Process for recovery and purification of nitrous oxide
10464813 ยท 2019-11-05
Assignee
Inventors
Cpc classification
Y02C20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
This invention is aimed at recovering and purifying nitrous oxide from the gas stream containing N.sub.2O to produce different grade of nitrous oxide by combination of unit operation including, but not limited to, wet scrubbing, adsorption, liquefaction, flash distillation or continuous distillation with reflux.
Claims
1. A system for of recovering and purifying N.sub.2O, the system comprising: a gas stream comprising N.sub.2O and impurities comprising light and heavy impurities, water, and organic compounds, the gas stream first entering a wet scrubbing absorption unit that is selected from the group consisting of: a caustic scrubbing unit, an acid scrubbing unit, water scrubbing unit, and combinations thereof; a compressor having at least one stage of compression that compresses the gas stream from the wet scrubber to a preset pressure greater than 1.0 MPa; a cooling and drying unit that cools the gas stream from the compressor to less than 10.0 C. and removes condensed water; an adsorption unit comprising at least two parallel adsorption beds, each bed having at least one adsorbent layer adapted to remove heavy impurities, water and organic compounds from the gas stream from the cooling and drying unit; a buffer tank that stores the gas stream from the adsorption unit; a liquefaction unit that partially liquefies the gas stream from the buffer tank to create: (1) a first recycle gas mixture containing N.sub.2O and at least one non-condensation gas, and (2) a liquid mixture containing N.sub.2O; a releaser in fluid communication with the buffer tank and a distillation unit, wherein the releaser transmits the first recycle gas mixture from the liquefaction unit back to the adsorption unit and passes the liquid mixture from the liquefaction unit to the distillation unit, wherein the buffer tank is adapted to permit the gas to flow back to the adsorption unit via the releaser to repressurize the adsorption unit to the preset pressure, wherein the distillation unit is selected from a group consisting of a flash drum, a distillation column with reflux, and combinations thereof, wherein the distillation unit removes light impurities and organic compounds from the liquid mixture, and directs: (1) a second recycle gas mixture containing N.sub.2O and at least one non-condensation gas directly back to the compressor, and (2) purified liquid mixture to a holding tank; wherein, the gas stream exiting the wet scrubber has less than 500.0 ppm of NO.sub.2 and CO.sub.2, the gas stream exiting the adsorption unit has less than 0.5 ppm of NO.sub.2 and less than 1.0 ppm of CO.sub.2, and the purified liquid mixture has a N.sub.2O concentration of greater than 99.9% by volume.
2. The system according to claim 1, wherein prior to entering the wet scrubbing absorption unit, the gas stream contains 5.0 to 99.9% N.sub.2O by volume, and wherein the light impurities are selected from the group consisting of N.sub.2, O.sub.2, NO, CO, Ar, H.sub.2, methane, and C.sub.2 compounds; the heavy impurities are selected from the group consisting of CO.sub.2, NO.sub.2, CO, H.sub.2O, and C.sub.2+ compounds; the organic compound is selected from the group consisting of methane, C.sub.2+ compounds, CH.sub.4, and C.sub.2 compounds; the first recycle gas mixture and the second recycle gas mixture both include molecules selected from the group consisting of Ar, N.sub.2, O.sub.2, CO, NO, and methane; and the purified liquid mixture has a N.sub.2O concentration ranging from 99.9% to 99.9999% by volume.
3. The system according to claim 1, wherein the compressor has at least two stages of compression and the second recycle gas mixture is introduced to the compressor between the first and the second stage; and the preset pressure of the gas mixture exiting the second stage of compression ranges from between 2.0 to 5.0 MPa.
4. The system according to claim 1, wherein the parallel adsorption beds are alternately used in continuous swing operation and the first recycle gas mixture is used to regenerate the adsorption unit; and the adsorbent layer comprises molecular sieves selected from the group consisting of 13X, 3A, 4A, SA, CaX, silica gel, calcium Y zeolite, zinc X zeolite, molecular sieve with high ratio of silica to alumina, active alumina, activated carbon, and combinations thereof.
