CN110548364A - method and device for recovering special gas adsorbed by molecular sieve - Google Patents
method and device for recovering special gas adsorbed by molecular sieve Download PDFInfo
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- CN110548364A CN110548364A CN201910991072.XA CN201910991072A CN110548364A CN 110548364 A CN110548364 A CN 110548364A CN 201910991072 A CN201910991072 A CN 201910991072A CN 110548364 A CN110548364 A CN 110548364A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 100
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 278
- 239000012535 impurity Substances 0.000 claims abstract description 55
- 238000001179 sorption measurement Methods 0.000 claims abstract description 35
- 238000011084 recovery Methods 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001307 helium Substances 0.000 claims abstract description 12
- 229910052734 helium Inorganic materials 0.000 claims abstract description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000078 germane Inorganic materials 0.000 claims description 29
- 238000007664 blowing Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002826 coolant Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
- B01D2257/553—Compounds comprising hydrogen, e.g. silanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
Abstract
The invention discloses a method and a device for recovering special gas adsorbed by a molecular sieve, which mainly adopt hydrogen or helium as carrier gas, blow gas into an adsorption column of the molecular sieve at normal temperature to impact the special gas in the molecular sieve, thereby realizing the direct recovery of the special gas in the molecular sieve at normal temperature, and having low recovery cost, easy operation, environmental protection, safety, recovery rate of more than 90 percent and considerable economic benefit. Because the recovery method of the invention does not need heating, other impurities such as moisture and the like absorbed in the molecular sieve are not easy to desorb, so that the content of the impurities in the recovered special gas is low, and the utilization value is high. In addition, the carrier gas adopted by the invention does not introduce impurities, and the special gas can be separated from the carrier gas by directly condensing the special gas at low temperature subsequently, and the separated carrier can be directly recycled. Therefore, the invention makes up the technical defect that the special gas adsorbed in the molecular sieve can not be directly recovered in the prior industry, and greatly reduces the purification cost of the special gas.
Description
Technical Field
the invention relates to the technical field of special gas recovery, in particular to a method and a device for recovering special gas adsorbed by a molecular sieve.
Background
In the field of high-purity special gases, such as arsine, phosphine, germane and the like, molecular sieves, such as 3A, 4A, 5A, 13X and the like, are generally used for removing impurities, such as moisture and the like, in the special gases. The purification by using the molecular sieve has the advantages of high efficiency, capability of deeply removing water and other small molecular impurities, capability of being heated and recycled and the like, thereby being widely applied to the purification of various gases.
However, molecular sieves adsorb impurities and also adsorb a large amount of specialty gases. For example, arsine passes through an adsorption column with the volume of 100L filled with 4A molecular sieve, and the 4A molecular sieve can adsorb 20-30 kg of arsine while adsorbing water. Arsine can be decomposed at 230 ℃, and if the molecular sieve is directly activated, arsine can be directly lost and the molecular sieve is easily deactivated. If the molecular sieve is directly pumped out for replacing and then activated, the molecular sieve adsorbing the arsine enters a tail gas absorption spray tower, so that a large amount of oxidant is consumed, and the arsine in the molecular sieve cannot be recovered. It can be seen that activation of a 100L molecular sieve column results in loss of tens of thousands of yuan. Especially for germane, which is a special gas with high price, the market price per kg is as high as tens of thousands yuan, and more than ten thousands yuan can be lost when the molecular sieve is activated once. In actual industrial production, the molecular sieve needs to be activated once for treating 100-200 kg of special gas, and the special gas adsorbed in the molecular sieve cannot be recovered, so that the cost of an enterprise is increased by more than 10%.
Therefore, it is of great importance to develop a method and equipment for efficiently recovering the special gas adsorbed in the molecular sieve.
