CN114405464B - High-efficiency oxygen-making molecular sieve and preparation method thereof - Google Patents
High-efficiency oxygen-making molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 167
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 41
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 14
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 abstract description 33
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 150000002926 oxygen Chemical class 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000001179 sorption measurement Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- 238000001035 drying Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
- C01B13/027—Zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- 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
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/0018—Zeolites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention provides a high-efficiency oxygen-making molecular sieve and a preparation method thereof, belonging to the field of molecular sieves. The preparation method comprises the following steps: mordenite with a silicon-aluminum molar ratio of 10-20:1 and Ca 2+ Mixing the exchange solutions, performing ion exchange, and roasting to obtain a Ca-MOR molecular sieve; the Ca-MOR molecular sieve and the binder are mixed according to the mass ratio of 80-90: 10-20, and the rolling ball is formed and baked. The surface of the oxygen-making molecular sieve is hydrophobic, is little influenced by water vapor in the use process, and has strong hydrothermal stability; this oxygen-producing molecular sieve and N 2 The effect of the catalyst is strong, and the nitrogen-oxygen separation effect is good; the molecular sieve has stable structure, can be recycled and has long service life.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a high-efficiency oxygen-making molecular sieve and a preparation method thereof.
Background
The application of oxygen is very wide, the traditional method for obtaining oxygen is a cryogenic method, but the method has large investment and high energy consumption, and is only suitable for large-scale oxygen production. Along with the rapid development of pressure swing adsorption technology, pressure swing adsorption separation oxygen production technology is increasingly widely used. The core of pressure swing adsorption oxygen production is the development of adsorbents, the current oxygen production adsorbents are mainly molecular sieves, and the oxygen production adsorbents are prepared from the initial AThe molecular sieve is a later X-type molecular sieve and an LSX-type molecular sieve, and then the Li-LSX molecular sieve with the best oxygen production performance and high lithium exchange degree is acknowledged at present. However, the Li-LSX molecular sieve adsorbent has the advantages of long preparation process flow, multiple influencing factors and multiple exchange requirements to lead Li to be present + The exchange degree is higher than 70 percent, so that the good oxygen production effect can be achieved. Chinese patent CN101380565A, CN113264538A discloses a molecular sieve of LiNaKLSX, the exchange degree of Li reaches more than 90%, the exchange times sometimes need 8-10 times, the cost of Li exchange accounts for 70-80% of the preparation cost of the adsorbent, the operation is complex and complicated, and the Li price is high, and the production cost is high.
Chinese patent CN101708456 a selects a Ca multiple exchange LSX molecular sieve with low price, but the oxygen production effect is inferior to Li-LSX molecular sieve; chinese patent CN 107486146A, CN 108854947A, CN108862303A carries out ion exchange on LSX molecular sieve through Ag, sr, ca-Li and other ions, but the Na and K contents are reduced to a certain degree by exchanging for a plurality of times, so that the oxygen production performance is improved.
The LSX molecular sieve has a silicon-aluminum ratio slightly larger than 2, has strong acting force with polar water molecules, and greatly reduces the oxygen production capacity due to the existence of water when the LSX molecular sieve is used for producing oxygen by space division. Meanwhile, the LSX molecular sieve has poor hydrothermal stability, the structure can be destroyed after multiple times of activation, the oxygen production performance is obviously reduced, and the service life is short.
Disclosure of Invention
Aiming at the defects of the existing oxygen-making molecular sieve, the invention provides the high-efficiency oxygen-making molecular sieve and the preparation method thereof, and the oxygen-making performance of the high-efficiency oxygen-making molecular sieve is little influenced by water vapor, and has high stability, good oxygen-making effect and long service life; the high-efficiency oxygen-making molecular sieve has the advantages of simple preparation process, low production cost and high preparation efficiency.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in one aspect, the invention provides a method for preparing an efficient oxygen-making molecular sieve, comprising the following steps:
mordenite (MOR) and Ca with a silicon-aluminum molar ratio of 10-20:1 are mixed 2+ Mixing the exchange solutions, performing ion exchange, and roasting to obtain a Ca-MOR molecular sieve;
mixing Ca-MOR molecular sieve with adhesive, rolling to form and roasting.