5. The system according to claim 1, wherein the gas stream is an off gas stream from adipic acid production process or nitric acid production process; and prior to entering the wet scrubbing absorption unit, the gas stream contains 28.0 to 70.0% N.sub.2O by volume, 1.0 to 6.0% O.sub.2 by volume, 20.0 to 60.0% N.sub.2 by volume, 0.2 to 1.0% Ar by volume, 2 to 10.0% CO.sub.2 by volume, 0.1 to 1.0% CO by volume, 1.0 ppm to 0.5% NO.sub.2 by volume, 1.0 ppm to 1.0% NO by volume, and 1.0 ppm to 0.1% hydrocarbons by volume.
Description
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
(1) In the accompanying drawings forming a material part of this description, there are shown:
(2)
(3)
(4)
DETAILED DESCRIPTION OF THE INVENTION
(5) This invention is aimed at recovering and purifying nitrous oxide (N.sub.2O) from a N.sub.2O containing gas stream to produce different purification grades of nitrous oxide. The source of the gas stream can be from any process, such as, from an industrial process. A good example of an industrial process is the off gas stream from the production of adipic acid.
(6) The source of the gas stream contains 5.0 to 99.9% nitrous oxide by volume, preferably 20 to 70.0% by volume of nitrous oxide, more preferably 25.0 to 60.0% of nitrous oxide by volume.
(7) The off gas stream from adipic acid production plant, which uses nitric acid as oxidant, usually contains 28.0-55.0% nitrous oxide by volume.
(8) The main impurities in the N.sub.2O enriched stream include but not limited to, N.sub.2, O.sub.2, H.sub.2, Ar, NOx (NO and NO.sub.2), CO, CO.sub.2, moisture, methane, and other trace organic compounds.
(9) The impurities having molecular mass being equal or bigger than N.sub.2O, are hereinafter referred to as heavy impurities. The impurities having molecular mass being less than N.sub.2O, are hereinafter referred to as light impurities. Alternatively, the heavy impurities typically have a boiling points that are equal to or bigger than the boiling point of N.sub.2O. The light impurities have a boiling points that are less than the boiling point of N.sub.2O.
(10) The light impurities include but not limited to N.sub.2, O.sub.2, NO, CO, Ar, H.sub.2. The heavy impurities include but not limited to CO.sub.2, NO.sub.2, H.sub.2O. The organic compounds include but not limited to C.sub.2.sup.+, CH.sub.4 and C.sub.2. Generally, methane and C.sub.2 incorporate into the light impurities, while C.sub.2.sup.+ to heavy impurities.
(11)
(12) The units 2, 3 and 4 in
(13) The units 5 and 6 in
(14) The liquefaction unit 7 in
(15) The non-condensation gas includes but not limited to Ar, N.sub.2, O.sub.2, CO, NO, methane. Thus, the impurities in the stream are removed by releasing them as part of the non-condensation gas.
(16) The distillation unit 9 in
(17) The storage tank unit 10 in
(18) In this system, heavy impurities such as NO.sub.2 and CO.sub.2 are removed by combination of using absorption from caustic and water wet scrubbers in the wet scrubbing absorption unit 2; and adsorption from the adsorption unit 5. NO.sub.2 and CO.sub.2 can be removed by using adsorption unit 5 alone.
(19) The molecular mass of carbon dioxide is almost the same as nitrous oxide (CO.sub.2: 44.01 and N.sub.2O: 44.01). The boiling point difference is only 1.86 C. (N.sub.2O: 38.27 C. and CO.sub.2: 40.13 C.) at 1.0 MPa (1 MPa=10.sup.6 Pa). It is hard and not effective to separate CO.sub.2 from N.sub.2O by distillation. CO.sub.2 concentration level in the final product should be controlled by wet scrubbing and adsorption processes along with the removal of other heavy impurities such as NO.sub.2.
(20) Due to the molecular mass of CO and NO being less than nitrous oxide, the light impurities CO and NO are removed through the combination of the liquefaction unit 7 and the releaser unit 8, after liquefied as part of the non-condensation gases. They can be further controlled to trace level by flash distillation or continuous distillation with reflux companied with removal of methane, argon, oxygen and nitrogen.
