CN102160990A - Method for preparing lithium oxygen generation adsorbent - Google Patents
Method for preparing lithium oxygen generation adsorbent Download PDFInfo
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- CN102160990A CN102160990A CN 201110068122 CN201110068122A CN102160990A CN 102160990 A CN102160990 A CN 102160990A CN 201110068122 CN201110068122 CN 201110068122 CN 201110068122 A CN201110068122 A CN 201110068122A CN 102160990 A CN102160990 A CN 102160990A
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Abstract
The invention discloses a method for preparing a lithium oxygen generation adsorbent. The method comprises the following steps: mixing a molecular sieve to be modified and lithium salt aqueous solution according to a molar ratio of 1:(1-6), wherein the molar concentration of the lithium salt aqueous solution is between 0.4 and 4mol/L; filling mixed suspension into a high pressure reacting kettle to perform heat exchange reaction under the pressure of between 0.04 and 0.26MPa (surface) and temperature between 110 and 140 DEG C for 2 to 10 hours for 2 to 4 times; and filtering, cleaning, drying and activating the reacted molecular sieve. The exchange velocity of the molecular sieve and metal ions and utilization efficiency of exchanging metal ions are improved by increasing the pressure and temperature of a molecular sieve exchange system, so that the adsorption capacity of the molecular sieve to nitrogen is improved; furthermore, the improvement of the utilization efficiency of exchanging metal ions can simplify the waste liquid recycling process while reducing waste liquid, and the environmental pollution and preparation cost are reduced.
Description
Technical field
The present invention relates to a kind of method of modifying of molecular sieve, specifically, relate to a kind of preparation method of efficient lithium type system oxygen absorbent.
Background technology
Along with industrial expansion, the consumption of oxygen in all trades and professions increases day by day, and traditional deep cooling legal system oxygen is because energy consumption is big, the start-stop car time is long, be not suitable for shortcomings such as producing oxygen on a small scale and replaced by pressure swing adsorption method system oxygen technology gradually.
The omnibus control system key technology is the development of efficiently making oxygen absorbent, and its system oxygen principle is: because the quadrupole moment of nitrogen
Quadrupole moment greater than oxygen
, the strong and selective absorption nitrogen of the cation in the molecular sieve and the active force of nitrogen makes in the air nitrogen oxygen separate and makes oxygen.Because Li
+Be the metal ion of radius minimum in many elements, charge density is high, and is the strongest with the effect of nitrogen, so 5A type, 13X type and LSX molecular sieve, especially LiX and LiLSX molecular sieve that system oxygen absorbent commonly used all is lithiums have been exchanged.And the adsorption capacity of lithium type system oxygen absorbent depends on Li substantially
+Exchange degree.Patent US5268023 points out, have only when exchange degree greater than 70% the time, the adsorption capacity of LiX just can increase sharply, the optimum exchange degree that provides of document is 88% at present; Patent US4859217 also points out, works as Li
+Exchange degree be 99% o'clock, the adsorbance of nitrogen can reach 1.03mmol/g under the normal pressure, so improve Li
+Exchange degree also just become the key of efficient system oxygen absorbent.But because Li
+In the aqueous solution, be easy to form hydrated ion, also just difficult with the exchange of metal ion on the framework of molecular sieve, traditional constant pressure hydro-thermal exchange process is based upon often and prolongs swap time, increases the exchange number of times, increases on the bases such as consumption of exchange slaine in order to improve its exchange degree, energy consumption is big, waste liquid is many, waste is serious, is difficult to realize industrialization.
Patent US6806219, US5174979 etc. are by repeatedly exchanging or increasing Li
+Consumption reach higher exchange degree, with the capacity of the absorption nitrogen that improves molecular sieve, this undoubtedly method is consuming time, take energy, Li
+Utilization rate is low and waste liquid is many.
