wash column, liquid stock get in the first step rectifying tower; Working pressure is 0.4MPa in the tower, and stage number is 20, after separating; The top of tower ejecta is an oxygen, through discharging ice chest after the main heat exchanger re-heat.First step rectifier bottoms liquid gets in the nitrogen wash column through liquid oxygen pump pressurization back.Working pressure is 0.8MPa in the nitrogen wash column, and stage number is 40, discharges after a nitrogen wash column top expellant gas part is advanced the main heat exchanger re-heat, and all the other low-temperature receivers as condenser/evaporator use.The nitrogen wash column bottom is connected in the rectifying tower of the second stage, and second stage rectifying tower working pressure is 0.8MPa, and stage number is 22.Second stage rectifier bottoms is connected in the third stage rectifying tower, and third stage rectifying tower working pressure is 0.8MPa, and stage number is 60.Third stage rectifier bottoms is connected in the fourth stage rectifying tower, and fourth stage rectifying tower working pressure is 0.6MPa, and stage number is 26; Fourth stage rectifying tower top is connected in the level V rectifying tower, and level V rectifying tower working pressure is 0.7MPa, and stage number is 23; Fourth stage rectifier bottoms is connected in the 6th grade of rectifying tower; The 6th grade of rectifying tower working pressure is 0.7MPa, and stage number is 100, and the 6th grade of rectifying tower top is connected in the 7th grade of rectifying tower; The 7th grade of rectifying tower working pressure is 0.7MPa, and stage number is 30.First step rectifying tower and second stage rectifier bottoms make the electricity consumption reboiler, and the third stage, the fourth stage, level V, the 6th grade, the 7th grade rectifier bottoms are used electric heater.The reboiler thermal source of first step rectifier bottoms is selected low temperature nitrogen for use, and low temperature nitrogen derives from by the cooled normal temperature nitrogen of main heat exchanger.First step rectifying tower top be provided with condenser/evaporator, low-temperature receiver adopts liquid nitrogen.The reboiler thermal source of second stage rectifier bottoms is selected low temperature nitrogen for use, and low temperature nitrogen derives from by the cooled normal temperature nitrogen of main heat exchanger.Rectifying tower top, the second stage be provided with condenser/evaporator, low-temperature receiver adopts liquid nitrogen.Liquid nitrogen pressure is 0.1～0.15MPa, makes the interior rising vapor condensation of tower become phegma, sets up the rectifying operating mode.The inlet low-temperature receiver of the condenser/evaporator of other rectifying tower cats head is normal temperature nitrogen and the mixed according to a certain percentage gas of low temperature nitrogen; After converging, the cryogenic gas of condenser/evaporator outlet gets in the main heat exchanger; The temperature of low temperature nitrogen is that-180 ℃ and normal temperature nitrogen mixture body are made low-temperature receiver, and temperature is controlled at-110～-150 ℃; Under this temperature, can avoid the krypton xenon crystallization in the steam in the tower, can form the phegma of the needs of rectifying operating mode in the tower simultaneously again.
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 impurities successively, 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 fed in the first step rectifying tower 1, obtain one-level krypton xenon liquid concentrator at the bottom of the tower, wherein methane content is no more than 5000 * 10
-6Nitrogen wash column 2 middle and upper parts are introduced in a krypton xenon liquid concentrator pressurization back; Cat head top feeds liquid nitrogen as solvent; The middle and upper part of tower feeds nitrogen, and the tower still feeds rising tolerance in the nitrogen control tower, after one time krypton xenon liquid concentrator absorbs in nitrogen wash column; The krypton xenon liquid concentrator that obtains is derived by the tower still, and the nitrogen that obtains, oxygen mixture are derived by cat head.Wherein, liquid nitrogen comes from the condenser/evaporator of one-level rectifying tower, and nitrogen comes from through the nitrogen after the main heat exchanger re-heat and the outlet nitrogen of one-level rectifying tower condenser/evaporator.Krypton xenon liquid concentrator is sent in the rectifying tower of the second stage, and most of nitrogen is discharged from from cat head, obtains secondary krypton xenon liquid concentrator at the bottom of the tower.Secondary krypton xenon liquid concentrator is sent in the third stage rectifying tower, and most of methane is discharged from from cat head, obtains krypton xenon liquid concentrator at the bottom of the tower three times, and krypton xenon content is about 99.9%.Three krypton xenon liquid concentrators are introduced in the fourth stage rectifying tower, and the krypton xenon separates through the krypton xenon, will contain the krypton enriched material and send in the level V rectifying tower, obtains the pure krypton of product fluid at cat head, and 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 6th grade of rectifying tower, 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 is discharged and is collected at the bottom of the tower.To contain the xenon fluid and send in the 7th grade of rectifying tower, and at the bottom of tower, obtain the liquid pure xenon, 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 the CF in the xenon fluid
4Will be at cat head along with fluid is discharged from collection along cryogenic pipelines.All return main heat exchanger after the low wet that all condenser/evaporators are discharged converges, carry out cold recovery.Rectifying tower, cryogenic pipelines and valve all wrap in the ice chest that is filled with thermal insulation material such as super glass wool, pearlstone etc.