Disclosure of Invention
to overcome the above disadvantages and shortcomings of the prior art, a first object of the present invention is to provide a method for recovering a specialty gas adsorbed by a molecular sieve, and a second object of the present invention is to provide an apparatus for recovering a specialty gas adsorbed by a molecular sieve. The method and the device are matched for use, the special gas adsorbed in the molecular sieve can be efficiently recovered, the recovery rate is up to more than 90%, the loss of the special gas purification is obviously reduced, and the purification cost of the special gas is reduced.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering special gas adsorbed by a molecular sieve, which comprises the following steps:
(1) blowing non-impurity gas to the molecular sieve adsorbed with the special gas to desorb the special gas on the molecular sieve to obtain mixed gas containing the non-impurity gas and the special gas;
(2) Condensing the special gas in the mixed gas to separate the special gas from the non-impurity gas;
(3) And (3) recovering the special gas condensed in the step (2).
Preferably, the non-impurity gas includes at least one of hydrogen and helium. Most preferably, the non-contaminant gas is hydrogen. The hydrogen has small molecular radius, high molecular motion speed and excellent diffusivity, can continuously invade gaps of the molecular sieve and continuously impact special gas molecules adsorbed on the molecular sieve to break loose the adsorption effect of the molecular sieve, and further desorb. In addition, hydrogen is inexpensive.
Preferably, the specialty gas comprises at least one of arsine, phosphine, and germane.
Preferably, the blowing manner of the non-impurity gas is continuous blowing, and the blowing direction is blowing from bottom to top. The continuous blowing can make the non-impurity gas continuously impact the special gas molecules in the molecular sieve to make the special gas molecules quickly desorbed. Blowing from bottom to top can make the non-impurity gas flow along the natural flow direction of the gas, fully invade into the molecular sieve and make the special gas in the molecular sieve desorb.
Preferably, the flow rate of the non-impurity gas is 60-100L/min, and the blowing time is 8-12 h. Preferably, the flow rate of the non-impurity gas is 60L/min. Because the recovery rate of the special gas is obviously improved along with the increase of the flow rate of the non-impurity gas, but the recovery rate of the special gas is not obviously improved when the flow rate reaches above 60L/min, the invention takes 60L/min as the optimal flow rate of the non-impurity gas, the recovery cost of the flow rate is lower, and the purity of the recovered special gas is higher.
Preferably, the temperature of the special gas condensed and recovered in the step (2) is below-170 ℃, and the adopted condensing medium is liquid nitrogen, liquid argon, liquid helium or other refrigerants capable of providing a cooling environment below-170 ℃ and the like. The melting point of the special gas is-100 to-170 ℃, so that the gaseous special gas is condensed and converted into liquid or solid at the temperature below-170 ℃, and the hydrogen is still gaseous at the temperature, so that the special gas and the hydrogen can be easily separated. Most preferably, said step (2) condenses the specialty gas at the temperature of liquid nitrogen. The temperature of the liquid nitrogen is-196 ℃, the condensing efficiency to the special gas is higher, and the price of the liquid nitrogen is cheaper.
preferably, in the step (3), when the condensed special gas is recovered, the special gas is firstly converted into a gaseous state and then directly filled into a gas cylinder so as to directly recover the special gas. Compared with the method for directly recovering the special gas by only recovering the key elements such as germanium, arsenic and phosphorus in the special gas, the method for directly recovering the special gas is more efficient and has higher recovery rate.
The recovery method of the invention adopts hydrogen or helium as carrier gas to bring out the special gas from the molecular sieve built-in without heating. Under the continuous flushing of the carrier gas flow, the desorbed special gas is mixed in the carrier gas flow to form mixed gas. Under the condensation condition of the invention, the special gas in the mixed gas is converted into liquid or solid state, but the non-impurity gas is still gaseous, so that the special gas is separated from the non-impurity gas. Finally, the discharged non-impurity gas can be returned to the initial process by a gas circulator, and the non-impurity gas can be used as carrier gas to flow into the molecular sieve adsorbed with special gas, or can be recycled for standby by a gas cylinder or other equipment. After the blowing is finished, the condensed special gas is converted into a gas state again and then directly recovered into the gas cylinder.