(21) Flash distillation is a single-stage continuous operation where a liquid mixture is partially vaporized: the vapor produced and the residual liquid are in equilibrium, which are then separated and removed. The feed is preheated before entering the flash drum. As such, part of the feed may be vaporized. The heated mixture then flows through a pressure-reducing valve to the flash drum, and separation between the vapor and liquid takes place.
(22) Flash distillation is used most for separation components that boil at widely different temperature. It is not effective in separating components of comparable volatility or of trace level, which requires the use of continuous distillation with reflux.
(23) For high concentration of carbon monoxide (CO), catalytic conversion of carbon monoxide to carbon dioxide over catalyst may be applied, in which oxygen existing in the gas stream. Then the product CO.sub.2 is removed by caustic and water wet scrubbers.
(24) For high concentrations of NO and NO.sub.2, ozone could be introduced before wet scrubbing process. Ozone will rapidly oxidize insoluble NO and NO.sub.2 to soluble oxidized compounds such as N.sub.2O.sub.5. Ozone is produced on site and on demand by passing oxygen through an ozone generator.
(25) There might be organic compounds in gas stream, which could be from production plant or from compressor (lubricating oil). In this system, organic compounds C.sub.2.sup.+ (C.sub.2.sup.+ means organic compounds having carbon number over two) can be removed by adsorption in adsorption unit 5 to trace level. Trace CH.sub.4 and C.sub.2 (C.sub.2 means organic compounds having carbon number equal two) can be removed by flash distillation or continuous distillation with reflux in unit 9 along with other light impurities.
(26) Present invention removes most part of heavy impurities including but not limited to CO.sub.2 and NO.sub.2 by wet scrubbing absorption unit 2 and controls heavy impurities to trace level in the products by adsorption unit 5. Most part of Ar, N.sub.2 and O.sub.2 in the N.sub.2O enriched stream can be separated by releaser 8 as non-condensation gases after liquefying. The flash drum or distillation column with reflux is used to further purify and lower the light impurities concentration such as CO, NO, Ar, CH.sub.4, N.sub.2 and O.sub.2 to meet the allowed limited amount the product.
(27) The system offers the flexibility of producing different grades of N.sub.2O, such as industrial grade, medicinal grade, and electronic grade with purity ranging from 90% to 99.999.sup.+% to meet different requirements from different customers.
(28) The process uses the system shown in
(29) The N.sub.2O enriched off gas stream 1 is fed to the wet scrubbing absorption unit 2 to remove most part of NO.sub.2 and CO.sub.2. The wet scrubbing unit comprises of caustic scrubber, an acid scrubbing unit, water scrubber and combinations thereof in series. NO.sub.2 and CO.sub.2 will be controlled to preset values at the outlet of the wet scrubbing unit 2, for example, less than 500 ppm (ppm means 10.sup.6 by volume).
(30) After cleaning water droplets from the gas stream, one or multi-stage compressor unit 3 is used to boost the gas stream to a preset pressure.
(31) Higher pressure is required for the disclosed system. If the pressure of the incoming gas stream is low, the pressure needs to be boosted before the gas stream enters the adsorption unit 5. The compressed pressure of the gas stream is mainly determined by the pressure requirement for the product and the pressure drop across whole production process.
(32) For example, the inlet pressure of the off gas stream from the adipic acid production process is usually about 0.12-0.20 MPa. The pressure needs to be boosted to 2.0 to 5.0 MP, preferably 2.0 to 4.0 MP; more preferably 3.0 MPa to 4.0 MPa before the gas stream enters adsorption unit 5.
(33) The saturation pressure of nitrous oxide N.sub.2O is 1.801 MPa at temperature of 20 C. The operation pressure should be over 3.602 MPa to liquefy N.sub.2O at 20 C., if the inert gas (non-condensation gas such as argon, nitrogen and oxygen) is about 50.0% of the total gas mixture. The pressure drop passing through different operation units should be taken into account too.
(34) The gas stream is mixed with another stream (vapor) coming from the unit 9 at the inlet of the second stage of the compressor unit 3 (for a compressor has at least two stages). The mixed gas stream then passes through the cold and dry unit 4. Unit 4 further decreases the temperature and removes condensed water or mist.
