CN109476483A - From the method for admixture of gas recycling and nitrous oxide purification containing nitrous oxide - Google Patents
From the method for admixture of gas recycling and nitrous oxide purification containing nitrous oxide Download PDFInfo
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- CN109476483A CN109476483A CN201780044589.7A CN201780044589A CN109476483A CN 109476483 A CN109476483 A CN 109476483A CN 201780044589 A CN201780044589 A CN 201780044589A CN 109476483 A CN109476483 A CN 109476483A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
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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
- B01D53/02—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
- 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
- B01D53/22—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 diffusion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/22—Nitrous oxide (N2O)
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- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/30—Improvements relating to adipic acid or caprolactam production
-
- Y—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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The present invention relates to from the nitrous oxide (N for example by being pyrolyzed ammonium nitrate2O the method for the admixture of gas recycling and nitrous oxide purification that) are generated in the industrial process of production process, adipic acid production process, nitric acid production process and caprolactam production process etc..
Description
Technical field
The present invention relates to from for example passing through the nitrous oxide (N of the pyrolysis of ammonium nitrate2O) production process, adipic acid are raw
Generated in the industrial process of production process, nitric acid production process and caprolactam production process etc. admixture of gas recycling and it is pure
Change the method for nitrous oxide.Particularly, the present invention relates to the lifes from nitrous oxide, adipic acid, nitric acid and caprolactam etc.
The method that the exhaust gas generated during producing recycles nitrous oxide with high-purity and in high yield.
Background technique
Recently, to nitrous oxide (N in the microelectronic technique of semiconductor, LCD and OLED2O demand) dramatically increases.
Nitrous oxide is used to pass through the process with silane reaction formation silicon oxide layer by chemical method or plasma deposition.One
Nitrous oxide is also used to nitrogenize thin silicon films.
Nitrous oxide is industrially produced by the pyrolysis of ammonium nitrate.At this time, it may be necessary to purify by from thermal decomposition product
The nitrous oxide of high-purity is obtained except impurity such as denitrifications.Nitrous oxide is contained in from such as adipic acid production process, nitre
In the exhaust gas that the process of sour production process and caprolactam production process etc. generates.It needs by from the gas containing nitrous oxide
Body mixture recycles nitrous oxide industrially to recycle nitrous oxide.
Nitrous oxide is one of representative greenhouse gases, global warming potential (global warming
Potential, GWP) it is 310 times higher than carbon dioxide.Therefore, by recycling nitrous oxide, can not only subtract
Few greenhouse gas emission, and economic benefit can be obtained.Therefore, it is necessary to establish recycling/purification process of nitrous oxide from
And the admixture of gas containing nitrous oxide that is generated from the pyrolysis by ammonium nitrate and from adipic acid, nitric acid and caprolactam
Production process discharge the exhaust gas containing nitrous oxide with high efficiency obtain nitrous oxide.
However, can be used for the height of semiconductor, LCD and OLED industry from the waste gas recovery containing nitrous oxide and purifying
The method of purity nitrous oxide is not yet widely used in industry.So far the recycling for the high-purity nitrous oxide reported in patent
It is as follows with the technology and methods of purifying.
U.S. Patent number US 6,348,083 is described from production adipic acid, nitric acid, glyoxalic acid, nitrous oxide or phenol
Industrial process in the method and apparatus of waste gas recovery and/or nitrous oxide purification that generate.In that patent, exhaust gas contains
Concentration is the nitrous oxide of 5 volume of volume %~99.9 % of gas and selected from being made of nitrogen, oxygen and carbon monoxide
Group at least one gaseous impurity.Exhaust gas passes through one or more osmosis modules (permeation module) (UF membrane moulds
Part), thus gas of the recycling containing the nitrous oxide that concentration is 85 volume of volume %~90 %.However, in addition in the patent
Other than the impurity provided, the exhaust gas containing nitrous oxide generated in adipic acid production process contains carbon dioxide, dioxy
Change nitrogen, nitric oxide, organic hydrocarbon and vapor.Therefore, using separation (UF membrane) skill of the osmosis modules proposed in the patent
Art is not enough to effectively remove such impurity, shows to recycle to be used only for the high-purity nitrous oxide of semiconductor with high yield to be somebody's turn to do
Method is unsuccessful.In addition, the separation membrane material and UF membrane work of the permeable membrane module for the patent is not expressly described
Sequence.
U.S. Patent Publication No. US 2014/0366576 describes a kind of method comprising for aoxidizing two from containing one
Nitrogen, impurity, the wet scrubbing of the exhaust gas purification nitrous oxide of moisture and organic hydrocarbon, absorption, liquefaction, flash distillation or reflux continuous steaming
It evaporates.Here, remove carbon dioxide and nitrogen dioxide by wet scrubbing, by be adsorbed and removed trace impurity such as carbon dioxide,
Nitrogen dioxide, vapor and organic hydrocarbon.Then, liquefied gas.Separation is 30 bodies comprising concentration in escaper (emitter)
The admixture of gas containing nitrous oxide of the nitrous oxide of product % and include concentration is about 98 volume % a oxidation two
The liquid mixture containing nitrous oxide of nitrogen.An oxidation will be contained comprising nitrous oxide that concentration is about 98 volume %
Distillation equipment is added to obtain the high-purity nitrous oxide of at least 99.999 volume % purity in the liquid mixture of phenodiazine.So
And in above-mentioned patent, concentration, which is not used, will send to the device of the admixture of gas containing nitrous oxide of escaper.Cause
This, the admixture of gas containing nitrous oxide comprising the nitrous oxide that concentration is 30 volume % is before through distillation equipment
It is emitted into air from escaper.Therefore, as shown in the embodiment of above-mentioned patent, the rate of recovery of nitrous oxide down to supply extremely
About the 50% of total nitrous oxide content contained in the adipic acid exhaust gas of purification procedures.