Further, in a preferred embodiment of the present invention, mordenite is combined with Ca during the ion-exchange process 2+ The mass ratio of the exchange solution is 1:5-15.
Preferably, mordenite is combined with said Ca 2+ The mass ratio of the exchange solution is 1: 8-12.
Further, in a preferred embodiment of the present invention, the number of times of the ion exchange is 1 to 2 times, each time for 2 to 8 hours.
Preferably, the number of ion exchange times is 1 and the exchange time is 4 to 7 hours.
Further, in the preferred embodiment of the present invention, ca in the ion exchange process 2+ The temperature of the exchange solution is 25-150 ℃.
Preferably, the Ca in the ion exchange process 2+ The temperature of the exchange solution is 50-100 ℃.
Further, in the preferred embodiment of the present invention, the Ca 2+ The Ca source in the exchange solution includes at least one of calcium chloride, calcium nitrate and calcium sulfate.
Further, in the preferred embodiment of the present invention, the Ca 2+ Exchange Ca in solution 2+ Concentration of Na in mordenite + The concentration ratio of (2) is 1.01-3:1.
Preferably, the Ca mentioned above 2+ Exchange Ca in solution 2+ Concentration of (c) and Na in the mordenite + The concentration ratio of (2) is 1.5-2.5:1.
Further, in a preferred embodiment of the present invention, the mass ratio between the Ca-MOR molecular sieve and the binder is 4-12:1.
Preferably, the mass ratio between the Ca-MOR molecular sieve and the binder is 6-10:1;
preferably, the binder mainly comprises at least one of water, kaolin, lignin, methylcellulose, starch and aluminum sol.
Further, in the preferred embodiment of the present invention, the above-mentioned calcination temperature is 500-600 ℃ and the calcination time is 0.5-2.5h.
Preferably, the temperature of the roasting is 520-580 ℃, the time of the first roasting is 1.5-2.5 h, and the time of the second roasting is 0.5-1.5;
on the other hand, the invention also provides a high-efficiency oxygen-making molecular sieve, which is prepared by the preparation method.
Further, in a preferred embodiment of the present invention, ca in the high-efficiency oxygen-producing molecular sieve 2+ The degree of exchange is higher than 50%.
Compared with the prior art, the invention has at least the following beneficial effects:
the oxygen-making molecular sieve provided by the invention has the advantages that the surface is hydrophobic, the influence of water vapor is small in the use process, and the hydrothermal stability is strong; this oxygen-producing molecular sieve and N 2 The effect of the catalyst is strong, and the nitrogen-oxygen separation effect is good; the molecular sieve has stable structure, can be recycled and has long service life.
The preparation method of the oxygen-making molecular sieve provided by the invention uses low-cost calcium to exchange MOR molecular sieve, reduces the consumption of lithium, and can meet the requirement of Ca after ion exchange for 1-2 times 2+ The exchange degree is more than 50%, multiple ion exchange is not needed, the preparation process is simple, the cost is low, and the production efficiency is high.
Drawings
FIG. 1 is an XRD result of an oxygen-generating molecular sieve A1;
FIG. 2 shows the physical adsorption results of the oxygen-generating molecular sieve A1;
FIG. 3 shows the results of nitrogen static adsorption capacity and nitrogen-oxygen selectivity measurement of the oxygen-producing molecular sieve A1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the following examples, which are to be construed as merely illustrative and not limitative of the scope of the invention, but are not intended to limit the scope of the invention to the specific conditions set forth in the examples, either as conventional or manufacturer-suggested, nor are reagents or apparatus employed to identify manufacturers as conventional products available for commercial purchase.