(35) The adsorption unit 5 comprises at least two adsorption beds. The one- or multi-layer beds are packed with different kind of adsorbents, such as activated carbon, active alumina, and 13X molecular sieve. The adsorption unit 5 removes moisture, CO.sub.2 and NO.sub.2 to a requisite level, and removes trace organic compounds which probably come from the off gas stream or compressor lubricant.
(36) The adsorption unit can also be used to remove trace hydrocarbons C.sub.2.sup.+.
(37) In practice, inorganic molecular sieve could be used to replace activated carbon to remove trace organic compounds for safety reason. In addition, two parallel adsorption beds can be alternately used for continuous operation: one is in adsorption, another one is in regeneration. The adsorption process is a critical step to lower the concentrations of CO.sub.2 and NO.sub.2 to the requisite values in the product.
(38) The gas stream from unit 5 is then stored in a buffer tank unit 6.
(39) At preset pressure and temperature, the liquefier in the liquefaction unit 7 will partially liquefy the gas stream from unit 6. The two phase fluid stream containing both gas and liquid from the liquefaction unit 7 is fed to the releaser unit 8.
(40) Unit 8 separates the non-condensation gas, mainly argon, nitrogen and oxygen with trace CO, NO and methane. The non-condensation gas is then sent (or released) back to adsorption unit 5 to regenerate the spent adsorption beds (purging and cooling down). The liquid mixture from the bottom of the releaser unit 8 is fed to distillation unit 9, the flash drum or distillation column with reflux.
(41) The light hydrocarbons methane and C.sub.2, which are difficult to be removed completely by adsorption, can be removed by flash distillation along with other light impurities such as CO and NO in unit 9.
(42) A vapor containing N.sub.2O over 90% by volume and non-condensation gas from unit 9 is sent (or recycled) back to the second stage of the compressor 3. The liquid phase that is the purified liquid N.sub.2O, from the bottom of unit 9 is sent to unit 10 for storage or distribution.
(43) There are some heat exchangers and mixers (not shown in
(44) Purpose of the heat exchange between the liquid mixture out of the releaser unit 8 and the gas stream from adsorption unit 5 are to increase the temperature of the liquid mixture to feed to unit 9 and to lower the temperature for the gas stream for liquefaction. After heat exchange, the gas stream is stored in buffer tank 6 and is liquefied by refrigerator in unit 7. The temperature of the liquid mixture after heat exchange is a critical parameter to determine the light impurities level in the product. How much of light impurities is removed to the vapor (and remained in the liquid) depends on the condition of the feed to unit 9, i.e. how much of the feed is entering as vapor state, which in turn is controlled by the amount of heating. In other words, the degree of vaporization affects the concentration (distribution) of light impurities in vapor phase and liquid phase.
(45) As an example, the procedure to obtain a 99.9% purity nitrous oxide production is describing in detail.
(46) The N.sub.2O enriched off gas stream with pressure 0.15 MPa is fed to the caustic wet scrubber to remove most part of NO.sub.2 and CO.sub.2. The water scrubber is added to clean caustic droplets from the gas stream. The pressure drop across the two wet scrubbings is about 0.05 MPa. As the control parameters, NO2 and CO.sub.2 are to be less than 500.0 ppm after scrubbing process. The pumps are used to feed the caustic solution and water to the upper part of the scrubbers, respectively.
(47) After separation of the caustic droplets, the gas stream is mixed with the vapor (95.6% N.sub.2O by volume with pressure 1.0 MPa and temperature 39.7 C.) from the distillation unit 9 rights before the second stage of the compressor.
(48) Two-stage compressor is adopted to boost the pressure from 0.10 MPa to 1.0 MPa (first stage) and to 3.04 MPa (second stage). The cooling agent is water for cooling down the compressed gas stream from 139.2 C. to 38.0 C.
(49) Cool and dry unit is used to cool down the gas to 10 C. and remove the condensation water.