The present inventor studied in detail the shortcomings that overcoming the problems, such as the conventional method that existing patent proposes and.As a result, this
Inventor removes impurity by the way that UF membrane process to be introduced into absorption process and is introduced into distillation process to recycle high-purity
Nitrous oxide successfully overcomes the above problem, and the UF membrane process can be by from useless containing low concentration nitrous oxide
Gas removes nitrogen or/and oxygen to cause to complete the present invention with high concentration concentrating dinitrogen monoxide.
The present invention relates to from admixture of gas, i.e., in the production process of nitrous oxide, adipic acid, nitric acid and caprolactam
The exhaust gas of generation is aoxidized with the high-purity (at least 99.999 volume %) one that (at least 90%) recycling can be used for semiconductor in high yield
The method of phenodiazine.By the method for the recycling high-purity nitrous oxide that the present inventor proposes in the present invention, not with first patent
Together, be the UF membrane process of nitrous oxide is optionally sequestered from nitrogen and/or oxygen using seperation film, and include concentration
Up to 80 volume of volume %~95 % and by distillation purifying to purify at least nitrous oxide of 99.999 volume % the step of,
Show that this is the method with (at least 90%) in high yield.It is difficult to separate by UF membrane and distillation the invention also includes removing
Impurity absorption process.That is, proposing in the present invention includes following in the method for recycling high-purity nitrous oxide in high yield
Step: 1) by from the exhaust gas of nitrous oxide containing low concentration remove nitrogen and/or oxygen one oxygen is concentrated with high concentration
The UF membrane process of change phenodiazine, 2) remove the absorption process of a small amount of impurity contained in exhaust gas and 3) from above-mentioned containing having passed through
The admixture of gas separating high-purity nitrous oxide of UF membrane process and the nitrous oxide of absorption process concentration and purifying
Distillation process.
Summary of the invention
The object of the present invention is to provide from admixture of gas, the i.e. life of nitrous oxide, adipic acid, nitric acid and caprolactam
Produce during generate exhaust gas in high yield (at least 90%) recycling can be used for semiconductor, LCD and OLED production process it is high-purity
Spend the method for (at least 99.999 volume %) nitrous oxide.
To achieve the goals above, the present invention provides recycling and the purification process of nitrous oxide, and it includes following steps:
Pretreatment process selects free gas by admixture of gas of the supply containing nitrous oxide or exhaust gas to remove
At least one of the impurity of group of fine water droplets, fine droplets contained in mixture and subparticle impurity composition；
UF membrane process, by remove complete nitrogen contained in the admixture of gas of above-mentioned pretreatment process and/or
Oxygen carrys out concentrating dinitrogen monoxide；
Absorption process is selected from two as contained in the admixture of gas for completing above-mentioned UF membrane process by being adsorbed and removed
At least one of carbonoxide, nitrogen dioxide, vapor and impurity of group of organic hydrocarbon composition；With
Distillation process passes through a series of of compression, cooling and the distillation for completing the admixture of gas of above-mentioned absorption process
Step recycles nitrous oxide.
The present invention also provides the recycling of nitrous oxide and purification process comprising following steps:
Pretreatment process selects free gas by admixture of gas of the supply containing nitrous oxide or exhaust gas to remove
At least one of the impurity of group of fine water droplets, fine droplets contained in mixture and subparticle impurity composition；
Absorption process is selected from two as contained in the admixture of gas for completing above-mentioned pretreatment process by being adsorbed and removed
At least one of carbonoxide, nitrogen dioxide, vapor and impurity of group of organic hydrocarbon composition；
UF membrane process completes nitrogen and/or oxygen contained in the admixture of gas of above-mentioned absorption process by removing
Gas carrys out concentrating dinitrogen monoxide；With
Distillation process, compression, cooling and the distillation of the admixture of gas by completing above-mentioned UF membrane process it is a series of
Step recycles nitrous oxide.
The effect of invention
The recycling of nitrous oxide of the invention and purification process are conducive to by from nitrous oxide, adipic acid, nitric acid
310 times higher than carbon dioxide of global warming potential (GWP) is shown with the waste gas recovery generated in the production process of caprolactam
Nitrous oxide effectively reduce greenhouse gases.The method of recycling and nitrous oxide purification of the invention also promotes with high-purity
Degree (at least 99.999 volume %) and in high yield (at least 90%) recycling and purifying can be used for semiconductor, LCD and OLED and produced
The nitrous oxide of journey.
Detailed description of the invention
The application of the preferred embodiments of the invention is best understood with reference to attached drawing, in which:
Fig. 1 and Fig. 2 is the schematic diagram for showing the example of method of nitrous oxide purification according to the present invention.
Fig. 3 is shown in the method for nitrous oxide purification according to the present invention including triple membrane separation devices
The schematic diagram of the example of the UF membrane process of (triple membrane separation device).
Specific embodiment
Hereinafter, the present invention is described in detail.
The present invention provides recycling and the purification process of nitrous oxide comprising following steps:
Pretreatment process selects free gas by admixture of gas of the supply containing nitrous oxide or exhaust gas to remove
At least one of the impurity of group of fine water droplets, fine droplets contained in mixture and subparticle impurity composition；
Absorption process is selected from two as contained in the admixture of gas for completing above-mentioned pretreatment process by being adsorbed and removed
At least one of carbonoxide, nitrogen dioxide, vapor and impurity of group of organic hydrocarbon composition；
UF membrane process completes nitrogen and/or oxygen contained in the admixture of gas of above-mentioned absorption process by removing
Gas carrys out concentrating dinitrogen monoxide；With
Distillation process, compression, cooling and the distillation of the admixture of gas by completing above-mentioned UF membrane process it is a series of
Step recycles nitrous oxide.
The recycling of nitrous oxide of the invention and purification process include the pretreatment process of following sequences, UF membrane work
Sequence, absorption process and distillation process, or the pretreatment process including another sequence, absorption process, UF membrane process and distillation
Process.
At this point, the recycling of nitrous oxide of the invention and the example of purification process are shown in the schematic diagram of Fig. 1 and Fig. 2.