The existing oxygen-making molecular sieve mainly has the problems of high production cost, complex process flow, more oxygen-making performance influencing factors, poor stability and short service life. Aiming at the problems, the invention provides the Ca-MOR oxygen-making molecular sieve which has relatively low cost, simple preparation process, small influence of water vapor on oxygen-making performance, good stability, good oxygen-making effect and long service life.
The technical scheme of the embodiment is as follows:
the preparation method of the high-efficiency oxygen-making molecular sieve comprises the following steps:
step S1: mordenite with a silicon-aluminum molar ratio of 10-20:1 and Ca 2+ Mixing the exchange solutions, performing ion exchange, and roasting to obtain the Ca-MOR molecular sieve.
Mordenite (MOR) is a zeolite molecular sieve having strong polarity, N 2 Is a quadrupole-distance molecule, and can form strong interaction force with cations of a molecular sieve framework; meanwhile, the MOR molecular sieve is provided with a twelve-membered ring main pore canal which is connected by eight-membered rings, N 2 The rotation of the molecule in the pore canal is limited, so N 2 Can be adsorbed well.
The scheme selects mordenite with the silicon-aluminum molar ratio of 10-20:1, preferably, the silicon-aluminum molar ratio of the mordenite is 12-18:1; more preferably, the mordenite has a silica to alumina molar ratio of 15:1. Mordenite has too high a silica alumina content, and the exchangeable cationic sites thereof are reduced, which is disadvantageous for the subsequent Ca 2+ Is a swap of (2); if the mordenite silica-alumina ratio is too low, the hydrophobicity becomes poor, and the oxygen production effect is greatly affected by water vapor. The inventor finds that when the silicon-aluminum mole ratio in mordenite is 15:1 in the experimental research process, the oxygen-making performance of the obtained oxygen-making molecular sieve is better.
Further, in the ion exchange process, mordenite and Ca 2+ The mass ratio of the exchange solution is 1:5-15, preferably, the mass ratio is 1: 8-12; more preferably, the mass ratio is 1:10. Ca in such a mass ratio 2+ The exchange solution is subjected to ion exchange, so that Ca can be effectively improved 2+ Reducing the exchange frequency and exchange efficiencyTime. Further, the ion exchange times are 1 to 2 times; 2 to 8 hours each, preferably 4 to 7 hours each, more preferably 5 hours each. In the invention, the ion exchange is carried out under the condition, and Ca in the high-efficiency oxygen-making molecular sieve can be realized after the exchange for 1 to 2 times 2+ The degree of exchange is higher than 50%, and when Ca 2+ When the exchange degree is higher than 50%, the oxygen generating effect is better. Multiple exchanges are required to exchange Li compared to Li-LSX molecular sieve adsorbents + The method has simple operation, low production cost and high efficiency, and can realize good oxygen production effect only when the exchange degree is higher than 70%.
Further, ca in the ion exchange process 2+ The temperature of the exchange solution is 25-150 ℃, and Ca at 150 ℃ can be realized in practice by a hot-press exchange method 2+ Ion exchange. Preferably, the ion exchange temperature is 50-100 ℃; more preferably, the ion exchange temperature is 80 ℃. Further, the Ca 2+ Exchange Ca in solution 2+ Concentration of Na in mordenite + The concentration ratio of (2) is 1.01-3:1; preferably, the concentration ratio is 1.5-2.5:1; more preferably, the concentration ratio is 2:1. Increasing Ca 2+ The temperature and concentration of the exchange solution help to accelerate Ca 2+ With Na in mordenite + Is a switching speed of (a). The inventor has found that, when Ca 2+ The temperature of the exchange solution was 80℃and Ca 2+ Concentration of Na in mordenite + When the concentration ratio of Ca to Ca is 2:1 2+ Is optimal.
Further, in the preferred embodiment of the present invention, the Ca 2+ The Ca source in the exchange solution includes at least one of calcium chloride, calcium nitrate and calcium sulfate. More preferably, the Ca source is calcium chloride.