(50) One heat exchanger is used to further lower the temperature of the gas stream to 1.0 C. through heat exchange between the gas stream and the non-condensation gas from the releaser unit 8 (32.6% N.sub.2O by volume with pressure 1.1 MPa and temperature 66.1 C.). The non-condensation gas after the heat exchange is then used for regeneration of the spent adsorption beds (purge, regeneration, heating, and cooling) in the adsorption unit 5. The gas stream from buffer tank 6 is used to repressurize the spent adsorption bed for next cycle.
(51) The two parallel adsorption beds are multi-layers beds packed with activated carbon, active alumina, 13X molecular sieve for the removal of organic compounds (C.sub.2.sup.+), moisture, carbon dioxide, nitrogen dioxide, respectively. The critical parameters for the gas stream out of the adsorption bed are: the concentration of CO.sub.2 is less than 1.0 ppm and NO.sub.2 is less than 0.5 ppm. The two parallel adsorption beds are in swing operation; one is in adsorption, another one is in regeneration.
(52) The gas stream out of the adsorption bed with 1 C. is fed to another heat exchanger, wherein the gas stream undergoes the heat exchange with the saturated liquid from the bottom of the releaser unit 8 to heat and increase the temperature to a preset value (from 66.4 C. to 39.7 C.) for flash evaporation at the distillation unit 9.
(53) The liquid temperature (or the pressure) is critical to the successful operation of the flash drum. After the last heat exchange, the gas stream with 29.2 C. is stored in the buffer tank 6. The gas stream from the buffer tank 6 is then sent to the liquefaction unit 7 and is liquefied by refrigerator in the liquefaction unit 7.
(54) The two phase fluid stream from the liquefaction unit 7 is fed to the releaser unit 8 to separate and remove the non-condensation gas, mainly nitrogen, argon, and oxygen with trace of CO, NO and organic compounds such as methane. The non-condensation gas is fed to the adsorption unit to cool down the gas stream. The liquid stream from the bottom of the releaser unit 8 with increased temperature is sent to the flash drum. The flash fraction (about 60%) depends on the operation conditions and the restricted concentration for the impurities in the final products. The vapor with trace of non-condensation gas is fed and mixed with the gas stream in the second stage of the compressor. The liquid phase is the product and is sent to liquid tank unit 10.
(55) A person skilled in the art would understand that some detectors should be installed to monitor and test the concentrations, temperature, flow rate and pressure.
EXAMPLES
(56) Based on the database and thermodynamic method, a series of simulations have been done by the commercial software ASPEN Plus.
(57) The off gas stream from an adipic acid production plant, which uses nitric acid as oxidant, usually contains 28.0-55.0% nitrous oxide by volume. Compositions from an off gas stream from a typical adipic acid plant was listed in the Table 1. The similar off gas stream was used in the following simulations.
(58) It should be pointed that the N.sub.2O enriched off gas stream from the said adipic acid plant was mixed with air first to produce dilute HNO.sub.3 by oxidation of NOx and passing through 3 sequential water scrubbers, then the gas stream was sent into the droplet separator to separate the droplet and aerosols.
(59) The analytical result for the off-gas stream shown in Table 1 was from the off gas stream after the droplet separator in the plant with dry base. The NO was the main component in NOx in Table 1.
(60) TABLE-US-00001 TABLE 1 Analytical result for the off-gas stream (dry base) Results (v/v) Results (v/v) Item (Sample 1) (Sample 2) Test Methods N.sub.2O 47.47% 49.45% GC-ECD* N.sub.2 41.90% 40.52% GC-TCD** NOx*** 68 ppm 78 ppm Nitrogen Oxides Analyzer O.sub.2 3.90% 3.50% GC-TCD CO 0.21% 0.23% GC-TCD CO.sub.2 6.51% 6.29% GC-TCD Hydrocarbons <2 ppm <2 ppm GC *GC-ECD: Gas Chromatography- electron capture detector **GC-TCD: Gas Chromatography- thermal conductivity detector ***NO.sub.X: NO, and NO.sub.2
Example 1
Production of 99.9% Purity N2O
(61) In this example, a system comprising wet scrubbing unit, compressor, cool and dry unit, adsorption unit, liquefier, releaser, and flash drum, was used to produce 99.9% N.sub.2O.
(62) The simulation result was shown in Table 2.
