Abstract:
During the conventional temperature swing adsorption (TSA) process, NF 3  co-adsorbed with the impurities is vented during regeneration. This invention is a novel TSA cycle in which the co-adsorbed NF 3  is recovered. In this novel TSA cycle, a control scheme is used to stop the adsorption prior to the saturation of the adsorber with impurities and use a recovery purge gas (either co-current or counter-current) to release the co-adsorbed NF 3  off the saturated adsorber. The effluent of the inert purge gas can be combined with the effluent of the on-stream vessel or can be recycled to the feed of the on-stream vessel. 10%-100% of the co-adsorbed NF 3  is recovered and made available as product in this novel TSA cycle. Thus the overall process yield of NF 3  is increased. The removing of the co-adsorbed NF 3  from the adsorber also prevents adsorber degradation thus prolonging the useful life of the adsorber.

Description:
BACKGROUND OF THE INVENTION 
       [0001]    NF 3  is a gas used in the manufacture of displays, semiconductors and photovoltaics. One undesirable property of NF 3  is its Global Warming Potential (GWP) which is 17,000 times greater than the GWP of CO 2 . 
         [0002]    Background atmospheric abundances and trends of nitrogen trifluoride (NF 3 ), a potent anthropogenic greenhouse gas, have been measured for the first time by Weiss, R. F., J. Mühle, P. K. Salameh, and C. M. Harth (2008), Nitrogen trifluoride in the global atmosphere,  Geophys. Res. Lett.,  35, L20821, doi:10.1029/2008GL035913. The mean global tropospheric concentration of NF 3  has risen quasi-exponentially from about 0.02 ppt (parts-per-trillion, dry air mole fraction) at the beginning of the measured record in 1978, to a Jul. 1, 2008 value of 0.454 ppt, with a rate of increase of 0.053 ppt/yr, or about 11% per year, and an interhemispheric gradient that is consistent with these emissions occurring overwhelmingly in the Northern Hemisphere. This rate of rise corresponds to about 620 metric tons of NF 3  emissions globally per year, or about 16% of the global NF 3  production estimate of 4,000 metric tons/yr. 
         [0003]    Concern about the growing concentration of NF 3  in the earth&#39;s atmosphere has created a need for NF 3  manufacturing methods which reduce or eliminate NF 3  emissions to the atmosphere. 
         [0004]    Manufacturing methods for NF 3  often employ a temperature swing adsorption (TSA) to remove impurities which would otherwise solidify during the NF 3  cryogenic distillation unit operation. 
         [0005]    In a conventional TSA cycle, a large portion of the NF 3  gas that is co-adsorbed with the impurities is vented during the regeneration step. 
         [0006]    The following patents are representatives on refining NF 3  by adsorption. 
         [0007]    U.S. Pat. No. 4,156,598 describes the conventional TSA process used in NF 3  refining: “Normally the adsorbers are operated until there is a detectable quantity of nitrous oxide leaving the adsorber at which time the adsorber is switched to the regenerated adsorber. The spent adsorber is then regenerated by permitting nitrogen to flow through the adsorber at an elevated temperature.” Using this process the co-adsorbed NF 3  is vented along with the adsorbed impurities, thereby causing NF 3  to be released to the atmosphere and lowering the yield of NF 3 . 
         [0008]    U.S. Pat. No. 4,933,158 describes an improvement to U.S. Pat. No. 4,156,598 wherein the adsorber or the absorber is selected to try to maximize the adsorber capacity for the impurities so that the “the loss of NF 3  by the adsorption is much smaller”. However, the amount of NF 3  lost per cycle is roughly equivalent since the capacity of NF 3  on the improved adsorber is similar. No process improvement is described to recover this co-adsorbed NF 3 . 
         [0009]    U.S. Pat. No. 5,069,887 describes a process where NF 3  is adsorbed and impurities (CF 4 ) are not adsorbed. In a second step, helium is used to purge the voids of impure NF 3 . In a third step the pressure is reduced to desorb the NF 3  which is condensed in a LIN-cooled trap. Impurities are not co-sorbed so no recovery separation is needed and column effluent is not recycled to the feed. 