Hereinafter, with reference to the recycling and purifying of the schematic diagram of Fig. 1 and Fig. 2 nitrous oxide that the present invention will be described in more detail
Method.
U.S. Patent number US 6,348,083, first patent are described from production adipic acid, nitric acid, glyoxalic acid, one
The membrane separation technique of the waste gas recovery generated in the industrial process of nitrous oxide or phenol at least nitrous oxide of 90 volume %.
However, the membrane separation technique can not recycle the sufficiently pure high-purity nitrous oxide with for semiconductor, this is because only making
It is difficult to remove various impurity contained in exhaust gas with the technology.
U.S. Patent Publication No. US 2014/0366576 describes a kind of method comprising for aoxidizing two from containing one
Nitrogen, impurity, the wet scrubbing of the exhaust gas purification nitrous oxide of moisture and organic hydrocarbon, absorption, liquefaction, flash distillation or reflux continuous steaming
It evaporates.However, the above method is not used for that will be contained with high concentration admixture of gas of the concentration containing nitrous oxide to pass through
Having concentration is at most that the admixture of gas of the nitrous oxide of 30 volume of volume %~60 % is supplied to escaper and distilling apparatus
To recycle any individual device of at least nitrous oxide of 99.999 volume %.Therefore, contain concentration from escaper discharge
It is the admixture of gas of the nitrous oxide of about 30 volume %, shows the rate of recovery of nitrous oxide down to about 50%.
It is different from the prior art that these patents propose, this hair comprising UF membrane process, absorption process and distillation process
The recycling of bright nitrous oxide and purification process promote from the gas for containing low-purity nitrous oxide (at most 60 volume %)
The mixture recycling at least high-purity nitrous oxide of 99.999 volume %, and its rate of recovery is also satisfactorily up at least
90%.
Firstly, in the method (100) of recycling of the invention and nitrous oxide purification, pretreatment process (10) be in order to
It is removed by admixture of gas of the supply containing nitrous oxide or exhaust gas and is selected from the fine water as contained in admixture of gas
At least one of drop, fine droplets and impurity of group of subparticle impurity composition.
The mixture containing nitrous oxide gas or exhaust gas supplied in pretreatment process (10) is preferably such as one
In the industrial process of nitrous oxide production process, adipic acid production process, nitric acid production process and caprolactam production process etc.
The gas of generation.
The oxidation that the above-mentioned admixture of gas containing nitrous oxide or exhaust gas are 0.3~60 volume % containing concentration
Phenodiazine, concentration are the nitrogen of 5~60 volume %, concentration is the oxygen of 0~40 volume %, the titanium dioxide that concentration is 0~5 volume %
Carbon, concentration are the carbon monoxide of 0~1 volume %, concentration is the nitrogen dioxide of 0~2 volume %, concentration is 0~2 volume % one
Nitrogen oxide, concentration is the vapor of 0~1 volume %, the organic hydrocarbon that concentration is 0~1 volume % or a small amount of fine water droplets, micro-
Thin oil droplet and subparticle impurity.Admixture of gas or exhaust gas containing nitrous oxide can be by using such as being commonly used for work
Feeder (11) supply of the booster (booster) of industry or compressor etc..
Above-mentioned pretreatment process (10) be in order to remove for example on a small quantity be included in nitrous oxide, adipic acid, nitric acid and
The fine water droplets in the above-mentioned gas mixture containing nitrous oxide that are generated in the production process of caprolactam, fine droplets
With the impurity of subparticle impurity etc..Nitrous oxide, adipic acid, nitric acid and caprolactam production process in the gas that generates
Mixture contains a small amount of fine water droplets, fine droplets and subparticle impurity.
In order to remove above-mentioned fine water droplets or fine droplets, use the first flocculator (12).First flocculator (12) is logical
It crosses and collects the device that fine droplets form big drop, 200~300 mesh stainless (steel) wires can be equipped with, commonly used in the industry
Device can be used as flocculator, but always not be limited to this.Subparticle impurity can be by using the filter device (13) for being equipped with filter cloth
It removes.At this point, filter cloth can be the form of bag hose or box (cartridge).Above-mentioned filter cloth or filter device are not particularly limited, and
And any conventional filter cloth or filter device instead can be used herein.
Between temperature range of the above-mentioned pretreatment process (10) preferably between 10 DEG C and 40 DEG C, 1 bar (bar) and 2 bars
It is carried out under pressure limit, but pretreated carry out condition is without being limited thereto.
Next, in the method (100) of recycling of the invention and nitrous oxide purification, above-mentioned UF membrane process (20)
Be in order to by using the seperation film of the separating property with excellent nitrous oxide from completing above-mentioned pretreatment process (10)
Admixture of gas contained in nitrogen and/or oxygen is optionally sequestered and concentrating dinitrogen monoxide.Or this method be for
Nitrogen and/or oxygen contained in the admixture of gas for completing pretreatment process (10) and absorption process (30) are selectively
Separation and concentrating dinitrogen monoxide.
Above-mentioned UF membrane process (20) is in order to by nitrous oxide and the admixture of gas containing nitrous oxide or useless
Nitrogen and/or oxygen contained in gas are optionally sequestered, and separated nitrous oxide is then concentrated.Contain to be concentrated one
The admixture of gas of nitrous oxide includes the nitrous oxide that concentration is 0.3~60 volume %.Admixture of gas also contains concentration
Nitrogen and concentration for 5~60 volume % are the oxygen of 0~40 volume % as major impurity.In UF membrane process (20),
It is preferred that from nitrogen and/or oxygen separation nitrous oxide and with the concentration of the concentration of 80~95 volume %.At this point, with based on film point
The rate of recovery from the nitrous oxide of the percentage of contained nitrous oxide in the admixture of gas supplied in process (20) increases,
The loss of nitrous oxide is reduced.For point with high-recovery and high concentration concentrating dinitrogen monoxide, for UF membrane process
There must be high osmosis of the nitrous oxide relative to the high separation and nitrogen dioxide of nitrogen and oxygen from film.