Announce a kind of ion-exchange process for preparing lithium type low silicon aluminum X-shape zeolite molecular sieve among the patent CN 101125664A, proposed the ion-exchange process that a kind of aqueous solution exchange and high temperature solid-state roasting hocket.Detailed process is: at first under 90 ℃, with molar concentration is the LiCl solution exchange 2 times of 0.4mol/L, each 2h, exchange degree can reach more than 86.6%, be the ratio of 1: 1.5 (mol ratio of sodium ion and lithium ion in the zeolite molecular sieve) with the solid phase exchange process according to zeolite molecular sieve and lithium chloride then, temperature programming to 350 ℃ constant temperature 180min, last exchange degree can reach more than 96%.Though the method that this aqueous solution exchange combines with solid phase roasting exchange has solved the problem of later stage exchange lithium salts waste, but the skewness that can occur lithium salts and molecular sieve unavoidably that mixes of solid phase and solid phase, so just cause the inhomogeneous of molecular sieve exchange, and also might at high temperature enter into the cage of molecular sieve from the salt that molecular sieve exchanges, will cause the molecular sieve adsorption performance decrease if wash halfway words.
Announced a kind of lithium-containing modified low silicon-aluminum X type molecular sieve preparation of adsorbent method among the patent CN 101766987A, the method of modifying that a kind of exchange and roasting hocket has been proposed, detailed process is: at first making molecular sieve and molar concentration is LiCl solution exchange 4h under 60 ℃ of 0.5mol/L, at 100 ℃ of following 380 ℃ of roasting 2h of temperature control behind the dry 2h, obtain one and hand over the LSX molecular sieve of a roasting after the filtering and washing; And then with molar concentration be the LiCl solution of 1.5mol/L at 80 ℃ of following exchange 2h, at 100 ℃ of 420 ℃ of roasting 3h of temperature control behind the dry 2h down, obtain two and hand over the LSX molecular sieves of two roastings after the filtering and washing; Last and molar concentration are that the LiCl solution of 1.8mol/L exchanges 4h down at 100 ℃, just obtain the Li exchange degree behind the filtration washing and be 95.3% Li-LSX molecular screen primary powder.Though the method that exchange and roasting hocket can improve the stability of framework of molecular sieve, reduce the damage of subsequent treatment process to framework of molecular sieve, but this every exchange once obviously makes whole modifying process seem complicated with regard to the method for roasting, and energy consumption can increase, and clearly this complicated technology is difficult in the large-scale industrial production to be realized.
Summary of the invention
What the present invention will solve is the technical problem that the lithium salts consumption is big, utilization rate is low, exchange rate is low, exchange degree is low and adsorption capacity is low that switching method exists in the lithium exchange process in the prior art, a kind of preparation method of new lithium type system oxygen absorbent is provided, and technology is simple, exchange degree is high, cost is low and nitrogen adsorption capacity height.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
A kind of preparation method of lithium type system oxygen absorbent, this method comprises the steps:
A. will treat that the molecular sieve of modification and Aqueous Lithium Salts are according to 1: 1～6 mixed in molar ratio, the molar concentration of Aqueous Lithium Salts is 0.4～4mol/L, and the mol ratio of the wherein said molecular sieve for the treatment of modification and Aqueous Lithium Salts is meant the molar content ratio that contains lithium ion in valent metal ion and the Aqueous Lithium Salts in the molecular sieve;
B. step (a) mixing rear suspension liquid is packed into and have in the autoclave of agitating device, add heat exchange reaction, exchange pressure is 0.04MPa (table)～0.26MPa (table), and the exchange temperature is 110 ℃～140 ℃, exchange 2～4 times, be 2h～10h each swap time;
C. the molecular sieve after step (b) reaction being finished filters, washs, dry, activation, obtains lithium type system oxygen absorbent.
The molecular screening for the treatment of modification in the described step (a) is from wherein a kind of of 5A molecular sieve, 13X molecular sieve or LSX molecular sieve.
Aqueous Lithium Salts in the described step (a) is selected from wherein at least a of the lithium chloride aqueous solution, the lithium nitrate aqueous solution or the lithium sulfate aqueous solution, is preferably the lithium chloride aqueous solution.
The molecular sieve for the treatment of modification in the described step (a) is the completed state after former powdery attitude or the granulation.
The invention has the beneficial effects as follows:
The present invention is by improving pressure, the temperature of molecular sieve switching architecture, the exchange rate of molecular sieve and metal ion and the utilization ratio of exchange metal ion have been improved, thereby improved the adsorption capacity of molecular sieve to nitrogen, and whole molecular sieve modified technology has also greatly been simplified in the reduction that totally exchanges number of times and swap time, the raising that exchanges the metal ion utilization ratio in addition also makes the process of waste liquid recovery simplify when reducing waste liquid, has reduced environmental pollution and preparation cost.