         [0010]    U.S. Pat. No. 5,417,742 describes the process recovery of perfluorocarbons (PFC) from gas streams using adsorption in TSA or Pressure Swing Adsorption (PSA) modes. The PFC in a permanent gas are adsorbed on a zeolite, then feed flow is stopped and the temperature is raised and/or the pressure lowered to desorb the PFC which is transferred to further purification or sent to another process to be used captively. During the desorption step, the effluent is not combined with the impure gas stream. Impurities are not co-sorbed on the zeolite so no recovery separation is needed. 
         [0011]    U.S. Pat. No. 5,425,240 describes an improved TSA process for the purification of O 2  in which the adsorption is performed at cryogenic temperatures. The regeneration step is conducted with product gas, i.e. pure O 2 , so a substantial amount of purified product gas is vented. 
         [0012]    The following patents are representatives on pressure swing adsorption (PSA) where the column purge is recycled to the feed. 
         [0013]    U.S. Pat. No.  5 , 254 , 154  describes an improved PSA process in which during the regeneration step, the column is depressurized countercurrent and a portion of withdrawn residual gas is mixed with the impure gas to be treated. This would be ineffective with NF 3  since it is a strongly adsorbed species. The impurities are also more strongly adsorbed than NF 3  and would also not be removed with a depressurization step. For the NF 3  process, heating of the adsorber is a requirement during the regeneration portion of the cycle. 
         [0014]    U.S. Pat. No. 5,620,501 describes an improved PSA process in which the void-space gas is stored in an intermediate vessel during evacuation of the adsorber (regeneration). This improvement requires that the product gas and sorbed impurity gas be easily removed by pressure reduction of the adsorber. Since both NF 3  and the adsorbed impurities are strongly bound on the adsorber, heat input is required. 
         [0015]    U.S. Pat. No. 5,254,154 describes an improved PSA process in which during the regeneration step, the column is depressurized countercurrent and a portion of withdrawn residual gas is mixed with the impure gas to be treated. This would be ineffective with NF 3  since it is a strongly adsorbed species. The impurities are also more strongly adsorbed than NF 3  and would also not be removed with a depressurization step. For the NF 3  process, heating of the adsorber is a requirement during the regeneration portion of the cycle. 
         [0016]    U.S. Pat. No. 5,620,501 describes an improved PSA process in which the void-space gas is stored in an intermediate vessel during evacuation of the adsorber (regeneration). This improvement requires that the product gas and sorbed impurity gas be easily removed by pressure reduction of the adsorber. Since both NF 3  and the adsorbed impurities are strongly bound on the adsorber, heat input is required. 
         [0017]    This invention is a novel TSA cycle in which 10-100% of the co-adsorbed NF 3  is recovered. In the TSA cycle, a control scheme is used to stop the adsorption prior to the saturation of the adsorber with impurities and use an inert purge gas (either co-current or counter-current) to release 10-100% of the NF 3  off the saturated adsorber. The effluent of the inert purge gas can be combined with the effluent of the on-stream vessel or can be recycled to the feed of the on-stream vessel. 
         [0018]    The benefits of this novel TSA cycle is that 10%-100% of the co-adsorbed NF 3  is not vented to the atmosphere but made available as product. Thus the overall process yield of NF 3  is increased. 
         [0019]    An additional benefit is in prolonging the useful life of the adsorber. When heated rapidly with adsorbers during the regeneration step in a conventional TSA, NF 3  can decompose and react with the adsorber structure thereby degrading the material&#39;s performance in adsorbing impurities. The recovery step removes the NF 3  in a controlled fashion reducing or preventing adsorber degradation. 
       BRIEF SUMMARY OF THE INVENTION 
       [0020]    A process for removing at least one impurity from a crude NF 3  gas stream in a system having at least two vessels each containing an adsorber, comprising steps of: 
         [0021]    flowing the crude NF 3  gas stream through the first adsorber in the first vessel to selectively adsorb the at least one impurity; 
         [0022]    redirecting the flow of the crude NF 3  gas stream through the second adsorber in the second vessel after a predetermined time or when effluent of the first adsorber reaches a predetermined level of the at least one impurity; 
         [0023]    flowing a recovery purge gas through the first adsorber to selectively desorb co-adsorbed NF 3  from the first adsorber; 
         [0024]    discontinuing the flow of the recovery purge gas when a predetermined time, or when effluent of the recovery purge gas reaches a predetermined level of the at least one impurity or a predetermined percentage of co-adsorbed NF 3 ; 
         [0025]    flowing a regeneration purge gas through the first adsorber to purge adsorbed at least one impurity and remaining co-adsorbed NF 3  from the first adsorber; and discontinuing the flow of the regeneration purge gas. 