Particularly, nitrous oxide/nitrogen and the nitrous oxide/oxygen choosing of the seperation film of UF membrane process (20) are used for
Selecting property (selectivity) is preferably at least 20, more preferably at least 30, most preferably at least 40.Above-mentioned separation permeability of the membrane is excellent
It is selected as at least 80GPU, more preferably at least 100GPU, most preferably at least 120GPU.Seperation film is preferably conventional polymer separation
Film, further preferably polysulfones based polymer resin, polyimides based polymer resin, or combinations thereof resin as gas separate
The polymer separation film of the main component of layer.As described in number of patent application 10-2016-0082598, by industrially as gas point
Nitrous oxide/nitrogen of the separation membrane module of polysulfones based polymer resin and polyimides based polymer the resin composition of absciss layer
30~50 are selectively turned out to be with nitrous oxide/oxygen, and its permeability is preferably at least 100 to 150GPU.
Pressure between temperature range of the above-mentioned UF membrane process (20) preferably between 10 DEG C and 100 DEG C, 2 bars and 15 bars
It is carried out under range.The first compressor (21) can be used and the first cooler (22) adjusts temperature and pressure.In UF membrane process
(20) in, the admixture of gas being discharged from pretreatment process (10), and can be by by the by the first compressor (21) compression
One cooler (22) removes the temperature that the heat of compression carrys out steadily regulating gas mixture.
In UF membrane process (20), one or more seperation films are connected in serial or parallel with each other, wherein containing first
The admixture of gas of the nitrous oxide of the osmosizing portion concentration of film carries out subsequent absorption process or distillation process, and remainder
(remaining part) is connected to other second or third seperation film.That is, can be used have by another compressor or
Do not have to be recycled to the connection structure of the rear end of the front end of the first compressor or the first compressor in the case where another compressor
Multistage membrane separation device carries out the process.For example, will be discharged when carrying out UF membrane process (20) using second level membrane separation device
The admixture of gas containing nitrous oxide to the remainder of first order membrane separation device (or first membrane separation device, 24) supplies
To second level membrane separation device (or second membrane separation device, 25), again by osmosizing portion to concentrating dinitrogen monoxide.
At this point, the admixture of gas containing nitrous oxide for the concentration being discharged from the osmosizing portion of second level membrane separation device (25) is the
Compression, is then recycled to first order membrane separation device (24) in two compressors (21).From second level membrane separation device (25)
The admixture of gas of remainder discharge can decompose contained therein one by being commonly used in industrial pyrolysis or catalytic decomposition
Atmosphere is emitted into after nitrous oxide.An oxidation two will be contained from the concentration of the osmosizing portion of first order membrane separation device (24) discharge
The admixture of gas of nitrogen is supplied to next absorption process or distillation process.
For example, as shown in figure 3, being expelled to first order UF membrane dress when carrying out UF membrane process using three-level seperation film
The admixture of gas containing nitrous oxide for setting the remainder of (24) is supplied to second level membrane separation device (25), and then again
It is secondary by osmosizing portion to concentrating dinitrogen monoxide.At this point, the concentration being discharged from the osmosizing portion of second level membrane separation device (25)
The admixture of gas containing nitrous oxide be recycled to first order membrane separation device (24).
From the osmosizing portion of first order membrane separation device (24) be discharged the admixture of gas containing nitrous oxide supply to
The three-level membrane separation device (26) being connect with the 4th other compressor (27) and third cooler (28).It is supplied in admixture of gas
To after three-level membrane separation device (26) by the admixture of gas containing nitrous oxide remaining in remainder supply again to
The front end of first compressor (21).The concentration being discharged from the osmosizing portion of first order membrane separation device (24) contains nitrous oxide
Admixture of gas by other compressor (27), be then gathered in the osmosizing portion of three-level membrane separation device (26), gas exists
Wherein it is concentrated.Then, gas is supplied to next absorption process or distillation process.Remainder from second level membrane separation device (25)
The admixture of gas of the nitrous oxide containing low concentration of discharge by pyrolysis or can be urged in wherein contained nitrous oxide
Change and decomposes to be emitted into atmosphere after decomposing.
In above-mentioned UF membrane process (20), supply lateral pressure is preferably 2 bars~15 bars, more preferable 5 bars~10 bars.Infiltration
Lateral pressure is preferably vacuum to 3 bars, and more preferable 1 bar~2 bars.Infiltration temperature is preferably 10 DEG C~100 DEG C, and more preferable 25 DEG C~50
℃。
As shown in Figure 1, the amount of the impurity such as carbon dioxide, nitrogen dioxide, carbon monoxide, moisture and organic hydrocarbon is few,
But it can be removed to remaining side (residual side) part in UF membrane process (20).From the first membrane separation device (24)
Admixture of gas, a small amount of nitrogen containing the nitrous oxide that concentration is 80 volume of volume %~95 % of per-meate side discharge
And/or oxygen and a small amount of other impurities such as carbon dioxide, nitrogen dioxide, moisture and organic hydrocarbon can be supplied to absorption process
(30).As shown in Fig. 2, when removing such as carbon dioxide, nitrogen dioxide, water from admixture of gas in above-mentioned absorption process (30)
Divide and when concentrated gas mixture, is purified in UF membrane process (20) in UF membrane process (20) after the impurity of organic hydrocarbon etc.
Can be supplied to containing the admixture of gas of nitrous oxide that concentration is 80 volume of volume %~95 % to distillation process (40).
Next, in the recycling of nitrous oxide and purification process (100), absorption process (30) be in order to by using
Be adsorbed and removed selected from the carbon dioxide as contained in the admixture of gas of completion UF membrane process (20), nitrogen dioxide, moisture and
At least one of the impurity of group of organic hydrocarbon composition, or in order to by using being adsorbed and removed selected from by completing to pre-process work
In the impurity of the group of carbon dioxide contained in the admixture of gas of sequence (10), nitrogen dioxide, moisture and organic hydrocarbon composition extremely
Few one kind.