Claims (7)
1. rectificating method that from liquid oxygen, extracts the krypton xenon; It is characterized in that this method is collected the back with the liquid oxygen that extracts through storage tank and got into fractionating column system, removes the impurity in the liquid oxygen through the rectifying tower and the nitrogen wash column that are provided with in the fractionating column system; Extract the krypton xenon, specifically may further comprise the steps:
(1) liquid oxygen is fed in the first step rectifying tower in the fractionating column system, carry out rectifying separation, obtain oxygen at cat head, obtain krypton xenon liquid concentrator at the bottom of the tower, working pressure is 0.11MPa～0.4MPa in the first step rectifying Tata, 3～20 of stage number;
(2) the krypton xenon liquid concentrator that step (1) tower still is obtained is sent into nitrogen wash column; Cat head top feeds liquid nitrogen as solvent, and the tower still feeds rising tolerance in the nitrogen control tower, after krypton xenon liquid concentrator absorbs in nitrogen wash column; The nitrogen that obtains, oxygen mixture are derived by cat head; The krypton xenon liquid concentrator that obtains is derived by the tower still, and working pressure is 0.4～0.8MPa in the nitrogen wash column, and stage number is 20～40;
(3) the krypton xenon liquid concentrator that step (2) nitrogen wash column tower still is obtained is sent in the rectifying tower of the second stage, obtains nitrogen at cat head, and the tower still obtains krypton xenon secondary concentration liquid, and second stage rectifying tower working pressure is 0.4～0.8MPa, and stage number is 5～22;
(4) the krypton xenon secondary concentration liquid that step (3) tower still is obtained is sent in the third stage rectifying tower, obtains nitrogen and methane at cat head, and the tower still obtains three liquid concentrators of krypton xenon, and third stage rectifying tower working pressure is 0.4～0.8MPa, and stage number is 25～60;
(5) three liquid concentrators of krypton xenon that step (4) tower still obtained are sent in the fourth stage rectifying tower, carry out rectifying separation, and cat head obtains the krypton enriched material, obtains xenon concentrate at the bottom of the tower, and fourth stage rectifying tower working pressure is 0.1～0.6MPa, and stage number is 5～26;
(6) the krypton enriched material that step (5) cat head is obtained is sent in the level V rectifying tower, carries out rectifying separation, and cat head obtains molar content and is not less than 99.999% pure krypton product, and level V rectifying tower working pressure is 0.2～0.7MPa, and stage number is 7～23;
(7) xenon concentrate that step (5) tower still is obtained is sent into the 6th grade of rectifying tower, carries out rectifying separation, cat head obtain molar content be not less than 99.99% contain the xenon fluid, the 6th grade of rectifying tower working pressure is 0.1～0.7MPa, stage number is 50～100;
(8) the xenon fluid that contains that step (7) cat head is obtained is sent in the 7th grade of rectifying tower, carries out rectifying separation, at the bottom of tower, obtains molar content and is not less than 99.999% pure xenon product, and the 7th grade of rectifying tower working pressure is 0.1～0.7MPa, and stage number is 5～30.
2. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 1 is characterized in that, is provided with reboiler at the bottom of the described first step rectifying Tata; Cat head is provided with condenser/evaporator, and nitrogen feeds in the tower bottom reboiler of first step rectifying tower after introducing the cooling of separation column process main heat exchanger; Use as thermal source; Nitrogen further is cooled to liquid nitrogen, with liquid nitrogen throttling step-down, extracts a part of liquid nitrogen and introduces in the condenser/evaporator of first step rectifying tower cat head as low-temperature receiver; Part liquid nitrogen directly gets into nitrogen wash column, gets in the nitrogen wash column after the low temperature nitrogen re-heat of first step rectifying tower condenser/evaporator outlet.
3. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 1 is characterized in that, is provided with reboiler at the bottom of the tower of described second stage rectifying tower; Cat head is provided with condenser/evaporator, and after nitrogen was lowered the temperature through main heat exchanger, a part fed in the tower bottom reboiler of second stage rectifying tower; Use as thermal source; Another part nitrogen is cooled to liquid nitrogen, after the throttling step-down, extracts a part of liquid nitrogen and introduces in the condenser/evaporator of second stage rectifying tower cat head as low-temperature receiver; As low-temperature receiver, remaining liquid nitrogen compiles the back and discharges as product in the condenser/evaporator of part introducing third stage rectifying tower.
4. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 1; It is characterized in that; The low-temperature receiver of described third stage rectifying tower, fourth stage rectifying tower, level V rectifying tower, the 6th grade of rectifying tower and the 7th grade of rectifying tower is selected low temperature nitrogen and the mixed gas of normal temperature nitrogen for use, avoids sink temperature to hang down excessively and causes the krypton xenon to solidify.
5. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 1 is characterized in that, returns main heat exchanger after the nitrogen that the condenser/evaporator of rectifying tower cats head at different levels is discharged converges, and carries out the cold recovery utilization.
6. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 1 is characterized in that rectifying tower, the cryogenic pipelines and the valve that connect between the rectifying tower wrap in the ice chest that is filled with thermal insulation material.
7. a kind of rectificating method that from liquid oxygen, extracts the krypton xenon according to claim 6 is characterized in that described thermal insulation material comprises super glass wool or pearlstone.
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Address after: 201203, room 1, building 88, 402 Darwin Road, Zhangjiang hi tech park, Shanghai Patentee after: Shanghai Qiyuan Technology Development Co.,Ltd. Patentee after: SHANGHAI QIYUAN AIR SEPARATE TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 201203, room 1, building 88, 402 Darwin Road, Zhangjiang hi tech park, Shanghai Patentee before: Shanghai Qiyuan Technology Development Co.,Ltd. Patentee before: Shanghai Qiyuan Air Separation Technology Development Co.,Ltd. |
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