Further, the above-mentioned calcination temperature is 500 to 600 ℃, preferably 520 to 580 ℃; more preferably, the temperature is 550 ℃; the calcination time is 0.5 to 2.5 hours, preferably 1.5 to 2.2 hours, more preferably 2 hours. A high-temperature roasting step, on the one hand, ca can be removed 2+ To bind water to make Ca 2+ Enters into a molecular sieve pore canal; on the other hand removeThe water in the molecular sieve is low in water content, so that the competitive adsorption of water and nitrogen is reduced.
Step S2: mixing Ca-MOR molecular sieve with adhesive, rolling to form and roasting.
Further, the mass ratio between the Ca-MOR molecular sieve and the binder is 4-12:1, preferably 6-10:1. In this step, the binder only plays a role of shaping the powder of the ca—mor molecular sieve, and therefore, the selection of the binder is not particularly limited as long as the object of the present invention is not restricted. Further, the binder is preferably water or an organic binder, and more preferably, the binder mainly includes at least one of water, kaolin, lignin, methylcellulose, starch, and aluminum sol.
Further, the above-mentioned calcination temperature is 500 to 600 ℃, preferably 520 to 580 ℃; more preferably, the temperature is 550 ℃; the calcination time is 0.5 to 2.5 hours, preferably 0.5 to 1.5 hours, more preferably 1 hour. Through high-temperature roasting, the Ca-MOR molecular sieve can be bonded and formed to form a stable space structure, so that the service life of the oxygen-making molecular sieve is prolonged.
On the other hand, the invention also provides a high-efficiency oxygen-making molecular sieve, which is prepared by the preparation method. Further, ca in the high-efficiency oxygen-producing molecular sieve 2+ The degree of exchange is higher than 50%. The surface of the oxygen-making molecular sieve is hydrophobic, is little influenced by water vapor in the use process, and has strong hydrothermal stability; this oxygen-producing molecular sieve and N 2 The effect of the catalyst is strong, and the nitrogen-oxygen separation effect is good; the molecular sieve has stable structure, can be recycled and has long service life.
Example 1
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
adding 5g of calcium chloride into 500g of water, uniformly stirring, adding 50g of MOR molecular sieve powder (silicon-aluminum molar ratio is 15:1), carrying out ion exchange for 5 hours at 80 ℃ under stirring, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve powder.
The molecular sieve A1 is prepared by uniformly mixing 40g of prepared molecular sieve powder, 2.7g of water, 0.5g of kaolin and 0.8g of lignin, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h.
Example 2
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
adding 5g of calcium chloride into 500g of water, uniformly stirring, adding 50g of MOR molecular sieve powder (the molar ratio of silicon to aluminum is 15:1), carrying out ion exchange for 5 hours at 80 ℃ under the stirring condition, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve powder Ca-MOR-1.
Adding 5g of calcium chloride into 400g of water, uniformly stirring, adding 40g of Ca-MOR-1 molecular sieve powder, carrying out ion exchange for 5 hours at 80 ℃ under the stirring condition, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve powder Ca-MOR-2.
The molecular sieve powder 35gCa-MOR-2, 2.76g of water, 0.44g of kaolin and 0.7g of lignin are uniformly mixed, formed on a ball mill, dried overnight at 110 ℃, and then baked at 550 ℃ for 1 hour to prepare the oxygen-producing molecular sieve A2.
Example 3
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
adding 5g of calcium chloride into 500g of water, uniformly stirring, adding 50g of MOR molecular sieve powder (silicon-aluminum molar ratio is 15:1), carrying out ion exchange for 5 hours at 25 ℃ under stirring, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve powder.
Uniformly mixing 40g of the prepared molecular sieve powder, 2.7g of water, 0.5g of kaolin and 0.8g of lignin, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h to prepare the oxygen-making molecular sieve A3.
Example 4
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
5g of calcium chloride is added into 500g of water, stirred uniformly, 50g of MOR molecular sieve powder (silicon-aluminum mol ratio is 15:1) is added, ion exchange is carried out for 2 hours at 150 ℃ under stirring, filtration, washing and drying are carried out, and high-temperature roasting is carried out for 2 hours at 550 ℃ in a muffle furnace, thus obtaining the molecular sieve powder.