Absorption process (30) be in order to from the admixture of gas containing nitrous oxide or exhaust gas remove such as carbon dioxide,
The impurity of nitrogen dioxide, moisture and organic hydrocarbon etc..Such impurity cannot remove in UF membrane process (20) or distillation process (40)
It goes.The admixture of gas or exhaust gas being discharged from the production process of nitrous oxide, adipic acid, nitric acid and caprolactam contain concentration
It is 0 volume % for nitrogen dioxide that the carbon dioxide of 0 volume of volume %~5 %, concentration are 0 volume of volume %~2 %, concentration
The vapor and concentration of~1 volume % is the organic hydrocarbon of 0 volume of volume %~1 %.In the absorption process of this paper, pass through suction
It is attached to remove such impurity, so that the concentration of nitrogen dioxide, carbon dioxide and vapor respectively adjusts at most 1.0ppm, and have
The concentration of machine hydrocarbon preferably adjusts at most 0.1ppm.
In absorption process (30), carbon dioxide and nitrogen dioxide can be filled with adsorbent for example commonly used in industry
Sodium hydroxide (NaOH), calcium hydroxide (Ca (OH)2) or potassium hydroxide (KOH) adsorption tower or wherein sodium hydroxide
(NaOH), calcium hydroxide (Ca (OH)2) or potassium hydroxide be coated in silica or zeolite (for example,) on suction
It is removed in attached dose by gas-solid reaction.At this point, vapor generates during reaction.Gas-solid reaction filler can be moved back in consumption
It removes and fresh adsorbent is used to fill.In above-mentioned absorption process (30), adsorbed by the neutralization of carbon dioxide or nitrogen dioxide
React generate vapor and organic hydrocarbon can by using commonly used in industry, be mounted with silica or zeolite (X, Y,
CaY, ZnX, 5A, 13X etc.) or alumina silicate or active carbon adsorbent equipment or by adsorption layer absorption that these adsorbents form Lai
It removes.
Absorption process (30) can carry out under 10 DEG C~50 DEG C of temperature range, 1 bar~10 bars of pressure limit.
Absorption process (30) can be realized with adsorption tower (31,32).At this point, being filled in the absorption in adsorption tower (31,32)
The size of agent is preferably in the range of 3mm to 30mm, but best size is considered as in the adsorption capacity and adsorption layer of adsorbent
The pressure loss selects.Above-mentioned adsorption tower can adsorb to remove containing whole carbon dioxide, nitrogen dioxide, moisture and organic hydrocarbon
The single tower of layer.It is preferable, however, that preparing each adsorption tower respectively, suction can be removed using containing carbon dioxide and nitrogen dioxide respectively
The adsorption tower of attached layer and the adsorption tower that adsorption layer is removed containing moisture and organic hydrocarbon.It is excellent in order to be operated continuously in absorption process
Choosing prepares at least two in each adsorption tower, i.e., removes the adsorption tower of adsorption layer containing carbon dioxide and nitrogen dioxide and contain water
Divide and organic hydrocarbon removes another adsorption tower of adsorption layer, and is used to regenerate and operate in turn.
In a preferred embodiment of the invention, the first adsorption tower (31) is used for from the gas mixing containing nitrous oxide
Object removes carbon dioxide and nitrogen dioxide, and is also equipped with the second adsorption tower (32) to remove the gas containing nitrous oxide
Vapor contained in mixture and pass through the carbon dioxide or titanium dioxide in absorption process (30) in the first adsorption tower (31)
The vapor and organic hydrocarbon that neutralize adsorption reaction and generate of nitrogen.
Nitrogen dioxide, titanium dioxide in the admixture of gas containing nitrous oxide purified in above-mentioned absorption process (20)
The concentration of carbon and moisture is at most respectively 1.0ppm (volume), and the concentration of organic hydrocarbon therein is at most 0.1ppm (body
Product).
It is containing concentration respectively by UF membrane process (20) and absorption process (30) concentration and the admixture of gas purified
At least nitrous oxide of 80 volume %, preferably at least 90 volume %, concentration are at most the nitrogen dioxide of 1.0ppm, carbon dioxide
And vapor, concentration are at most the organic hydrocarbon and a small amount of carbon monoxide and nitric oxide of 0.1ppm.
Next, in the method (100) of recycling of the invention and nitrous oxide purification, distillation process (40) be in order to
The admixture of gas of pretreatment process (10), UF membrane process (20) and absorption process (30) is completed in compression, cooling and distillation, from
And recycle nitrous oxide.
Distillation process (40) is in order to by being distilled at low temperature using the difference of vapour pressure (boiling point), by from by advance
The admixture of gas containing nitrous oxide of science and engineering sequence (10), UF membrane process (20) and absorption process (30) purifying and concentration
Nitrogen, oxygen, the carbon monoxide of trace and nitric oxide are removed to recycle high-purity nitrous oxide (at least 99.999 bodies
Product %).
Distillation process (40) can carry out under -160 DEG C~-10 DEG C of temperature range, 3 bars~30 bars of pressure.Temperature and
Pressure can be adjusted in third compressor (41) and the second cooler (42).The heat of compression removes in the second cooler (42), and
And cooling gas is until temperature reaches the condensing temperature of nitrous oxide.Then, gas is supplied to destilling tower (44).It carries out
The operating condition of distillation process can be determined according to the vapor-liquid equilibrium vapour pressure of nitrous oxide.
During cooling in the second cooler (42) in distillation process (40), fine droplets are produced, it can be
It is removed in second flocculator (43).It is stainless that second flocculator (43) can be equipped with 200~300 mesh as the first flocculator (12)
Steel mesh.
Destilling tower (44) in distillation process (40) (can aoxidize for the metal or ceramics for being 5mm~30mm filled with size
Aluminium) filler packed tower or the tray tower that is made of multiple sieve trays or float valve tray.The theoretical trays of destilling tower (44)
It counts preferably in the range of 5~50, more preferably in the range of 10~30.