         [0026]    10-100% of the co-adsorbed NF 3  is recovered by passing the recovery purge gas through the first adsorber. 
         [0027]    The process further comprises the steps of 
         [0028]    redirecting the flow of the crude NF 3  gas stream back through the first adsorber in the first vessel after a predetermined time or when effluent of the second adsorber reaches a predetermined level of the at least one impurity; 
         [0029]    flowing the recovery purge gas through the second adsorber to selectively desorb the co-adsorbed NF 3  from the second adsorber; 
         [0030]    discontinuing the flow of the recovery purge gas when a predetermined time or when effluent of the recovery purge gas reaches a predetermined level of the at least one impurity or a predetermined percentage of co-adsorbed NF 3 ; 
         [0031]    flowing the regeneration purge gas through the second adsorber to purge adsorbed at least one impurity and remaining co-adsorbed NF 3  from the second adsorber; and 
         [0032]    discontinuing the flow of the regeneration purge gas. 
     
    
     
       BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS 
         [0033]      FIG. 1  shows a schematic apparatus for recovering of NF 3  with countercurrent flow. 
           [0034]      FIG. 2  shows a schematic apparatus for recovering of NF 3  with cocurrent flow. 
           [0035]      FIG. 3  shows a normalized recovery of % NF 3  and % N 2 O as a function of time for Example 1. 
           [0036]      FIG. 4  shows a normalized recovery of % NF 3  and % N 2 O as a function of time for Example 2. 
           [0037]      FIG. 5  shows a normalized recovery of % NF 3  and % N 2 O as a function of time for Example 3. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0038]    The present invention discloses a novel TSA cycle. It teaches how to recover the NF 3  in the traditional Temperature Swing Adsorption (TSA) process for the purification of NF 3 . The invention is independent of the synthesis method for the NF 3  and is also independent of any previous or subsequent purification unit operations (for example, wet scrubbers to remove hydrolyzable impurities, distillation to remove non-adsorbable impurities). 
         [0039]    The system will be described as comprising two parallel arranged columns or vessels (column and vessel are interchangeable), each containing an adsorbent or adsorber (adsorbent and adsorber are interchangeable). However, the invention is not limited to a system having two vessels and two adsorbers, and may have more than two vessels and two adsorbers. 
         [0040]    A conventional TSA process consists of two steps: adsorption and regeneration. The novel TSA process in the present invention has an additional step, recovery, between the adsorption and regeneration steps. The novel TSA process consists of three steps adsorption, recovery and regeneration 
         [0041]    In the adsorption step, an impure NF 3  feed stream (the crude NF 3 ) containing adsorbable impurities is passed through the first adsorber in the first vessel. The adsorber preferentially adsorbs the adsorbable impurities thereby substantially removing the adsorbable impurities from the NF 3 . A portion of the NF 3  is also co-adsorbed. This comprises the adsorption step which is continued until either a predetermined processing time has elapsed or the impurities breakthrough the adsorber into the adsorber effluent at an unacceptable concentration. The impure NF 3  feed flow is then redirected to the second adsorber in the second vessel. 
         [0042]    In the recovery step, 10-100% of the co-adsorbed NF 3  is recovered by passing a recovery purge gas, usually an inert purge gas through the first vessel, either counter-current or co-current, under the appropriate conditions to substantially desorb the adsorbed NF 3  while only minimally desorbing any adsorbed impurities and combining the effluent inert purge gas with the impure NF 3  feed stream directed to the on-stream second vessel. The recovery step is continued for a predetermined time, or when effluent of the recovery purge gas reaches either a predetermined level of the at least one impurity, or a predetermined percentage of co-adsorbed NF 3 ; such as from 10% to 100%. 100% indicates all of the NF 3  is recovered, 
         [0043]    In the final regeneration step, a flow of regeneration purge gas, usually an inert purge gas heated to above the reversal temperature of the adsorbed impurities is vented through the vessel to remove the adsorbed impurities and remaining co-sorbed NF 3  to complete the TSA cycle. 