The molecular sieve powder 40g, water 2.7g, kaolin 0.5g and lignin 0.8g are mixed uniformly, formed on a ball mill, dried at 110 ℃ overnight, and then baked at 550 ℃ for 1h to prepare the oxygen-producing molecular sieve A4.
Example 5
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
adding 5g of calcium chloride into 500g of water, uniformly stirring, adding 50g of MOR molecular sieve powder (the molar ratio of silicon to aluminum is 10:1), carrying out ion exchange for 5 hours at 50 ℃ under the stirring condition, filtering, washing, drying, and roasting for 2.5 hours at 500 ℃ in a muffle furnace to obtain the molecular sieve powder.
40g of the prepared molecular sieve powder and 0.35g of starch are uniformly mixed, formed on a ball mill, dried overnight at 110 ℃, and then baked at 500 ℃ for 1.5 hours to prepare the oxygen-producing molecular sieve A5.
Example 6
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
5g of calcium chloride is added into 500g of water, stirred uniformly, 50g of MOR molecular sieve powder (silicon-aluminum molar ratio is 20:1) is added, ion exchange is carried out for 8 hours at 120 ℃ under the stirring condition, filtration, washing and drying are carried out, and high-temperature roasting is carried out for 2 hours at 580 ℃ in a muffle furnace, thus obtaining the molecular sieve powder.
Mixing 40g of the prepared molecular sieve powder and 10.0g of methyl cellulose uniformly, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h to prepare the oxygen-producing molecular sieve A6.
Example 7
The embodiment provides a high-efficiency oxygen-making molecular sieve, and the preparation method comprises the following steps:
adding 5g of calcium chloride into 500g of water, uniformly stirring, adding 50g of MOR molecular sieve powder (silicon-aluminum molar ratio is 17:1), carrying out ion exchange for 2 hours at 100 ℃ under stirring, filtering, washing, drying, and roasting for 1.5 hours at 600 ℃ in a muffle furnace to obtain the molecular sieve powder Ca-MOR-1.
Adding 5g of calcium chloride into 400g of water, uniformly stirring, adding 40g of Ca-MOR-1 molecular sieve powder, carrying out ion exchange for 8 hours at 100 ℃ under the stirring condition, filtering, washing, drying, and roasting for 1.5 hours at 600 ℃ in a muffle furnace to obtain the molecular sieve powder Ca-MOR-2.
Uniformly mixing 35gCa-MOR-2 molecular sieve powder and 4.0g of aluminum sol, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 600 ℃ for 0.5h to prepare the oxygen-producing molecular sieve A7.
Comparative example 1
The comparative example provides an oxygen-making molecular sieve Ca-LSX molecular sieve, the preparation method comprises the following steps:
100g of calcium chloride is added into 500g of water, stirred uniformly, 50g of LSX molecular sieve powder is added, ion exchange is carried out for 5 hours at 80 ℃ under the stirring condition, filtration, washing and drying are carried out, and high-temperature roasting is carried out for 2 hours at 550 ℃ in a muffle furnace, thus obtaining the molecular sieve powder.
Uniformly mixing 40g of the prepared molecular sieve powder, 2.7g of water, 0.5g of kaolin and 0.8g of lignin, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h to prepare the oxygen-making molecular sieve B1.
Comparative example 2
This comparative example provides a Li-LSX molecular sieve, the method of preparation comprising:
adding 50g of lithium chloride into 500g of water, uniformly stirring, adding 50g of LSX molecular sieve powder, carrying out ion exchange for 5 hours at 80 ℃ under the stirring condition, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain the molecular sieve powder. Uniformly mixing 40g of the prepared molecular sieve powder, 2.7g of water, 0.5g of kaolin and 0.8g of lignin, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h to prepare the oxygen-making molecular sieve B2.