The specific embodiment
The present invention discloses a kind of preparation method of lithium type system oxygen absorbent, its principle is that molecular sieve is mixed mutually with Aqueous Lithium Salts, pressure and temperature by the rising system in autoclave, make the exchange of molecular sieve and lithium ion be easy to more carry out, with the exchange degree of raising molecular sieve lithium and the utilization rate of lithium salts, and then improve the adsorption capacity of lithium type system oxygen absorbent to nitrogen.
The present invention is described in further detail below by specific embodiment:
Following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way, embodiment all selects to use the 13X molecular screen primary powder as the molecular sieve for the treatment of modification, the molecular sieve of wherein treating modification and the mol ratio of Aqueous Lithium Salts are meant the molar content ratio that contains lithium ion in valent metal ion and the Aqueous Lithium Salts in the molecular sieve, and the ratio of each exchange is in 1: 1～6 scopes.The 50g 13X molecular screen primary powder of being mentioned in an embodiment contains valent metal ion 0.30mol approximately, if 50g 5A molecular screen primary powder then contains valent metal ion 0.27mol approximately, if 50g LSX molecular screen primary powder contains valent metal ion 0.35mol approximately; And those skilled in the art should know, and above three kinds of molecular sieves of 5A molecular screen primary powder, LSX molecular screen primary powder and granulation aftershaping state are suitable for following each embodiment too.
Embodiment 1
Take by weighing 50g 13X molecular screen primary powder, with the 500mL molar concentration is that the LiCl solution of 1mol/L mixes, and places the autoclave that has agitating device, is that 0.1MPa (table), temperature are under 120 ℃ the condition behind the exchange 5h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 500mL molar concentration is 1mol/L under the similarity condition obtaining molecular sieve, also be 5h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 1.03mmol/g.
Embodiment 2
Take by weighing 50g 13X molecular screen primary powder, with the 500mL molar concentration be the Li of 1mol/L
2SO
4Solution mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 3h at pressure, filters, and finishes for the first time exchanging;
Join the Li that the 500mL molar concentration is 1mol/L once more with obtaining molecular sieve
2SO
4Carry out the exchange second time in the solution under the similarity condition, also be 3h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 0.90mmol/g.
Embodiment 3
Take by weighing 50g 13X molecular screen primary powder, with the 800mL molar concentration is that the LiCl solution of 0.4mol/L mixes, and places the autoclave that has agitating device, is that 0.2MPa (table), temperature are under 130 ℃ the condition behind the exchange 5h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 800mL molar concentration is 0.4mol/L under the similarity condition obtaining molecular sieve, also be 5h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 0.98mmol/g.
Embodiment 4
Take by weighing 50g 13X strip molecular sieve, with the 500mL molar concentration is that the LiCl solution of 2mol/L mixes, and places the autoclave that has agitating device, is that 0.1MPa (table), temperature are under 120 ℃ the condition behind the exchange 10h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 500mL molar concentration is 2mol/L under the similarity condition obtaining molecular sieve, also be 10h swap time, obtain the molecular sieve of exchange for the second time, filter and spend deionised water, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 0.93mmol/g.
Embodiment 5
Take by weighing 50g 13X molecular screen primary powder, with the 350mL molar concentration be the LiNO of 3mol/L
3Solution mixes, and places the autoclave that has agitating device, is that 0.1MPa (table), temperature are under 120 ℃ the condition behind the exchange 2h at pressure, filters, and finishes for the first time exchanging;
Join the LiNO that the 350mL molar concentration is 3mol/L once more with obtaining molecular sieve
3Carry out the exchange second time in the solution under the similarity condition, also be 2h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 0.98mmol/g.
Embodiment 6
Take by weighing 50g 13X molecular screen primary powder, with the 350mL molar concentration is that the LiCl solution of 3mol/L mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 10h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 350mL molar concentration is 3mol/L under the similarity condition obtaining molecular sieve, also be 10h swap time, by that analogy, exchanges altogether 4 times.With molecular sieve filtration, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.29mmol/g.
Embodiment 7
Take by weighing 50g 13X molecular screen primary powder, with the 350mL molar concentration is that the LiCl solution of 4mol/L mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 4h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 350mL molar concentration is 4mol/L under the similarity condition obtaining molecular sieve, also be 5h swap time, by that analogy, exchanges altogether 4 times.With molecular sieve filtration, spend deionised water after the 4th exchange finishes, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.21mmol/g.