         [0044]    The “reversal temperature” used here is well defined in the art. For a reference, please see Yang, R.,  Gas Separation By Adsorption Processes,  Boston, Butterworths, 1987, pp 171-172. 
         [0045]    In another embodiment the adsorption step is stopped short of impurity breakthrough leaving the bottom portion of the first adsorber with additional capacity for the adsorbable impurities. 
         [0046]    In the subsequent recovery step, 10-100% of the co-adsorbed NF 3  is recovered by passing a purge gas co-current through the first vessel and monitoring the effluent for NF 3  and desorbed impurities at the vessel outlet. The purge gas effluent from the recovery vessel is blended with the effluent from the on-stream vessel and sent directly to subsequent unit operations. The bottom unused portion of the recovery adsorber will adsorb the desorbing impurities, so the vessel effluent will contain only the inert purge and NF 3 . 
         [0047]    Optionally, when an impurity is detected as breaking through, the recovery vessel effluent could be blended with the crude feed of the on-stream vessel as described above to further capture additional NF 3  without sending the desorbing impurity downstream. 
         [0048]    Once a predetermined recovery time has elapsed, the desorbing impurity reaches a predetermined concentration, or a predetermined percentage of co-adsorbed NF 3  is recovered, the regeneration step is conducted similarly to the previous embodiment. 
         [0049]    In the current NF 3  purification processes, the recovery step minimizes the amount of NF 3  vented to the atmosphere, increases the overall process yield of NF 3 , and extends the useable life of the adsorber by limiting degradation caused by residual NF 3  during the regeneration step. 
         [0050]    Typical impurities removed by adsorption in NF 3  manufacturing processes include N 2 O, CO 2 , H 2 O, OF 2 , SF 6 , CF 4 , C 2 F 6  and combinations thereof. 
         [0051]    Typical adsorbers used in NF 3  manufacturing processes that selectively adsorb the impurities might also co-adsorb NF 3 . The adsorbers are any one which is known in the art. The adsorber preferably is an aluminosilicate zeolite selected from those having the FAU, MOR, CHA, OFF, ERI, FER, GME, LEV, EMT, BEA, MAZ, LTA, LTL, MFI, MEL, MTW, MEI, MFS, and NES frameworks or combinations of these. Examples include Na-MOR, Ca-LTA, Na-FAU and combinations thereof. 
         [0052]    A typical purge gas used in the recovery process is helium, nitrogen or argon. A typical regeneration gas is helium, nitrogen or argon. These serve only as examples, and the invention is not limited to these impurities, adsorbers, or regeneration gases. 
         [0053]    The preferred combination of adsorber is Na-MOR; and the recovery and regeneration gas is N 2 . 
         [0054]    The recovery temperature ranges from −20 to 120° C., preferably 4 to 65° C., more preferably 4 to 30° C. 
         [0055]    The recovery molar mass velocity (flow rate divided by the cross-sectional vessel area) ranges from 0.2 to 40 kg-mol/m 2  hr, preferably 0.5 to 15 kg-mol/m 2  hr, and most preferably 1 to 7 kg-mol/m 2  hr. The recovery gas residence time ranges from 0.1 to 25 minutes, preferably 0.3 to 10 minutes and most preferably 0.7 to 5 minutes. The recovery gas pressure ranges from 0.2 to 3 atm. 
         [0056]    The regeneration temperature ranges from 35 to 450° C. 
         [0057]    The analyzer may be any one of several methods useful in quantifying NF 3  and adsorbable impurity concentrations including but not limited to gas chromatography, Infrared spectroscopy, or mass spectrometry. 
         [0058]    There are several specific flow path options in the process and several embodiments as described below. 
         [0059]    One embodiment of the invention is illustrated in  FIG. 1 . 
         [0060]      FIG. 1  shows schematically an apparatus to practice the recovery step with countercurrent flow. 
         [0061]    The apparatus comprises two vessels  1  and  2  that containing adsorbers, an inlet conduit  3  for the crude NF 3 , an outlet conduit  13  for the refined NF 3 , a vent conduit  14  for waste gas, another inlet conduit  8  is for both a recovery and a regeneration purge gas such as supplying an inert gas, a flow element  10  to control the recovery/regeneration gas flow, and a heating element  11  and heating control system  12  to heat the recovery/regeneration purge gas as well as an optional NF 3 /impurity analyzer  17 . Two vessels are provided so that one vessel can be on-stream while the other vessel is in the recovery or regeneration step or on standby allowing for continuous operation. 