4The recovery method of the invention is not required to be heated, the special gas can be desorbed from the molecular sieve at normal temperature, and the moisture has great polarity and cannot be desorbed from the molecular sieve, but the heating of the molecular sieve realizes the desorption method, the special gas can be decomposed or converted during heating, and the heating process can also bring a large amount of moisture adsorbed in the molecular sieve, and the molecular sieve plays a role in the field of the special gas in order to remove the moisture.
The invention provides a device for recovering special gas adsorbed by a molecular sieve, which comprises a first gas conveying pipeline, a second gas conveying pipeline and a condenser, wherein the first gas conveying pipeline is connected with the condenser; the first gas conveying pipeline is used for blowing non-impurity gas into the molecular sieve adsorption column which adsorbs the special gas so as to desorb the special gas in the molecular sieve adsorption column; the second gas conveying pipeline is used for conveying the mixed gas desorbed from the molecular sieve adsorption column to the condenser; the condenser is used for condensing the special gas in the mixed gas to separate the special gas from the non-impurity gas. Here, the definition and preference of the special gas, non-impurity gas and molecular sieve are the same as those of the above recovery method of the present invention, and will not be described in detail.
Preferably, the first gas conveying pipeline is connected with an interface at the bottom of the molecular sieve adsorption column, one end of the second gas conveying pipeline is connected with an interface at the top of the molecular sieve adsorption column, and the other end of the second gas conveying pipeline is connected with the condenser. Therefore, the hydrogen flow or the helium flow can flow from bottom to top in the molecular sieve adsorption column, has the same direction as the natural flow, and can reach higher flow rate under lower blowing pressure, thereby being better immersed in the gaps of the molecular sieve to impact the special gas, and leading the special gas to be easier to desorb.
Preferably, the condenser is a shell-side condenser, the mixed gas flows through a shell side of the condenser, a condensing medium is filled in the condenser, and the second gas conveying pipeline is connected with a shell side gas inlet of the condenser. In the invention, the mixed gas in the shell-and-tube condenser is taken as the shell pass, and the condensing medium is taken as the shell-and-tube pass.
Preferably, the device of the invention further comprises a condensing medium conveying pipeline, a third gas conveying pipeline, a gas circulator and a gas cylinder; the condensing medium conveying pipeline is used for conveying condensing medium into the tubes of the condenser; the third gas conveying pipeline and the gas cylinder are respectively connected with a shell pass gas outlet of the condenser, the third gas conveying pipeline is used for discharging non-impurity gas separated by the condenser, the third gas conveying pipeline is further connected with the gas circulator, and the gas circulator is further connected with the first gas conveying pipeline, so that the non-impurity gas separated by the condenser can be reused as carrier gas, and is re-conveyed back to the first gas conveying pipeline through the gas circulator to be blown into the molecular sieve adsorption column. The gas cylinder is used for recovering the special gas condensed by the condenser. And after the blowing is finished, closing the first gas conveying pipeline, the second conveying pipeline, the condensing medium conveying pipeline and the third gas conveying pipeline, and performing auxiliary heating on the condenser to ensure that the condensed special gas is directly recovered by the gas cylinder after being converted into a gas state again. Preferably, the condensation temperature of the condenser is below-170 ℃, the adopted condensation medium is liquid nitrogen, liquid argon, liquid helium or other refrigerants capable of reaching the condensation temperature, and liquid nitrogen is most preferably adopted.
Preferably, all the pipelines of the device of the invention are provided with regulating valves for regulating flow.