Comparative example 3
This comparative example provides a Li-LSX molecular sieve, the method of preparation comprising:
adding 110g of lithium chloride into 1100g of water, uniformly stirring, adding 110g of LSX molecular sieve powder, carrying out ion exchange for 5 hours at 80 ℃ under the stirring condition, filtering, washing, drying, and roasting for 2 hours at 550 ℃ in a muffle furnace to obtain molecular sieve powder Li-LSX-1;
and continuing Li exchange according to the exchange steps, wherein the concentration of the lithium ions at the next time is 1.2 times of that at the last time, and continuously exchanging for 8 times to obtain the molecular sieve powder Li-LSX-8.
Uniformly mixing 40g of Li-LSX-8 molecular sieve powder, 2.7g of water, 0.5g of kaolin and 0.8g of lignin, forming on a ball mill, drying at 110 ℃ overnight, and roasting at 550 ℃ for 1h to prepare the oxygen-making molecular sieve B3.
The beneficial effects of the invention are described below with reference to experimental examples:
experimental example 1 structural characterization
The oxygen-generating molecular sieves A1-A7 of the above examples 1-7 were subjected to material characterization, which showed that the structure of the oxygen-generating molecular sieve was MOR, wherein the oxygen-generating molecular sieve A1 was taken as an example, and the material characterization results were as follows:
fig. 1 shows XRD characterization results of the oxygen-producing molecular sieve A1. It can be seen that the molecular sieve is mordenite, has good crystallinity and no other impurity crystals.
FIG. 2 shows the result of physical adsorption of the oxygen-producing molecular sieve A1. It can be seen that the molecular sieve contains a large number of micropores, the pore volume is large, and the nitrogen adsorption capacity is high.
Table 1 shows the sodium ion exchange results of the oxygen-generating molecular sieves A1-A7. It can be seen that the exchange degree is higher than 50% in the examples, and the ion exchange degree of the molecular sieves with different Si/Al ratios is different.
TABLE 1 ion exchange results for different molecular sieves
| Molecular sieve samples | A1 | A2 | A3 | A4 | A5 | A6 | A7 | B1 | B2 | B3 |
| Sodium ion exchange degree (%) | 62 | 69 | 59 | 71 | 73 | 55 | 58 | 76 | 54 | 75 |
Experimental example 2 performance test
The oxygen-generating molecular sieves A1 to A7 prepared in the above examples 1 to 7 and the molecular sieves B1 to B3 prepared in the comparative examples were subjected to nitrogen adsorption amount and nitrogen-oxygen separation performance test:
static adsorption amount measurement of nitrogen: pretreating molecular sieve at 350deg.C under vacuumizing for 12 hr, and adsorbing nitrogen gas with static adsorption instrument (Rise-1030) at 25deg.C under 10 -2 100KPa, the nitrogen adsorption of the sample was obtained.
Nitrogen oxygen selectivity determination: molecular sieve under the condition of vacuumizingPretreating at 350deg.C for 12 hr, and adsorbing nitrogen and oxygen with static adsorption instrument (Rise-1030) at 25deg.C under 10 -2 100KPa, the nitrogen and oxygen adsorption capacity of the sample is obtained respectively, and the nitrogen-oxygen separation coefficient is calculated.
The nitrogen-oxygen separation coefficient α is the ratio of the equilibrium adsorption amount of nitrogen-oxygen in the adsorption phase to the equilibrium mole fraction of nitrogen-oxygen in the gas phase.
X-equilibrium adsorption amount of adsorbate in the adsorption phase;
y—equilibrium mole fraction of adsorbate in the gas phase.
FIG. 3 shows the results of nitrogen static adsorption capacity and nitrogen-oxygen selectivity measurement of the oxygen-producing molecular sieve A1. It can be seen that the molecular sieve has high nitrogen static adsorption and good nitrogen-oxygen selectivity.
Table 2 shows the results of nitrogen static adsorption capacity and nitrogen-oxygen separation coefficient test of the oxygen-making molecular sieves A1-A7.