         [0062]    The process cycle including the countercurrent recovery step is as follows. 
         [0063]    During the Adsorption step, crude NF 3  gas stream flows in from  3 , to the adsorber in vessel  1  through valve  5 - 1 , then out of vessel  1  to outlet  13  through valve  7 - 1 . Flow through adsorber in vessel  1  is continued until breakthrough of the adsorbed impurities in the adsorber effluent as determined by run time or by detection of the impurities at optional analyzer  17  through valve  19 - 1 . 
         [0064]    Once the breakthrough of the adsorbed impurities in the adsorber effluent is determined, valves  5 - 2  and  7 - 2  are opened. Valve  5 - 1  remains open but valve  7 - 1  is closed to allow the crude NF 3  to flow through the adsorber in vessel  2 . Vessel  2  is now on-stream. Vessel  2  is in the preparation of recover. 
         [0065]    The recovery step is initiated by flowing recovery purge gas coming from inlet conduit  8  through the adsorber in vessel  1  by opening valves  9  and  6 - 1 . The recovery purge gas flow is set with  10  and recovery temperature is set with  12 . When the recovery purge gas passes through the first vessel, substantially desorbs the adsorbed NF 3  while only minimally desorbing the adsorbed impurities. 
         [0066]    The effluent gas, or recovery gas from the adsorber, that is, the purge gas containing NF 3  and a low concentration of one or more impurities is out from vessel  1 . The effluent gas combines with the feeding crude NF 3  gas stream through the open valve  5 - 1  and then is directed together with the feeding crude NF 3  gas stream to the on-stream second vessel for the adsorption step. 
         [0067]    An optional NF 3 /impurity analyzer  17  may be utilized to monitor recovery progress by opening valve  15 - 1 . 
         [0068]    The recovery step may be run for a set time or governed by the NF 3 /impurity concentrations in the recovery gas as observed at the analyzer  17  through valve  19 - 1 . Once 10-100% of the adsorbed NF 3  is removed from adsorber in vessel  1  and bled into the onstream vessel  2  through valve  5 - 1 , the recovery purge gas is turned off at  9 , valve  5 - 1  is closed and valve  4 - 1  is opened. 
         [0069]    The regeneration step is initiated by opening  9  and restarting the regeneration purge gas flow. The regeneration purge gas flows through valve  6 - 1 , the adsorber in vessel  1 , valve  4 - 1  and out the vent conduit  14  by setting the regeneration purge gas flow with  10  and recovery temperature with  12 . 
         [0070]    Once the adsorbed impurities and remaining co-adsorbed NF 3  are removed from the adsorber in vessel  1  and conducted out through the vent  14 , heating element  11  is turned off. After vessel  1  is cooled to ambient temperature the regeneration purge gas flow is reduced or turned off and vessel  1  is on standby until the on-stream vessel  2  becomes saturated. Once vessel  2  is saturated, the vessel  1  is placed onstream, and the NF 3  co-adsorbed on adsorber in vessel  2  is now recovered prior to regeneration in a similar fashion. 
         [0071]    Another embodiment of the invention is illustrated in  FIG. 2 . 
         [0072]      FIG. 2  shows schematically an apparatus to practice the recovery step with cocurrent flow. 
         [0073]    The main parts of the apparatus are identical to the embodiment illustrated in  FIG. 1  except conduit  23  is added to allow recovery gas to flow co-current through the adsorbers in the vessels. An optional mid-vessel analysis tap,  22 , can be added to leave a downstream portion of the adsorber free of adsorbed impurities to facilitate the NF 3  recovery step. 
         [0074]    The process cycle including the co-current recovery step is as follows. 
         [0075]    During the Adsorption step, crude NF 3  gas stream flows in from  3 , to the adsorber in vessel  1  through valve  5 - 1 , then out of vessel  1  to outlet  13  through valve  7 - 1 . Flow through adsorber in vessel  1  is continued until breakthrough of the adsorbed impurities in the adsorber effluent as determined by run time or by detection of the impurities at optional analyzer  17  through valve  19 - 1 , or by detection of the impurities at the optional mid-vessel tap  22 - 1  at analyzer  17  through valve  21 - 1 . 