(63) The initial fraction of N.sub.2O, in the gas stream was 47.42%, raised to 49.10% after wet scrubbing, to 54.66% after adsorption, to 98.81% in liquid phase in the releaser unit, and to 99.92% after the flash drum. The 99.92% N.sub.2O liquid was stored as the product. The N.sub.2O recovery ratio was 53.53%, where the recovery ratio was defined as the N.sub.2O mass fraction in the product to that in the off gas.
(64) For CO.sub.2, the initial fraction was 6.50%, reduced to 0.27% by wet scrubbing, then further reduced to 0.51 ppm by adsorption. After flash, the final fraction in the product was 0.94 ppm.
(65) For CO, the initial fraction was 0.21%. CO was difficult to be removed effectively by wet scrubbing and adsorption. Very small amount of CO could dissolve in water. CO can be removed by adsorption, however it was not economic compared to flash distillation. CO was released as non-condensation gas in releaser and reduced to 45.6 ppm, and further reduced to 2.46 ppm after flash in the product.
(66) For NO, the initial fraction was 50.0 ppm. NO was difficult to be reduced by wet scrubbing and adsorption. Very small amount of NO could dissolve in water. NO was released as non-condensation gas in the releaser and reduced to 6.0 ppm, and reduced to 0.944 ppm after flash in the product.
(67) TABLE-US-00002 TABLE 2 Production of 99.9% N.sub.2O From Feeding Wet Adsorption Liquefier Releaser Releaser Flash Flash Scrubbing To Wet Compressor Liquefier Releaser Adsorption Flash 2nd Stage Storage Scrubbing compressor Temperature 20.0 25.3 1.0 49.0 66.3 39.7 39.7 39.7 ( C.) Pressure 0.15315 0.101325 3.041325 3.001325 1.101325 1.001325 1.001325 1.001325 (MPa) Mass Flow 164.2169 153.7882 168.4743 168.4743 101.3516 67.1206 17.25173 49.86887 (kg/hr) Component Fraction by Volume O.sub.2 0.038963 0.040383 0.038783 0.038783 0.057258 2.20E03 7.76E03 2.42E04 N.sub.2 0.418598 0.433863 0.412509 0.412509 0.615926 9.67E03 0.035672 5.42E04 N.sub.2O 0.474245 0.490901 0.546589 0.546589 0.323656 0.988075 0.956375 0.999209 H.sub.2O 9.99E04 0.032358 6.85E07 6.85E07 6.76E10 2.04E06 1.19E08 2.75E06 CO 2.10E03 2.17E03 2.07E03 2.07E03 3.09E03 4.56E05 1.68E04 2.46E06 CO.sub.2 0.065038 2.68E04 5.07E07 5.07E07 3.05E07 9.06E07 9.15E07 9.04E07 NO 5.00E05 5.18E05 5.06E05 5.06E05 7.32E05 5.98E06 2.03E05 9.44E07 NO.sub.2 9.99E06 3.09E08 2.85E08 2.85E08 8.59E11 8.47E08 1.59E09 1.14E07
(68) For H.sub.2O, the initial fraction was 999.0 ppm; no matter how much water it contains, H.sub.2O in the gas stream will become nearly saturation after scrubbing. After cool and dry unit, the fraction of water will be reduced, and water was further reduced to 0.685 ppm by adsorption, the fraction of water in the product was about 2.75 ppm.
(69) For O.sub.2, the initial fraction was 3.90%. O.sub.2 was difficult to be reduced by wet scrubbing and adsorption (very small amount of O.sub.2 could dissolve in water), O.sub.2 was released as non-condensation gas in the releaser and reduced to 0.22%, and further reduced to 240 ppm after flash in the product.
(70) For N.sub.2, the initial fraction was 41.86%. N.sub.2 was difficult to be reduced by wet scrubbing and adsorption (very small amount of N.sub.2 could dissolve in water), N.sub.2 was released as non-condensation gas in the releaser and reduced to 0.97%, and further reduced to 542.0 ppm after flash in the product.
(71) In the whole process, critical parameters for successful operation includes the compressor discharge pressure, the CO.sub.2 and H.sub.2O concentrations after adsorption, the temperature and pressure in liquefier, the inlet temperature and pressure in the flash drum.