Embodiment 8
Take by weighing the spherical molecular sieve of 50g 13X, with the 450mL molar concentration is that the LiCl solution of 4mol/L mixes, and places the autoclave that has agitating device, is that 0.26MPa (table), temperature are under 140 ℃ the condition behind the exchange 2h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 450mL molar concentration is 4mol/L under the similarity condition obtaining molecular sieve, also be 2h swap time, exchanges altogether 2 times.Obtain the molecular sieve of twice exchange, filter and spend deionised water, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.01mmol/g.
Embodiment 9
Take by weighing 50g 13X molecular screen primary powder, with the 350mL molar concentration is that the LiCl solution of 3mol/L mixes, and places the autoclave that has agitating device, is that 0.2MPa (table), temperature are under 130 ℃ the condition behind the exchange 5h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 350mL molar concentration is 3mol/L under the similarity condition obtaining molecular sieve, be 10h swap time, by that analogy, exchanges altogether 4 times.Obtain the molecular sieve of exchange for the second time, spend deionised water, obtain the LiX molecular sieve to there not being anion to exist;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.06mmol/g.
Embodiment 10
Take by weighing 50g 13X molecular screen primary powder, with the 450mL molar concentration is that the LiCl solution of 4mol/L mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 5h at pressure, filter, finish exchange for the first time;
The molecular sieve of finishing exchange is for the first time joined in the LiCl solution that the 450mL molar concentration is 3mol/L once more, place autoclave, at pressure is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 4h, filters, and finishes exchange for the second time.The molecular sieve that to finish exchange for the second time then is that the LiCl solution of 2mol/L mixes with the 450mL molar concentration again, place autoclave, at pressure is that 0.1MPa (table), temperature are under 120 ℃ the condition behind the exchange 3h, filter, spend deionised water to there not being anion to exist, obtain the LiX molecular sieve;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.10mmol/g.
Embodiment 11
Take by weighing 50g 13X molecular screen primary powder, with the 500mL molar concentration be the LiNO of 3mol/L
3Solution mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 4h at pressure, filters, and finishes for the first time exchanging;
The molecular sieve of finishing exchange is for the first time joined the LiNO that the 500mL molar concentration is 3mol/L once more
3In the solution, placing autoclave, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 4h at pressure, filters, and finishes exchange for the second time.The molecular sieve that to finish exchange for the second time then is that the LiCl solution of 2mol/L mixes with the 350mL molar concentration again, places autoclave, is after 0.1MPa (table), temperature are to exchange 3h under 120 ℃ the condition, to filter at pressure, finishes the 3rd exchange.The molecular sieve that to finish for the third time exchange then is that the LiCl solution of 2mol/L mixes with the 350mL molar concentration again, place autoclave, at pressure is that 0.1MPa (table), temperature are under 120 ℃ the condition behind the exchange 3h, filter, spend deionised water to there not being anion to exist, obtain the LiX molecular sieve;
After the LiX molecular sieve drying that obtains, activation, the adsorption capacity of the nitrogen that records under the condition of room temperature, 0.1MPa (table) is 1.12mmol/g.
Embodiment 12
Take by weighing 50g 5A molecular screen primary powder, with the 400mL molar concentration is that the LiCl solution of 1.5mol/L mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 3h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 400mL molar concentration is 1.5mol/L under the similarity condition obtaining molecular sieve, also be 3h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiA molecular sieve to there not being anion to exist;
After the LiA molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 0.60mmol/g.
Embodiment 13
Take by weighing 50g LSX molecular screen primary powder, with the 400mL molar concentration is that the LiCl solution of 1mol/L mixes, and places the autoclave that has agitating device, is that 0.04MPa (table), temperature are under 110 ℃ the condition behind the exchange 3h at pressure, filter, finish exchange for the first time;
Join once more and carry out second time exchange in the LiCl solution that the 400mL molar concentration is 1mol/L under the similarity condition obtaining molecular sieve, also be 3h swap time, by that analogy, exchanges altogether 4 times.With the molecular sieve suspension filtered, spend deionised water after the 4th exchange finishes, obtain the LiLSX molecular sieve to there not being anion to exist;
After the LiLSX molecular sieve drying that obtains, activation, the adsorption capacity that records nitrogen under the condition of room temperature, 0.1MPa (table) is 0.97mmol/g.