         [0076]    Once the breakthrough of the adsorbed impurities in the adsorber effluent is determined, valves  5 - 2  and  7 - 2  are opened. Valves  5 - 1  and  7 - 1  are closed to allow the crude NF 3  to flow through the adsorber in vessel  2 . Vessel  2  is now on-stream. Vessel  2  is in the preparation of recover. 
         [0077]    The recovery step is initiated by flowing recovery purge gas coming from inlet conduit  8  (by opening valve  9 ), through conduit  23 , passing the adsorber in vessel  1  (by opening valve  17 - 1 ). The recovery purge gas flow is set with  10  and recovery temperature is set with  12 . When the recovery purge gas passes through the first vessel, substantially desorbs the adsorbed NF 3  while only minimally desorbing the adsorbed impurities. 
         [0078]    The effluent gas, or recovery gas, that is, the purge gas containing NF 3  and a low concentration of one or more impurities is out from vessel  1  and into the adsorber in vessel  2  through the opening of valves  18 - 1  and  20 - 2 . 
         [0079]    The effluent gas combines with the feeding crude NF 3  gas stream through the open valve  5 - 2  and then is directed to the on-stream second vessel for the adsorption step. 
         [0080]    An optional NF 3 /impurity analyzer  17  may be utilized to monitor progress through valve  19 - 1 . 
         [0081]    If the optional mid-vessel tap  22  is employed to leave a portion of the adsorber free of adsorbed impurities, optionally the recovery purge gas can flow through the adsorber in vessel  1 , substantially desorb the adsorbed NF 3  and then be blended with the refined NF 3  from vessel  2  by opening  17 - 1  and  7 - 1 . 
         [0082]    If the optional step is employed of flowing the recovered NF 3  directly to conduit  13 , the recovery gas flow can be redirected through vessel  2  as described above after a set time or governed by the NF 3 /impurity concentrations in the recovery gas as observed at the optional analyzer  17  through valve  19 - 1 . 
         [0083]    The recovery step may be run for a set time or governed by the NF 3 /impurity concentrations in the recovery gas as observed at the optional analyzer  17  through valve  19 - 1 . 
         [0084]    Once 10-100% of the adsorbed NF 3  is removed from the adsorber in vessel  1 , the recovery/regeneration purge gas is turned off at  9 , and valves  7 - 1 ,  17 - 1 ,  18 - 1 ,  20 - 2  are closed. Valves  6 - 1  and  4 - 1  are opened. 
         [0085]    The regeneration step is initiated by opening  9  and restarting the regeneration purge gas flow. The purge gas flows through  15 , valve  6 - 1 , the adsorber in vessel  1 , valve  4 - 1  and out the vent conduit  14  by setting the regeneration purge gas flow with  10  and recovery temperature with  12 . 
         [0086]    Once the adsorbed impurities and remaining co-adsorbed NF 3  are removed from the adsorber in vessel  1  and conducted out through the vent  14 , heating element  11  is turned off. After vessel  1  is cooled to ambient temperature the regeneration purge gas flow is reduced or turned off and vessel  1  is on standby until the on-stream vessel  2  becomes saturated. Once vessel  2  is saturated, the vessel  1  is placed onstream, and the NF 3  co-adsorbed on adsorber in vessel  2  is now recovered prior to regeneration in a similar fashion. 
         [0087]    These two embodiments show economical two-adsorber systems in  FIGS. 1 and 2 . If the back pressure restrictions of the on stream vessel flow does not allow for the blending of the effluent from the recovery vessel to the feed of the on stream vessel, a three-vessel system can be employed where the effluent from the recovery vessel is sent to a third vessel (the standby vessel). The standby vessel is a vessel with regenerated adsorber. Once the recovery operation is complete, flow to the standby vessel is halted and the heated regeneration of the recovery vessel is initiated. Once impurities have broken through the on stream vessel, the vessels identities are changed: the standby vessel becomes the on-stream vessel, the recovery vessel (now regenerated) becomes the standby vessel and the on stream vessel becomes the recovery vessel. 
       WORKING EXAMPLES 
       [0088]    A system described by  FIG. 1  containing two vessels was used in the working examples. Two vessels were filled with Na-MOR to purify crude NF 3  containing 70% NF 3 , 20% N 2 , 10% O 2  and 100 ppm N 2 O. The impurity to be removed was N 2 O. 