The invention has the beneficial effects that: the invention adopts hydrogen or helium as carrier gas, blows gas into the molecular sieve adsorption column at normal temperature to impact special gas in the molecular sieve, thereby realizing direct recovery of the special gas in the molecular sieve at normal temperature, and has the advantages of low recovery cost, easy operation, environmental protection, safety, recovery rate of more than 90 percent and considerable economic benefit. Because the recovery method of the invention does not need heating, other impurities such as moisture and the like absorbed in the molecular sieve are not easy to desorb, so that the content of the impurities in the recovered special gas is low, and the utilization value is high. In addition, the carrier gas adopted by the invention does not introduce impurities, and the special gas can be separated from the carrier gas by directly condensing the special gas at low temperature subsequently, and the separated carrier can be directly recycled. Therefore, the invention makes up the technical defect that the special gas adsorbed in the molecular sieve can not be directly recovered in the prior industry, and greatly reduces the purification cost of the special gas.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for recovering a specialty gas adsorbed by a molecular sieve according to the present invention.
In the figure, a first gas conveying pipeline 1, a second gas conveying pipeline 2, a third gas conveying pipeline 3, a condensing medium conveying pipeline 4, a tube array condenser 5, a gas circulator 6, a gas cylinder 7, a molecular sieve adsorption column 8, a cooling medium inlet 9, a regulating valve 10, a cooling medium outlet 11, a shell-side gas inlet 12 and a shell-side gas outlet 13.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention is further described below with reference to the accompanying drawings and examples. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
As shown in fig. 1, this embodiment 1 provides an apparatus for recovering a special gas adsorbed by a molecular sieve, which includes a first gas conveying pipeline 1, a second gas conveying pipeline 2, a third gas conveying pipeline 3, a condensing medium conveying pipeline 4, a shell and tube condenser 5, a gas circulator 6, and a gas cylinder 7. Specifically, the first gas delivery pipeline 1 is connected to an interface at the bottom of the molecular sieve adsorption column 8, which adsorbs the special gas, and is used for blowing the non-impurity gas into the molecular sieve adsorption column 8 to desorb the special gas in the molecular sieve. One end of the second gas conveying pipeline 2 is connected with an interface at the top of the molecular sieve adsorption column 8, and the other end of the second gas conveying pipeline 2 is connected with a shell side gas inlet 12 of the tube nest condenser 5, so that the mixed gas desorbed from the molecular sieve adsorption column 8 is conveyed to the tube nest condenser 5. The mixed gas passes through the shell side of the tube in the shell-and-tube condenser 5, the tube is filled with a condensing medium, the special gas in the mixed gas outside the tube is condensed by the condensing medium, but the non-impurity gas keeps a gaseous state, so that the special gas is separated from the non-impurity gas. The condensing medium conveying pipeline 4 is connected with a cooling medium inlet 9 at the bottom of the tube array condenser 5 and is used for conveying condensing medium into the tube array of the tube array condenser 5. The third gas conveying pipeline 3 and the gas cylinder 7 are respectively connected with a shell pass gas outlet 13 of the shell-and-tube condenser 5, the third gas conveying pipeline 3 is further connected with the gas circulator 6, and the gas circulator 6 is further connected with the first gas conveying pipeline 1. The third gas transport line 3 is used to discharge the non-impurity gas separated by the shell and tube condenser 5 and to re-transport the discharged non-impurity gas back into the first gas transport line 1 by the gas circulator 6 for re-use as a carrier gas. The gas cylinder 7 is used for recovering the special gas condensed by the tube still condenser 5. After the blowing is finished, evacuating the gas in the shell pass of the tube condenser 5, closing the first gas conveying pipeline 1, the second conveying pipeline 2, the third gas conveying pipeline 3 and the condensing medium conveying pipeline 4, performing auxiliary heating on the tube condenser 5 to convert the special gas condensed into solid or liquid state into gas state again, and then directly recovering the gas from the gas cylinder 7. In addition, the pipelines of the device are all provided with a regulating valve 10 for regulating the flow.
The special gas is arsine, phosphine or germane, the non-impurity gas is hydrogen or helium, and the condensing medium is liquid nitrogen, liquid argon or liquid helium. The top of the tube array condenser 5 is provided with a cooling medium outlet 11, and the gasified nitrogen or argon in the tube array can be discharged from the cooling medium outlet 11.