TABLE 2 results of static adsorption of Nitrogen and Nitrogen-oxygen separation coefficients for different molecular sieves
As can be seen from Table 2, the Ca-MOR oxygen-making molecular sieve of the invention has large oxygen-nitrogen separation coefficient, namely good nitrogen-oxygen selectivity; meanwhile, when the air contains a small amount of water, the nitrogen-oxygen selectivity of the molecular sieve in the comparative example is obviously reduced, but the oxygen-nitrogen separation coefficient of the Ca-MOR oxygen-making molecular sieve is still kept at a higher level, namely, the influence of water vapor is small; meanwhile, the Ca-MOR oxygen-making molecular sieve provided by the invention has good nitrogen-oxygen selectivity after high-temperature treatment, which proves that the sample has excellent thermal stability.
In conclusion, the surface of the oxygen-making molecular sieve provided by the embodiment is hydrophobic, and the oxygen-making molecular sieve is less influenced by water vapor in the use process and has strong hydrothermal stability; the molecular sieve for preparing oxygenN 2 The effect of the catalyst is strong, and the nitrogen-oxygen separation effect is good; the molecular sieve has stable structure, can be recycled and has long service life. The preparation method of the oxygen-making molecular sieve uses low-cost calcium to exchange MOR molecular sieve, reduces the consumption of lithium, and simultaneously can meet Ca after 1-2 times of ion exchange 2+ The exchange degree is more than 50%, multiple ion exchange is not needed, the preparation process is simple, the cost is low, and the production efficiency is high.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-efficiency oxygen-making molecular sieve is characterized by comprising the following steps:
mordenite with a silicon-aluminum molar ratio of 15:1 and Ca 2+ Mixing the exchange solutions, performing ion exchange, and performing first roasting to obtain a Ca-MOR molecular sieve;
mixing the Ca-MOR molecular sieve with a binder, and performing rolling ball forming and second roasting to obtain the high-efficiency oxygen-making molecular sieve;
the mass ratio of the Ca-MOR molecular sieve to the binder is 4-12:1, the temperature of the first roasting and the second roasting is 520-580 ℃, the time of the first roasting is 1.5-2.5 h, and the time of the second roasting is 0.5-1.5 h; ca in the high-efficiency oxygen-making molecular sieve 2+ The degree of exchange is higher than 50%.
2. The method for preparing high-efficiency oxygen-generating molecular sieve according to claim 1, wherein in the ion exchange process, the mordenite and the Ca 2+ The mass ratio of the exchange solution is 1:5-15.
3. The method for preparing high-efficiency oxygen-generating molecular sieve according to claim 1, wherein in the ion exchange process, the mordenite and the Ca 2+ The mass ratio of the exchange solution is1：8~12。
4. The method for preparing the high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the ion exchange time is 1-2 times, and each time is 2-8 hours.
5. The method for preparing the high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the ion exchange is performed for 1 time, and the exchange time is 4-7 hours.
6. The method for preparing high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the Ca in the ion exchange process 2+ The temperature of the exchange solution is 25-150 ℃.
7. The method for preparing high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the Ca in the ion exchange process 2+ The temperature of the exchange solution is 50-100 ℃.
8. The method for preparing the high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the Ca 2+ The Ca source in the exchange solution includes at least one of calcium chloride and calcium nitrate.
9. The method for preparing the high-efficiency oxygen-generating molecular sieve according to claim 1, wherein the mass ratio between the Ca-MOR molecular sieve and the binder is 6-10:1; the binder includes at least one of water, kaolin, lignin, methylcellulose, starch, and aluminum sol.
10. The efficient oxygen-making molecular sieve is characterized in that the efficient oxygen-making molecular sieve is prepared by adopting the preparation method of any one of claims 1-9.
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| JPH0656404A (en) * | 1992-06-15 | 1994-03-01 | Gold Star Co Ltd | Preparation of adsorbent for oxygen generator |
| CN113371730A (en) * | 2021-06-02 | 2021-09-10 | 昊华化工科技集团股份有限公司 | Modified calcium low-silicon zeolite molecular sieve and preparation method thereof |
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