CN104437352A - Preparation method of nitrogen adsorbent - Google Patents
Preparation method of nitrogen adsorbent Download PDFInfo
- Publication number
- CN104437352A CN104437352A CN201410617880.7A CN201410617880A CN104437352A CN 104437352 A CN104437352 A CN 104437352A CN 201410617880 A CN201410617880 A CN 201410617880A CN 104437352 A CN104437352 A CN 104437352A
- Authority
- CN
- China
- Prior art keywords
- carrier
- titanium
- calcium
- solid matter
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a nitrogen adsorbent. The preparation method is characterized in that ZSM-11 serves as a carrier of the adsorbent, and calcium, magnesium, titanium and aluminum salts are deposited and precipitated on the carrier to obtain the nitrogen adsorbent. The method specifically comprises the steps of adding magnesium salt, titanium salt and aluminum salt to 3wt% to 8wt% of a calcium salt solution; uniformly agitating to enable the mass ratio of calcium to magnesium to titanium to aluminum in the mixed solution to be (6-8):(2-3):(3-4):(1-2); adding the ZSM-11 carrier to the mixed solution, wherein the content of the added ZSM-11 carrier is 4 to 8 times the mass of calcium; dropwise adding a 2-4mol/L alkaline solution to the mixed solution at a constant speed until the pH value of the mixed solution is 10-12, wherein an alkaline solution is selected from sodium hydroxide, potassium hydroxide and ammonium hydroxide; filtering to obtain solid matter; washing with alcohol and deionized water for multiple times to remove impurities from the surface of the solid matter; drying the solid matter at the temperature of 100 to 120 DEG C; and roasting for 2 to 4 hours in the air at the temperature of 400 to 500 DEG C and roasting for 2 to 4 hours in the air at the temperature of 700 to 800 DEG C to obtain the nitrogen adsorbent. By adopting the preparation method, the intrinsic adsorbing rate of the prepared nitrogen adsorbent and the balancing characteristic of an adsorbing material can be improved, and a high adsorption rate is reached.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen adsorption agent.
Background technology
Various PSA, VSA and VPSA methods for air separation in 30 years of past have a great development, the main progressive last decade occurred.The industrialization of these methods and production range continuous expands may mainly owing to the improvement of adsorbent and process cycles, and the improved action of absorber design is less.For PSA O
2common adsorbents balance time be N
2-optionally, comprise the mixture of such as 13X, CaA, CaX and CaA and CaX.Advanced adsorbent has the equilibrium property of improvement as Δ N
2load (such as displacement volume) is high, nitrogen/oxygen selective is high and capacity is high.The lithium dimer sieve adsorbant highly exchanged described in US4 859 217 (Chao) is for O
2the Typical Representative of this advanced adsorbent produced.
The separative efficiency of admixture of gas such as air depends on many parameters, special in the type of high pressure, low pressure, adsorbent material used, the absorption affinity for separating of the adsorbent of mixture to be separated, the component of admixture of gas to be separated, the adsorption temp of mixture to be separated, the size and dimension of absorbent particles, the particle composition in described adsorbent bed and thermograde.At present, zeolite, particularly A, X, Y or LSX (low silica X) type is the prevailing adsorbent used in PSA method.Zeolite granular is usually containing monovalence, and divalence and Tricationic, such as alkali-metal, alkaline-earth metal or lanthanide series metal, they are the cations mixed thereafter in zeolite granular synthesis and/or by ion exchange technique.
Absorption method is divided into again Temp .-change adsorptive process (TSA), pressure swing adsorption method (PSA) and vacuum suction (VSA), adsorbent is absorption nitrogen when low temperature (or high pressure), after intensification (or step-down), nitrogen is desorbed, by periodic temperature (or pressure) change, thus make nitrogen separation out.Pressure-variable adsorption generally also at room temperature works.Vacuum suction energy consumption is high, strict to equipment requirement.The requirement and the raising product yield that reduce adsorbent can improving technique efficiency and the costs reducing light component product.The former generally represents with a size factor (BSF) pound adsorbent/TPDO (oxygenous ton/sky), and the latter is the mark of the light component of catching as product in charging.