Example 2
Production of 99.999% Purity N2O
(72) In this example, a system comprising a wet scrubbing unit, compressor, cool and dry unit, adsorption unit, liquefier and releaser, and a distillation column with reflux, was used to produce 99.999% N.sub.2O. The column has 10 theoretical trays and was operating with reflux ratio 2 (reflux ratio was the ratio of the reflux to the overhead product). The final result was listed in Table 3.
(73) For N.sub.2O, the initial fraction was 47.42%, after wet scrubbing, was raised to 49.10%, then to 56.52% after adsorption, to 98.81% after releaser unit, and to 99.9993% after distillation, and was stored as the product. The N.sub.2O recovery ratio was 52.82%.
(74) For CO.sub.2, the initial fraction was 6.50% and was reduced to 0.27% by wet scrubbing, then further reduced to 0.485 ppm by adsorption. The final fraction in product was 0.781 ppm.
(75) For CO, the initial fraction was 0.21%. CO was released as non-condensation gas in the releaser and reduced to 45.3 ppm, and further reduced to nearly zero ppm in the product.
(76) For NO, the initial fraction was 50.0 ppm. NO was released as non-condensation gas in the releaser and reduced to 6 ppm, and becomes nearly zero ppm in the product.
(77) TABLE-US-00003 TABLE 3 Production of 99.999% N.sub.2O From Feeding Wet Adsorption Liquefier Releaser Releaser Distillation Distillation Scrubbing Column Column To Wet Compressor Liquefier Releaser Adsorption Column 2nd Stage Storage Scrubbing compressor Temperature 20.0 25.3 1.0 49.0 66.1 39.4 40.0 38.7 ( C.) Pressure 0.15315 0.101325 3.041325 3.001325 1.101325 1.001325 0.98 0.97 (MPa) Mass Flow 164.4003 153.7882 177.3239 177.3239 102.0083 75.31555 26.09674 49.21882 (kg/hr) Component Fraction by Volume O.sub.2 0.038963 0.040382 0.037277 0.037277 0.05706 2.19E03 6.26E03 8.06E16 N.sub.2 0.418598 0.433868 0.395508 0.395508 0.613058 9.62E03 0.02756 2.90E18 N.sub.2O 0.474245 0.490898 0.565183 0.565183 0.326736 0.988135 0.966034 0.999993 H.sub.2O 9.99E04 0.032357 1.46E06 1.46E06 1.37E09 4.05E06 1.03E23 6.23E06 CO 2.10E03 2.17E03 1.98E03 1.98E03 3.07E03 4.53E05 1.30E04 9.30E21 CO.sub.2 0.065038 2.68E04 4.85E07 4.85E07 2.85E07 8.40E07 9.51E07 7.81E07 NO 5.00E05 5.18E05 4.89E05 4.89E05 7.32E05 5.95E06 1.70E05 1.03E16 NO.sub.2 9.99E06 3.09E08 2.79E08 2.79E08 8.03E11 7.72E08 2.40E21 1.19E07
(78) For H.sub.2O, the initial fraction was 1000 ppm. After cool and dry unit, it will be reduced, and further to 1.46 ppm after adsorption, the water fraction in the product was about 6.23 ppm.
(79) For O.sub.2, the initial fraction was 3.9%. O.sub.2 was released as non-condensation gas in the releaser and reduced to 0.22%, and further reduced to about zero ppm after distillation.
(80) For N.sub.2, the initial fraction was 41.86%. N.sub.2 was released as non-condensation gas in the releaser and reduced to 0.96%, and further reduced to about zero ppm after distillation.
(81) In the whole process, critical parameters for successful operation includes the compressor discharge pressure, the outlet concentration of CO.sub.2 and H.sub.2O after adsorption, the outlet temperature out of liquefier, the pressure in releaser unit, the theoretical tray number of distillation column and the reflux ratio, column operation pressure, and inlet feed temperature to the distillation column.
Example 3
Production of 99.9% Purity N2O without Wet Scrubbing
(82) In this example, a system comprises a compressor, cool and dry unit, adsorption unit, liquefier and releaser, and flash drum, was used to produce 99.9% N.sub.2O without wet scrubbing process. This was a simplified process which can produce qualified product.