         [0089]    The crude NF 3  gas was flowed through vessel  1  until the analyzer  17  detected 1 ppm N 2 O in the effluent of vessel  1 . Then, the crude NF 3  gas flow was switched to vessel  2  and vessel  1  went through a recovery and regeneration operations as described by the following examples. 
       Example 1 
       [0090]    A nitrogen purge gas was flowed counter-current through vessel  1  at a molar mass velocity of 28 kg-mol/m 2  hr with a residence time of 0.17 min and 1.1 atm pressure at ambient temperature for 3.5 hours (recovery operation) and then heated to 290° C. (regeneration operation). A gas chromatograph measured the concentration of NF 3  and N 2 O in the nitrogen effluent. The known flow rate with the measured concentrations of NF 3  and N 2 O allowed the integrated amounts of NF 3  and N 2 O in the nitrogen effluent to be calculated. The aggregate amounts of NF 3  and N 2 O detected at a given time were normalized to the total amount of NF 3  and N 2 O detected over the entire analysis period. These normalized amounts plotted versus time were shown in the annotated  FIG. 3 . 
       Example 2 
       [0091]    A nitrogen purge gas was flowed counter-current through vessel  1  at a molar mass velocity of 28 kg-mol/m 2  hr with a residence time of 0.17 min and 1.1 atm pressure at 54° C. for 4.5 hours (recovery operation) and then heated to 290° C. (regeneration operation). Analytical data were acquired and plotted as in Example 1. The normalized NF 3  ad N 2 O amounts plotted versus time were shown in the annotated  FIG. 4 . 
       Example 3 
       [0092]    A nitrogen purge gas was flowed counter-current through vessel  1  at a molar mass velocity of 5.6 kg-mol/m 2  hr with a residence time of 0.87 min and 1.1 atm pressure at ambient temperature for 4.3 hours (recovery operation) and then the molar mass velocity was increased to 28 kg-mol/m 2  hr and temperature to 290° C. (regeneration operation). Analytical data were acquired and plotted as in Example 1. The normalized NF 3  ad N 2 O amounts plotted versus time were shown in the annotated  FIG. 5 . 
         [0093]    The recovery step or operation shown in the examples above may be run for a set time or governed by the NF 3 /impurity concentrations in the recovery gas as observed at the optional analyzer. 
         [0094]    The regeneration step or operation can be performed as described before. 
         [0095]    The examples illustrated the surprising result that the most efficient NF 3  recovery was obtained when starting with a lower, ambient temperature flow. The NF 3  desorption was shown to be diffusion controlled where the N 2 O desorption was substantially equilibrium controlled. 
         [0096]    An equilibrium-controlled desorption has a stronger dependence on temperature versus a diffusion controlled desorption. Thus, in Example 2 versus Example 3, heating the recovery purge gas to an intermediate temperature of 54° C. did enhance the desorption of NF 3 , but simultaneously more strongly enhanced the desorption of N 2 O. However, the desorption of N 2 O in the recovery operation is not desirable. 
         [0097]    Example 1 versus Example 3 has shown that an equilibrium-controlled desorption was more strongly enhanced by higher flow. 
         [0098]    Thus, the recovery purge gas preferably has a lower temperature ambient −40° C., more preferably 4-30° C.; and lower molar mass velocity 0.5 to 15 kg-mol/m 2  hr, and most preferably 1 to 7 kg-mol/m 2  hr, in order to desorb the adsorbed NF 3  efficiently while only minimally desorbing the adsorbed impurities. 
         [0099]    While the regeneration purge gas (could be the same gas as the recovery purge gas) preferably has a higher temperature 50-450° C. and higher molar mass velocity 5-50 kg-mol/m 2  hr, in order to desorb the impurities. 
         [0100]    When the recovery purge gas and the regeneration gases are the same, the temperature of the regeneration purge gas is higher than the temperature of the recovery purge gas. The flow rate of the regeneration purge gas is also higher. 
         [0101]    The foregoing examples and description of the preferred embodiments should be taken as illustrating, rather than as limiting the present invention as defined by the claims. As will be readily appreciated, numerous variations and combinations of the features set forth above can be utilized without departing from the present invention as set forth in the claims. Such variations are not regarded as a departure from the spirit and scope of the invention, and all such variations are intended to be included within the scope of the following claims.