The condenser on the top of destilling tower (44) can be assemblied in by operating at a temperature of between -160 DEG C~-20 DEG C
(46) nitrous oxide is condensed and is back in destilling tower (44).At this point, reflux ratio is preferably 1~5.Steam generator
(45) it is assemblied in the lower part of destilling tower (44), to evaporate nitrous oxide and supply to destilling tower (44).Therefore, from being assemblied in
The steam generator (45) of the lower part of destilling tower (44) recycles highly purified nitrous oxide liquid.
Pass through the purity for the nitrous oxide that the method for recycling according to the present invention and nitrous oxide purification finally recycles
It is at least 99.999 volume %, and the rate of recovery of nitrous oxide is at least 90%.Recycling/purifying is high-purity according to the present invention
Degree nitrous oxide shows the purity of at least 99.999 volume %, therefore can be used for semiconductor, LCD and OLED technique.
The meaning of label in FIG. 1 to FIG. 3 is as follows.
100: the method for recycling and nitrous oxide purification
10: pretreatment process
11: feeder
12: the first flocculators
13: filter device
20: UF membrane process
21: the first compressors
22: the first coolers
23: the second compressors
24: the first membrane separation devices
25: the second membrane separation devices
26: third membrane separation device
27: the four compressors
28: third cooler
30: absorption process
31: the first adsorption towers
32: the second adsorption towers
40: distillation process
41: third compressor
42: the second coolers
43: the second flocculators
44: destilling tower
45: steam generator
46: flocculator
Reality of the invention and currently preferred embodiment be it is illustrative, as illustrated in the examples below.
However, it should be understood that those skilled in the art are in the case where considering the disclosure, it can be in the spirit and scope of the present invention
It inside modifies and improves.
<embodiment 1>
As shown in Figure 1, the recycling of the nitrous oxide carried out in the present invention and purification process are returning for pilot-scale
Receipts and purification process.The specific side of the method for the waste gas recovery and nitrous oxide purification that are generated from the production process of adipic acid
Method is described in detail with reference to Fig. 1.
(1) pretreatment process: in pretreatment process (10), the exhaust gas for resulting from adipic acid production process passes through supply dress
(11) supply is set, moisture, fine droplets contained in exhaust gas are then removed in the first flocculator (12) and filter device (13)
And dust.Above-mentioned first flocculator is equipped with 200 mesh stainless (steel) wires of 20cm thickness.The diameter of the stainless (steel) wire is 30cm, length
Degree is 60cm.Above-mentioned filter device is equipped with the bag hose made of polyester material.The diameter of the bag hose is 30cm, length
For 80cm.For the recycling of nitrous oxide of the invention and purification process, the exhaust gas that is generated in adipic acid production process
Flow velocity is 60Nm3/ hr is formed as follows.
Nitrous oxide (N2O): 35 volume %,
Nitrogen (N2): 55 volume %
Oxygen (O2): 5 volume %
Carbon dioxide (CO2): 4 volume %
Water (H2O): 1 volume %
Nitrogen dioxide (NO2): 200ppm
Nitric oxide (NO): 800ppm
Organic hydrocarbon: 100ppm
(2) UF membrane process: in UF membrane process (20), the admixture of gas being discharged from pretreatment process (10) is 50
DEG C, supplied by the first compressor (21) and the first cooler (22) to membrane separation device (24,25) under 7 bars of pressure.From
The admixture of gas and be discharged from the flocculator (46) of distillation process (40) another that the osmosizing portion of two membrane separation devices (25) is discharged
One admixture of gas is recycled to the first membrane separation device (24).The pressure of the osmosizing portion of membrane separation device maintains 1.2 bars.The
One membrane separation device (24) and the second membrane separation device (25) are equipped with 100m2Surface area, by Airlein, seperation film
The polysulfones system resin hollow fiber membrane module that one of production company provides.Contain the nitrous oxide that concentration is 90.1 volume %
Admixture of gas can be with 21.6Nm3The flow velocity of/hr flows in osmosizing portion, an oxidation two of the concentration containing 14.7 volume %
The admixture of gas of nitrogen can be from the first membrane separation device (24) with 56.3Nm3The flow velocity of/hr flows in remainder.Remainder
In admixture of gas supply to the second membrane separation device (25), containing concentration be 40.3 volume % nitrous oxide gas
Mixture is with 15.4Nm3The flow velocity of/hr is gathered in osmosizing portion, and the gas containing the nitrous oxide that concentration is 5.1 volume %
Body mixture is with 40.9Nm3The flow velocity of/hr is gathered in remainder.It is discharged by the osmosizing portion of the second membrane separation device (25)
Admixture of gas (flow velocity: 15.4Nm3/ hr) it is filled by using the second compressor (23) increase suppressing recirculation to the first UF membrane
Set (24).
Contain one from the admixture of gas that flocculator (46) are discharged in distillation process (40) with the concentration of 16.0 volume %
Nitrous oxide, flow velocity 2.5Nm3/hr.The admixture of gas supplied from the first membrane separation device (24) is comprising merging below
Admixture of gas: admixture of gas being supplied from pretreatment process (10), containing the nitrous oxide that concentration is 35 volume %
(flow velocity: 60Nm3/ hr), the oxygen for being 40.3 volume % containing concentration separated from the osmosizing portion of the second membrane separation device (25)
Change the admixture of gas (flow velocity: 15.4Nm of phenodiazine3/ hr), and from the recycling of the flocculator (46) of destilling tower (44) containing dense
Degree is the admixture of gas (flow velocity: 2.5Nm of the nitrous oxide of 16.0 volume %3/hr).It is concentrated most in UF membrane process
The concentration of whole nitrous oxide is about 90.1 volume %, and the rate of recovery is about 90%.It will be from the second membrane separation device (25)
The admixture of gas pyrolysis containing the nitrous oxide that concentration is 5.1 volume % of remainder discharge, to will discharge to atmosphere
The concentration of nitrous oxide decrease below 100ppm.