(83) The result was listed in Table 4.
(84) TABLE-US-00004 TABLE 4 Production of 99.9% N.sub.2O without Wet Scrubbing From Feeding Adsorption Liquefier Releaser Releaser Flash Flash To Compressor Liquefier Releaser Adsorption Flash 2nd Stage Storage compressor Temperature 20.0 1.0 49.0 66.3 39.6 39.6 39.6 ( C.) Pressure 0.15315 3.041325 3.001325 1.101325 1.001325 1.001325 1.001325 (MPa) Mass Flow 164.2169 169.5656 169.5656 101.4353 68.13675 18.19446 49.94228 (kg/hr) Component Fraction by Volume O.sub.2 0.038963 0.038587 0.038587 0.057228 2.20E03 7.50E03 2.34E04 N.sub.2 0.418598 0.410342 0.410342 0.615577 9.67E03 0.034403 5.23E04 N.sub.2O 0.474245 0.548891 0.548891 0.323999 0.987945 0.957799 0.999088 H.sub.2O 9.99E04 9.72E08 9.72E08 9.53E11 2.87E07 1.70E09 3.92E07 CO 2.10E03 2.06E03 2.06E03 3.09E03 4.55E05 1.62E04 2.37E06 CO.sub.2 0.065038 6.33E05 6.33E05 3.79E05 1.13E04 1.14E04 1.12E04 NO 5.00E05 5.04E05 5.04E05 7.31E05 5.97E06 1.97E05 9.14E07 NO.sub.2 9.99E06 9.77E06 9.77E06 2.93E08 2.88E05 5.51E07 3.92E05
(85) For N.sub.2O, the initial fraction was 47.42%. N.sub.2O was raised to 54.89% after adsorption, to 98.80% after the releaser unit, to 99.91% after the flash drum. The N.sub.2O recovery ratio was 53.53%.
(86) For CO.sub.2, the initial fraction was 6.50% and was reduced to 63.3 ppm by adsorption. After flash, the final fraction in product was 112.0 ppm. The length of adsorption column should be longer to handle the removing of CO.sub.2 without scrubbing unit.
(87) For CO, the initial fraction was 0.21%, CO may be removed by adsorption; flash process was adopted in this process. CO was released as non-condensation gas in the releaser and reduced to 45.5 ppm, and further reduced to 2.37 ppm in the product.
(88) For NO, the initial fraction was 50.0 ppm. NO was released as non-condensation gas in the releaser and reduced to 6.0 ppm, and to be 0.91 ppm in the product.
(89) For H.sub.2O, the initial fraction was 1000 ppm. After cool and dry unit, the fraction will be reduced, and to be 0.097 ppm after adsorption. The water fraction in the product was about 0.39 ppm.
(90) For O.sub.2, the initial fraction was 3.9%. O.sub.2 may be removed by adsorption; flash process was adopted in this process. O.sub.2 was released as non-condensation gas in the releaser and reduced to 0.22%, and further reduced to about 234 ppm in the flash drum.
(91) For N.sub.2, the initial fraction was 41.86%. N.sub.2 could be removed by adsorption; flash was adopted in this process. N.sub.2 was released as non-condensation gas in the releaser and reduced to 0.97%, and further reduced to 523.0 ppm in the flash drum.
(92) In the whole process, critical parameters for successful operation includes the compressor discharge pressure, the outlet concentration of CO.sub.2 and H.sub.2O from adsorption, the outlet temperature out of the liquefier, the releaser pressure, the operation pressure and the feed temperature to the flash drum.
Example 4
Distillation to Remove CO2
(93) In this example, a phase analysis for CO.sub.2 and N.sub.2O was carried out. The result of T-x-y diagram under 1.0 MPa was shown in
(94) Even under 2.5 MPa, the boiling point difference was 3.5 C. It was still hard to separate CO.sub.2 from N.sub.2O using distillation, as shown in
(95) For other heavy components, such as NO.sub.2, similar conclusion could be derived.
(96) Thus, distillation was not effective to remove CO.sub.2 from N.sub.2O.
(97) 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.