Improving adsorbent and reducing circulation timei is the two kinds of main method reducing BSF.Although circulation timei short-range missile to cause the shorter and adsorbent utilization rate of bed higher, product recovery rate is generally impaired, unless improved the rate of adsorption.This phenomenon can use the characterization of size of mass-transfer zone (MTZ) ideally, namely declines with the implantation degree of depth, and the mark that mass-transfer zone accounts for adsorbent bed increases.Because for heavy constituent, adsorbent utilization rate is much lower at equilibrium area in MTZ internal ratio, therefore along with this mark increases, displacement volume (such as Δ N
2load) decline.
Do many effort and attempt more perspicuously to associate the character of sorbing material and their performances in process cycles.Knownly can improve mass transfer rate with less absorbent particles and be included in during circulation improves: (1) Sircar (US5 071 449) adopts bi adsorbing layer separately, (2) Hirooka etc. (US5 122 164) adopt short circulation timei and sequential steps, and (3) Hay etc. (US5 176 721) are having in cross-flow varigrained bed.Gaffney etc. have determined the practical range of values of following Material Balance combination of properties with circulating research: the amount (US5 258 060) of (1) isothermal displacement volume and inert diluent; (2) isothermal displacement volume and selective (US5 266 102).
These examples of prior art are two kinds of typical methods of interaction balance-selective absorbent character and processing performance.In first method, adsorbent is formed fixing, then by regulating granularity and bed design consider respectively and regulate mass transfer.In second method, change adsorbent composition thus change equilibrium property, then measuring mass transfer (if overall consideration).
Finally, the zeolite pore porosity that Moreau etc. (US5 672 195) suggestion is higher is to improve the O of PSA air separation
2productive rate and output.Be combined the preferred porosity ranges that require that 0.38 to 0.60 with minimum velocity coefficient in claim.Moreau addresses the zeolite that is purchased because of porosity and not to be suitable for their invention lower than 0.36.Moreau does not propose the effect of highly porous obvious skew.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of nitrogen adsorption agent.
For reaching this object, the present invention by the following technical solutions:
A preparation method for nitrogen adsorption agent, described adsorbent take ZSM-11 as carrier, precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
The equilibrium response of the intrinsic sorption rate characteristic of nitrogen adsorption agent prepared by this preparation method and sorbing material improves, and has higher adsorption rate.
Detailed description of the invention
Embodiment 1
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 4 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 2
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 5 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 3
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 6 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 4
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 7 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 5
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 6
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 7
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 8
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:4:1-2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Embodiment 9
Precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Claims (1)
1. a preparation method for nitrogen adsorption agent, is characterized in that: described adsorbent is carrier with ZSM-11, precipitation deposition calcium, magnesium, titanium, aluminium salt thus obtain nitrogen adsorption agent on carrier, concrete grammar is: in the calcium salt soln of 3-8wt%, add magnesium salts, titanium salt and aluminium salt, stir, make calcium in mixed liquor, magnesium, titanium, the mass ratio of aluminium is 6-8:2-3:3-4:1-2, ZSM-11 carrier is added in mixing, addition is 4-8 times of calcareous amount, the alkaline solution that concentration is 2-4mol/L is at the uniform velocity dripped subsequently in mixed liquor, alkaline matter is selected from NaOH, potassium hydroxide, ammoniacal liquor, the pH value of mixed liquor is made to reach 10 ~ 12, filtration obtains solid matter, repeatedly wash by ethanol and deionized water and remove solid matter surface impurity, solid matter is dry at 100-120 DEG C subsequently, last in atmosphere 400-500 DEG C roasting 2-4 hour, and at 700-800 DEG C roasting 2-4 hour in atmosphere, obtain nitrogen adsorption agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410617880.7A CN104437352A (en) | 2014-11-05 | 2014-11-05 | Preparation method of nitrogen adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410617880.7A CN104437352A (en) | 2014-11-05 | 2014-11-05 | Preparation method of nitrogen adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104437352A true CN104437352A (en) | 2015-03-25 |