(3) absorption process: absorption process (30) is to be divided from UF membrane process (20) from the first film by absorption
Admixture of gas (the 21.6Nm containing the nitrous oxide that concentration is 90.1 volume % of osmosizing portion discharge from device (24)3/
Hr the impurity such as carbon dioxide, nitrogen dioxide, vapor and organic hydrocarbon is removed in).In the absorption process, the first absorption
The diameter of each adsorption layer filled with adsorbent of tower (31) and the second adsorption tower (32) is respectively 20cm, and the length is 200cm.
First adsorption tower (31) is filled withI.e. by coating the adsorbent of 5-10mm silica preparation with sodium hydroxide,
And the second adsorption tower (32) is filled with 5-10mm zeolite 5A.First adsorption tower (31) is equipped with for supplying cooling water to remove
By the collet for the heat that adsorption reaction generates.First adsorption tower and the second adsorption tower operate at room temperature, under 1~2 bar of pressure.?
In first adsorption tower (31), carbon dioxide and nitrogen dioxide are removed by reacting with sodium hydroxide, and generate vapor.It should
Organic hydrocarbon contained in the vapor of generation and the admixture of gas of above-mentioned offer and vapor pass through the second adsorption tower (32)
In be adsorbed and removed.The flow velocity of the admixture of gas containing nitrous oxide purified by absorption process is 21.4Nm3/ hr,
Its composition is as follows:
Nitrous oxide (N2O): 90.2 volume %,
Nitrogen (N2): 8.9 volume %
Oxygen (O2): 0.9 volume %
Carbon dioxide (CO2): 0.2ppm
Vapor: 0.6ppm
Nitrogen dioxide (NO2): 0.1ppm
Nitric oxide (NO): 500ppm
Organic hydrocarbon: 0.1ppm
(4) distillation process: distillation process (40) be in order to by the admixture of gas that will be purified in absorption process (30) with
21.4Nm3The flow velocity of/hr supplies to distillation process (40), by removing nitrogen and oxygen and obtains high-purity nitrous oxide.
It is compressed in the distillation process by using third in absorption process (30) from the admixture of gas that the second adsorption tower (32) are discharged
Machine (41) is compressed with 20 bars of pressure, and then the temperature of admixture of gas is and the removing heat of compression in the second cooler (42)
It is reduced to -60 DEG C.At this point, issuable moisture and fine droplets remove in the second condenser (43), then gas mixing
Object is supplied to destilling tower (44).Destilling tower (44) is filled with 5/8 inch of stainless steel Pall ring.The diameter of filled layer is 15cm,
Its height is 5m.Nitrous oxide condensation in the flocculator (46) that the top of destilling tower (44) is assembled, then in destilling tower
(44) recycling in.The temperature of flocculator (46) is maintained -70 DEG C.The reflux ratio of destilling tower (44) is maintained 2 or so.Not cold
Liquefied admixture of gas (nitrous oxide 16.0 volume %, flow velocity 2.5Nm in condenser (46)3/ hr) it is recycled to UF membrane
Process (20).Liquid nitrous oxide evaporation, gas of evaporation in the steam generator (45) that the lower part of destilling tower (44) is assembled
Body is supplied to destilling tower (44).The temperature of steam generator (45) remains -23 DEG C.The steaming assembled from the lower part of destilling tower (44)
Vapour generator recycles highly purified nitrous oxide.The flow velocity of the liquid nitrous oxide recycled from distillation process (40) is about
34.0kg/hr is formed as follows.At this point, the purity of carbon dioxide is 99.9999 volume %.
Nitrous oxide (N2O): 99.9999 volume %
Nitrogen (N2): 0.8ppm
Oxygen (O2): 0.6ppm
Carbon dioxide (CO2): 0.2ppm
Water (H2O): 0.6ppm
Nitrogen dioxide (NO2): 0.1ppm
Nitric oxide (NO): 0.1ppm
Organic hydrocarbon: 0.1ppm
The rate of recovery of finally obtained nitrous oxide is about 90% in distillation process.
As described above, the recycling of nitrous oxide of the invention and purification process be conducive to by from nitrous oxide, oneself
The waste gas recovery generated in the production process of diacid, nitric acid and caprolactam shows 310 times of global warming higher than carbon dioxide
The nitrous oxide of potentiality (GWP) effectively reduces greenhouse gases.The recycling of nitrous oxide of the invention and purification process are also
Promote the exhaust gas generated from the production process of nitrous oxide, adipic acid, nitric acid and caprolactam with high-purity (at least 99.999
Volume %) and (at least 90%) recycling and purifying can be used for an oxidation two of semiconductor, LCD and OLED production process in high yield
Nitrogen.
Industrial availability
The recycling of nitrous oxide of the invention and purification process are conducive to by from nitrous oxide, adipic acid, nitric acid
310 times higher than carbon dioxide of global warming potential (GWP) is shown with the waste gas recovery generated in the production process of caprolactam
Nitrous oxide effectively reduce greenhouse gases.The recycling of nitrous oxide of the invention and purification process also promote from an oxygen
Change the exhaust gas that generates of production process of phenodiazine, adipic acid, nitric acid and caprolactam with high-purity (at least 99.999 volume %) and
(at least 90%) recycling and purifying can be used for the nitrous oxide of semiconductor, LCD and OLED production process in high yield.
Claims (10)
1. recycling and the purification process of a kind of nitrous oxide comprising following steps:
Pretreatment process is removed by admixture of gas of the supply containing nitrous oxide or exhaust gas and is selected from by the gas
At least one of the impurity of group of fine water droplets, fine droplets contained in mixture and subparticle impurity composition；
UF membrane process completes nitrogen and/or oxygen contained in the admixture of gas of above-mentioned pretreatment process by removing
Carry out concentrating dinitrogen monoxide；
Absorption process is selected from the titanium dioxide as contained in the admixture of gas for completing above-mentioned UF membrane process by being adsorbed and removed
At least one of carbon, nitrogen dioxide, vapor and impurity of group of organic hydrocarbon composition；With
Distillation process, the series of steps of compression, cooling and the distillation of the admixture of gas by completing above-mentioned absorption process
To recycle nitrous oxide.