Example 2: method for recovering germane adsorbed by molecular sieve
200kg of 13X molecular sieve is filled in a molecular sieve adsorption column to be recovered, and the molecular sieve is used for purifying 100kg of germane, and 10kg of germane is absorbed in the molecular sieve.
In this embodiment 2, the device of embodiment 1 is matched to recover germane in the molecular sieve adsorption column, which is specifically as follows:
(1) adopting non-impurity gas as hydrogen, blowing hydrogen flow into the molecular sieve adsorption column at the flow rate of 60L/min, and continuously blowing for 8 h;
(2) Condensing the mixed gas discharged from the molecular sieve adsorption column at the temperature of liquid nitrogen, discharging the residual uncondensed hydrogen from a third gas conveying pipeline, and returning the residual uncondensed hydrogen to the first gas conveying pipeline through a gas circulator;
(3) After the hydrogen is blown, evacuating the gas in the shell pass of the tube still condenser, converting the condensed solid germane into gas state again by auxiliary heat, and then directly recovering by using a gas cylinder.
Through detection and statistics, the recovered germane is 9.5kg, and the recovery rate is as high as 95%.
the impurity content of germane recovered in this example is shown in table 1. Therefore, the recovered germane has low impurity content, high purity and high utilization value.
TABLE 1 impurity content of recovered germane
| Gas phase impurity project | H2 | O2 | N2 | CH4 | CO | CO2 | Moisture content |
| Content (ppm) | 230 | 0.23 | 0.47 | ND | ND | ND | 1.9 |
Example 3: method for recovering arsine adsorbed by molecular sieve
The molecular sieve adsorption column to be recovered is filled with 200kg of 4A molecular sieve, which was used for purifying 200kg of arsine, and 30kg of arsine is absorbed in the molecular sieve.
In this embodiment 3, the apparatus of embodiment 1 is used to recover arsine in the molecular sieve adsorption column, which is specifically as follows:
(1) Adopting non-impurity gas as hydrogen, blowing hydrogen flow into the molecular sieve adsorption column at the flow rate of 60L/min, and continuously blowing for 8 h;
(2) Condensing the mixed gas discharged from the molecular sieve adsorption column at the temperature of liquid nitrogen, discharging the residual uncondensed hydrogen from a third gas conveying pipeline, and returning the residual uncondensed hydrogen to the first gas conveying pipeline through a gas circulator;
(3) After the hydrogen blowing is finished, the gas in the shell pass of the condenser is pumped out, the condensed solid arsine is converted into a gaseous state again through auxiliary heat, and then the gaseous arsine is directly recovered by using a gas cylinder.
Through detection and statistics, the recovered arsine in the embodiment is 28kg, and the recovery rate is up to 93.3%.
Example 4: the influence of the flow rate and the blowing time of the non-impurity gas on the recovery effect of the special gas is explored
The experimental method comprises the following steps: referring to the recovery method of example 2, 13X molecular sieves adsorbed with 10kg of germane were blown with hydrogen gas at flow rates of 10L/min, 20L/min, 40L/min, 60L/min, 80L/min and 100L/min, respectively, for 8 hours, and the recovered germane weights are as shown in Table 2 below.
TABLE 2 germane recovery effect at different hydrogen flow rates
As can be seen from Table 2, the higher the recovery rate of germane with the increase of the hydrogen flow rate, the less significant the increase of the recovery rate of germane when the hydrogen flow rate reaches 60L/min or more, and other impurities are carried over with the flow rate being too high. Therefore, the invention takes 60L/min as the preferable flow rate of the non-impurity gas, the recovery rate of germane reaches 95 percent, and the recovered germane has higher purity.
The experimental method comprises the following steps: referring to the recovery method of example 2, 13X molecular sieves, which absorbed 10kg of germane, were blown with hydrogen gas at a flow rate of 60L/min for 2 hours, 4 hours, 6 hours, 8 hours, 10 hours and 12 hours, respectively, and the weights of the recovered germane were as shown in Table 3 below.