In sum, the present invention in the adsorption capacity of the lithium type system oxygen absorbent for preparing under high pressure, the high temperature its nitrogen under the condition of room temperature, 0.1MPa (table) about 1mmol/g.
Although above the preferred embodiments of the present invention are described; but the present invention is not limited to the above-mentioned specific embodiment; the above-mentioned specific embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away under the scope situation that aim of the present invention and claim protect, can also make the concrete conversion of a lot of forms, these all belong within protection scope of the present invention.
Claims (5)
1. the preparation method of a lithium type system oxygen absorbent is characterized in that, this method comprises the steps:
A. will treat that the molecular sieve of modification and Aqueous Lithium Salts are according to 1: 1～6 mixed in molar ratio, the molar concentration of Aqueous Lithium Salts is 0.4～4mol/L, and the mol ratio of the wherein said molecular sieve for the treatment of modification and Aqueous Lithium Salts is meant the molar content ratio that contains lithium ion in valent metal ion and the Aqueous Lithium Salts in the molecular sieve;
B. step (a) mixing rear suspension liquid is packed into and have in the autoclave of agitating device, add heat exchange reaction, exchange pressure is 0.04MPa (table)～0.26MPa (table), and the exchange temperature is 110 ℃～140 ℃, exchange 2～4 times, be 2h～10h each swap time;
C. the molecular sieve after step (b) reaction being finished filters, washs, dry, activation, obtains lithium type system oxygen absorbent.
2. the preparation method of a kind of lithium type system oxygen absorbent according to claim 1 is characterized in that, the molecular screening for the treatment of modification in the described step (a) is from wherein a kind of of 5A molecular sieve, 13X molecular sieve or LSX molecular sieve.
3. the preparation method of a kind of lithium type system oxygen absorbent according to claim 1 is characterized in that, the Aqueous Lithium Salts in the described step (a) is selected from wherein at least a of the lithium chloride aqueous solution, the lithium nitrate aqueous solution or the lithium sulfate aqueous solution.
4. the preparation method of a kind of lithium type system oxygen absorbent according to claim 3 is characterized in that, the Aqueous Lithium Salts in the described step (a) is the lithium chloride aqueous solution.
5. the preparation method of a kind of lithium type system oxygen absorbent according to claim 1 is characterized in that, the molecular sieve for the treatment of modification in the described step (a) is the completed state after former powdery attitude or the granulation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105984881A (en) * | 2016-01-18 | 2016-10-05 | 明光市飞洲新材料有限公司 | Efficient lithium-based oxygen generation molecular sieve and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268023A (en) * | 1992-10-05 | 1993-12-07 | Air Products And Chemicals, Inc. | Nitrogen adsorption with highly Li exchanged X-zeolites with low Si/Al ratio |
| CN1356155A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Adsorbent for gas separation and its preparing process |
| CN1668374A (en) * | 2002-03-25 | 2005-09-14 | 科学与工业研究会 | Process for the preparation of molecular sieve adsorbent for selective adsorption of nitrogen and argon |
| CN101380565A (en) * | 2008-10-10 | 2009-03-11 | 上海恒业化工有限公司 | Active molecular sieve absorbent and preparation method thereof |
-
2011
- 2011-03-21 CN CN 201110068122 patent/CN102160990A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268023A (en) * | 1992-10-05 | 1993-12-07 | Air Products And Chemicals, Inc. | Nitrogen adsorption with highly Li exchanged X-zeolites with low Si/Al ratio |
| CN1356155A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Adsorbent for gas separation and its preparing process |
| CN1668374A (en) * | 2002-03-25 | 2005-09-14 | 科学与工业研究会 | Process for the preparation of molecular sieve adsorbent for selective adsorption of nitrogen and argon |
| CN101380565A (en) * | 2008-10-10 | 2009-03-11 | 上海恒业化工有限公司 | Active molecular sieve absorbent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105984881A (en) * | 2016-01-18 | 2016-10-05 | 明光市飞洲新材料有限公司 | Efficient lithium-based oxygen generation molecular sieve and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned |
Effective date of abandoning: 20110824 |
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| C20 | Patent right or utility model deemed to be abandoned or is abandoned |