Family
ID=52884562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410617880.7A Pending CN104437352A (en) | 2014-11-05 | 2014-11-05 | Preparation method of nitrogen adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437352A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649051A (en) * | 2012-05-15 | 2012-08-29 | 西南科技大学 | Preparation method of starch ester adsorbing material |
| JP2013000624A (en) * | 2011-06-14 | 2013-01-07 | Kasai:Kk | Boron adsorbent and manufacturing method therefor |
| CN102908978A (en) * | 2012-11-12 | 2013-02-06 | 江西理工大学 | Method for preparing efficient adsorbent through in-situ reaction |
-
2014
- 2014-11-05 CN CN201410617880.7A patent/CN104437352A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013000624A (en) * | 2011-06-14 | 2013-01-07 | Kasai:Kk | Boron adsorbent and manufacturing method therefor |
| CN102649051A (en) * | 2012-05-15 | 2012-08-29 | 西南科技大学 | Preparation method of starch ester adsorbing material |
| CN102908978A (en) * | 2012-11-12 | 2013-02-06 | 江西理工大学 | Method for preparing efficient adsorbent through in-situ reaction |
Non-Patent Citations (1)
| Title |
|---|
| 于庆君等: "纳米棒插接形貌ZSM-11基多孔分子筛材料的催化裂化性能研究", 《石油炼制与化工》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100377776C (en) | Method for preparing molecular sieve absorbent with high adsorption capacity | |
| KR100480219B1 (en) | Argon/oxygen selective x-zeolite | |
| US6537348B1 (en) | Method of adsorptive separation of carbon dioxide | |
| CN104907045B (en) | High-efficiency carbon dioxide material for trapping | |
| US6572838B1 (en) | Process for the preparation of molecular sieve adsorbent for selective adsorption of nitrogen and argon | |
| CN103785349B (en) | Preparation method of solid amine gas adsorption material | |
| CN110862631B (en) | Preparation method of efficient recyclable lithium extraction membrane material for salt lake brine | |
| CN100343399C (en) | Process for extracting lithium from salt lake brine by manganese dioxide | |
| CN102784624A (en) | Preparation method and use of carbon coated magnetic adsorption material | |
| CN109608655A (en) | A kind of bifunctional group MOFs material and the preparation method and application thereof | |
| JPH07194920A (en) | Augmented gas separation and zeolite composition therefor | |
| CN104437443B (en) | A kind of activation method improving adsorbing material storage natural gas performance | |
| CN106215911B (en) | It is a kind of to be used to detach high-efficiency adsorbent of CO and preparation method thereof | |
| CN101961640B (en) | Modified silica gel air drying agent and preparation method thereof | |
| CN110237823B (en) | Metal organic framework material with ethane preferential adsorption function and preparation method thereof | |
| RU2297276C2 (en) | Method of production of adsorbent-molecular sieve for selective adsorption of nitrogen and argon | |
| KR20130106989A (en) | Continuous oxygen separation method and apparatus using oxygen selective sorbent | |
| CN106588951B (en) | A kind of porous metal-organic framework compound and its preparation method and application based on zinc | |
| CN104437352A (en) | Preparation method of nitrogen adsorbent | |
| CN108607500A (en) | A kind of gel adsorber and preparation method carrying lithium for salt lake brine with high magnesium-lithium ratio | |
| CN111533145A (en) | Method for recovering lithium from byproduct mirabilite mother liquor of lithium oxide hydrogen production from spodumene | |
| CN110548481B (en) | Hollow-structure CO adsorbent with nano CuO coated by Y-type molecular sieve and preparation method and application thereof | |
| CN113117643A (en) | Modified biomass charcoal adsorption material, preparation method and application thereof, and method for regenerating modified biomass charcoal adsorption material | |
| CN105797678A (en) | Compound type intermediate-temperature carbon dioxide adsorbent and preparation method thereof | |
| CN103933933A (en) | Ce-LiX high-performance oxygen adsorption material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150325 |
|
| RJ01 | Rejection of invention patent application after publication |