TABLE 3 recovery of germane at different blowing times
As can be seen from table 3, the higher the recovery rate of germane as the blowing time increased, and when the blowing time reached 8 hours or more, the increase in the recovery rate of germane was insignificant. Therefore, the invention takes 8h as the preferable blowing time of the non-impurity gas, the recovery rate of the germane is as high as 95%, and the recovered germane has higher purity.
finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for recovering special gas adsorbed by a molecular sieve is characterized by comprising the following steps:
(1) Blowing non-impurity gas to the molecular sieve adsorbed with the special gas to desorb the special gas on the molecular sieve to obtain mixed gas containing the non-impurity gas and the special gas;
(2) condensing the special gas in the mixed gas to separate the special gas from the non-impurity gas;
(3) Recovering the special gas condensed in the step (2);
The non-impurity gas includes at least one of hydrogen and helium;
The specialty gas comprises at least one of arsine, phosphine, and germane.
2. The method for recovering a specialty gas from molecular sieve adsorption of claim 1 wherein said non-contaminant gas is blown continuously in a downward-upward direction.
3. the method for recovering the special gas adsorbed by the molecular sieve according to claim 1, wherein the flow rate of the non-impurity gas is 60-100L/min, and the blowing time is 8-12 h; preferably, the non-impurity gas is hydrogen.
4. the method for recovering a specialty gas from molecular sieve adsorption of claim 1 wherein said step (2) condensing and recovering said specialty gas is carried out at a temperature of-170 ℃ or less and wherein said condensing medium is liquid nitrogen, liquid argon or liquid helium; preferably, said step (2) condenses the specialty gas at the temperature of liquid nitrogen.
5. The method for recovering a specialty gas from molecular sieve adsorption of claim 1, wherein step (3) converts the specialty gas to a gaseous state and recovers the gaseous state into a cylinder during recovery of the condensed specialty gas.
6. The device for recovering the special gas adsorbed by the molecular sieve is characterized by comprising a first gas conveying pipeline, a second gas conveying pipeline and a condenser; the first gas conveying pipeline is used for blowing non-impurity gas into the molecular sieve adsorption column which adsorbs the special gas so as to desorb the special gas in the molecular sieve adsorption column; the second gas conveying pipeline is used for conveying the mixed gas desorbed from the molecular sieve adsorption column to the condenser; the condenser is used for condensing the special gas in the mixed gas to separate the special gas from the non-impurity gas; the non-impurity gas includes at least one of hydrogen and helium; the specialty gas comprises at least one of arsine, phosphine, and germane.
7. The apparatus for recovering a specialty gas from molecular sieve adsorption of claim 6, wherein said first gas delivery line is connected to an interface at the bottom of the molecular sieve adsorption column, one end of said second gas delivery line is connected to an interface at the top of the molecular sieve adsorption column, and the other end of said second gas delivery line is connected to said condenser.
8. The apparatus for recovering a specialty gas from molecular sieve adsorption of claim 6, wherein said condenser is a shell-side condenser, the mixed gas is fed out of the shell side of the tube, the tube is filled with a condensing medium, and said second gas feed line is connected to the shell side gas inlet of said condenser.
9. The apparatus for recovering a specialty gas from molecular sieve adsorption of claim 8, further comprising a condensing medium delivery line, a third gas delivery line, a gas circulator, and a gas cylinder; the condensing medium conveying pipeline is used for conveying condensing medium into the tubes of the condenser; the third gas conveying pipeline and the gas cylinder are respectively connected with a shell pass gas outlet of the condenser, the gas cylinder is used for recovering special gas condensed by the condenser, the third gas conveying pipeline is used for discharging non-impurity gas separated by the condenser, the third gas conveying pipeline is further connected with the gas circulator, and the gas circulator is further connected with the first gas conveying pipeline.
10. the device for recovering the special gas adsorbed by the molecular sieve according to any one of claims 6 to 9, wherein all pipelines of the device are provided with regulating valves for regulating flow.
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