2. recycling and the purification process of a kind of nitrous oxide comprising following steps:
Pretreatment process is removed by admixture of gas of the supply containing nitrous oxide or exhaust gas by the gas mixing
At least one of the impurity of group of fine water droplets, fine droplets contained in object and subparticle impurity composition；
Absorption process is selected from the titanium dioxide as contained in the admixture of gas for completing above-mentioned pretreatment process by being adsorbed and removed
At least one of carbon, nitrogen dioxide, vapor and impurity of group of organic hydrocarbon composition；
UF membrane process, by remove complete nitrogen contained in the admixture of gas of above-mentioned absorption process and/or oxygen come
Concentrating dinitrogen monoxide；With
Distillation process, a series of steps of compression, cooling and the distillation of the admixture of gas by completing above-mentioned UF membrane process
It is rapid to recycle nitrous oxide.
3. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein described contain nitrous oxide
Admixture of gas or exhaust gas be selected from by nitrous oxide production process, adipic acid production process, nitric acid production process and
The exhaust gas generated during the group of caprolactam production process composition.
4. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein the UF membrane process uses
Include one kind selected from the group being made of the resin of polysulfones based polymer resin, polyimides based polymer resin and a combination thereof
Or seperation film of the multiple material as the main component of gas separating layer.
5. recycling and the purification process of nitrous oxide according to claim 1 or 2, including other pyrolysis or are urged
Change the process decomposed, the admixture of gas in atmosphere is thrown by the UF membrane process and the distillation process to decompose
Contained in nitrous oxide.
6. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein above-mentioned recycling and purification process
In the purity of nitrous oxide that finally recycles be at least 99.999 volume %, the rate of recovery is at least 90%.
7. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein in 10 DEG C to 40 DEG C of temperature
Described in being carried out under range, 1 bar to 2 bars of pressure with the flocculator for removing moisture or oil droplet and the filter device for removing fine dust
Pretreatment process.
8. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein in 10 DEG C to 100 DEG C of temperature
It is carried out under degree, 2 bars to 15 bars of feed pressure and the osmotic pressure of vacuum to 3 bars by using single-layer or multi-layer membrane separation device
The UF membrane process.
9. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein by using selected from by hydrogen-oxygen
Change sodium (NaOH), calcium hydroxide (Ca (OH)2) and potassium hydroxide (KOH) composition group one or more adsorbents or wherein
Sodium hydroxide (NaOH), calcium hydroxide (Ca (OH)2) or potassium hydroxide be coated on the adsorbent on silica or zeolite, 10
DEG C to the absorption process is carried out under 50 DEG C of temperature, 1 bar to 10 bars of pressure, to remove carbon dioxide and nitrogen dioxide；
With by using selected from the one or more adsorbents of group being made of silica, zeolite, alumina silicate and active carbon at 10 DEG C
The absorption process is carried out under to 50 DEG C of temperature, 1 bar to 10 bars of pressure, to remove vapor and organic hydrocarbon.
10. recycling and the purification process of nitrous oxide according to claim 1 or 2, wherein at -160 DEG C to -10 DEG C
With the packed tower filled with metal or ceramic packing or the tray tower being made of multiple tower trays under temperature, 3 bars to 30 bars of pressure
Carry out the distillation process.
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| KR10-2016-0091920 | 2016-07-20 | ||
| KR1020160091920A KR101858190B1 (en) | 2016-07-20 | 2016-07-20 | Process for the recovery and purification of nitrous oxide from industrial emission gas mixtures |
| PCT/KR2017/006586 WO2018016750A1 (en) | 2016-07-20 | 2017-06-22 | Process for recovery and purification of nitrous oxide from nitrous oxide-containing gas mixture |
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| KR (1) | KR101858190B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072001A (en) * | 2019-12-11 | 2020-04-28 | 宿州伊维特新材料有限公司 | Nitrous oxide purification system and method of operating a system |
| CN115430283A (en) * | 2022-09-23 | 2022-12-06 | 全椒科利德电子材料有限公司 | Method for purifying nitrous oxide |
| WO2023123596A1 (en) * | 2021-12-30 | 2023-07-06 | 大连科利德光电子材料有限公司 | Oxygen adsorbent, preparation method and method for reducing oxygen content in nitrous oxide raw material gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20210309520A1 (en) * | 2018-09-28 | 2021-10-07 | Showa Denko K.K. | Nitrous oxide purification method |
| KR102247285B1 (en) * | 2019-10-07 | 2021-05-03 | 한국에너지기술연구원 | Hybrid gas separation process including membrane process and distillation process |
| KR102342829B1 (en) * | 2020-03-26 | 2021-12-24 | 주식회사 에프알디 | High purity nitrous oxide refining apparatus for manufacturing semiconductor and OLED and for medical |
| KR102394305B1 (en) * | 2020-05-22 | 2022-05-04 | 주식회사 에프알디 | Impurity removing apparatus applied in high purity nitrous oxide refining facilities for manufacturing semiconductor and OLED and for medical |
| CN111871146A (en) * | 2020-07-16 | 2020-11-03 | 中国能源建设集团广东省电力设计研究院有限公司 | Carbon dioxide capture system based on coupling membrane separation method and adsorption method |
| KR102461654B1 (en) * | 2020-12-02 | 2022-11-01 | 주식회사 에프알디 | High purity nitrous oxide refining apparatus for manufacturing semiconductor and OLED and for medical |
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| US6348083B1 (en) * | 1999-02-17 | 2002-02-19 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and installation for the recovery and/or purification of the nitrous oxide contained in a waste gas |
| CN105110304A (en) * | 2015-09-01 | 2015-12-02 | 上海交通大学 | Device and method for preparing high-purity nitrogen monoxide from adipic acid production tail gases |
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| CN111072001A (en) * | 2019-12-11 | 2020-04-28 | 宿州伊维特新材料有限公司 | Nitrous oxide purification system and method of operating a system |
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| WO2018016750A1 (en) | 2018-01-25 |
| KR101858190B1 (en) | 2018-05-16 |
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