CN111686680B - Sodium ion adsorbent and preparation method and application thereof - Google Patents
Sodium ion adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a sodium ion adsorbent, which comprises the following components: 10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 10 to 30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And 40 to 80 parts by mass of LiTi 2 (PO 4 ) 3 . The invention also provides a method for preparing the sodium ion adsorbent. The invention also provides the use of a sodium ion adsorbent of the invention or of a sodium ion adsorbent prepared by a process of the invention for removing sodium ions under gas-solid phase conditions, preferably at 300-600 ℃ in a gas-solid phase conditions, more preferably at 300-600 ℃ in a catalyst bed of a gas-solid phase reactor. The adsorbent of the invention has high thermal stability and high adsorption selectivity under high-temperature gas-solid phase.
Description
Technical Field
The invention belongs to the field of chemical industry. Specifically, the invention relates to a sodium ion adsorbent, and a preparation method and application thereof.
Background
In general, the sodium ions to be removed from the water are ion-exchanged using a cation exchange resin. However, after the ion exchange resin is used for a certain period of time, the deionization efficiency is decreased due to the gradual saturation of functional groups, and the deterioration of water quality is caused. Thus, in chemical production, when water enters the reactor as process steam or reaction raw material, trace sodium ions are inevitably carried, and the sodium ions are fatal poisons for the acid catalyst, and after long-term accumulation, the performance of the catalyst is reduced, so that the device is stopped or overhauled in advance.
For example, a ZSM-5 type catalyst is used in a Methanol To Propylene (MTP) plant, the reaction is an acid catalyzed reaction, about 30% process steam is added to the reaction feed, and the sodium ion mass content is required to be not higher than 60ppb. In a certain operation period, the sodium content in the reaction raw materials is 300ppm, so that the temperature rise of a catalyst deactivation bed layer is avoided after the first-stage catalyst of the reactor operates for 2500 hours; after 4000 hours of operation, the temperature of the catalyst of the second-stage catalyst deactivation bed layer does not rise, and the sodium poisoning causes the operation life of the catalyst to be greatly lower than the design value of 8000 hours.
In the prior art, an inorganic sodium removal adsorbent is mainly used in a liquid-solid phase system in fine chemical production to remove sodium ions in a solution. For example, li Xinyun et al (proceedings of Beijing university of industry, 1993, 19 (3): 27-31) reported that when antimonic acid loaded on silica gel is used as a sodium removal agent, the sodium content in mineral water is reduced from 82.54ppm to 0.03ppm after sodium removal treatment, but the operation temperature is lower (<At 30 deg.C). Zhu Chao beam et al (salt and chemical industry, 2012, 41 (8): 4-7) reported that the precursor NaMnO of sodium manganese oxide is prepared by adopting the conventional powder sintering method of oxide 2 The adsorbent is used for detecting Na in solution + The adsorption performance of (3). CN108014743A discloses a sodium ion characteristic adsorbent and a preparation method thereof, the adsorbent has a three-dimensional framework structure and a molecular formula of Na 1.6 Al 1.4 Si 1.4 (PO 4 ) 3 ·XCa 3 (PO 4 ) 2 The adsorbent can spontaneously absorb sodium ions in a tungsten solution containing sodium, and the sodium removal rate is up to more than 98%. CN105833830A discloses Na x MnO 2 The ion sieve type sodium adsorbent can be applied to removing impurity sodium in lithium chloride solution.
The prior art does not disclose a sodium ion adsorbent under gas-solid phase high temperature conditions and a preparation method thereof. In order to avoid the catalyst alkali poisoning, a layer of sodium ion adsorbent is added in a catalyst bed layer of the gas-solid multiphase reactor, so that the method is efficient, simple and convenient. Since most of the gas-solid phases are under high temperature and high pressure conditions, the adsorbent is required to have suitable molding strength, high thermal stability and sodium ion adsorption characteristics.
Disclosure of Invention
The invention aims to provide a sodium ion adsorbent suitable for gas-solid phase conditions and a preparation method thereof. The adsorbent of the invention has high thermal stability and high adsorption selectivity under high-temperature gas-solid phase.
The above object of the present invention is achieved by the following means.
In the context of the present invention, the term "NASICON" is an abbreviation for Na superior Conductor, which was first formed by Na + Conducting compound Na 1+x Zr 2 Si x P 3-x O 12 (X = 0-3) is named, and the crystal structure is formed by ZrO distributed at each corner 6 Polyhedron and PO 4 The tetrahedron is composed of three-dimensional framework, and sodium ions can move through narrow gaps between two different series of lattice nodes in the framework (see figure 1). The substitution of Zr with a transition metal of valence 3 or 4 does not alter its crystal structure, so Nasicon is also a generic term for this class of compounds, and the general formula of the non-silicon containing compound can be represented as Na n M 2 (PO 4 ) 3 (wherein n =3 when the transition metal M has a valence of 3; and n =1 when the transition metal M has a valence of 4).
In the present invention, na is not changed n M 2 (PO 4 ) 3 On the premise of the NASICON type skeleton structure, when sodium ions in the structure are replaced by other ions to form a gap structure, the sodium ions can be adsorbed with high selectivity, and Na is used in the invention + By substitution with Li + Due to Li + With Na + Is a family element and has a small radius (Na) + Ion radius of 0.102nm, li + 0.076 nm), na + The substituted sodium ion can obtain a certain size regular gap structure, and the gap has characteristic screening and memory effects on the original sodium ion, so that the sodium ion can be selectively adsorbed when the substance is contacted with the sodium ion in a gas phase medium or a liquid phase.
In a first aspect, the present invention provides a sodium ion adsorbent comprising the following components:
10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ,
10 to 30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And
40-80 parts by mass of LiTi 2 (PO 4 ) 3 。
Preferably, the sodium ion adsorbent of the present invention consists of:
10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ,
10 to 30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And
40 to 80 parts by mass of LiTi 2 (PO 4 ) 3 。
In a second aspect, the present invention provides a process for preparing the sodium ion adsorbent of the present invention, comprising the steps of:
(1) Taking a lithium-containing compound, an iron-containing or vanadium-containing compound and a phosphorus-containing compound as raw materials, weighing and mixing the raw materials according to the atomic ratio of Li to Fe to P or Li to V to P of 3; mechanically grinding the product after the first roasting by a planet ball mill, and then carrying out second roasting to prepare Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ;
(2) The method comprises the following steps of taking a lithium-containing compound, a tin-containing or manganese-containing compound and a phosphorus-containing compound as raw materials, weighing and mixing the raw materials according to the atomic ratio of Li to Sn to P or Li to Mn to P of 1 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 ;
(3) Lithium-containing compound, titanium dioxide and phosphorus-containing compound are used as raw materials, and the ratio of Li to Ti to P is 1:2:3 proportioning and weighingGrinding and mixing uniformly, then carrying out fifth roasting, mechanically grinding the product after the fifth roasting by a planet ball mill, and then carrying out sixth roasting to prepare LiTi 2 (PO 4 ) 3 ;
(4) Li prepared in the step (1) 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 The LiSn prepared in the step (2) 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 The LiTi prepared in the step (3) 2 (PO 4 ) 3 Uniformly mixing, tabletting and forming, and then carrying out static isobaric treatment;
(5) And (5) carrying out seventh roasting on the sample obtained in the step (4) to prepare the sodium ion adsorbent.
Preferably, in the method of the present invention, the lithium-containing compound is one or more of lithium carbonate, lithium nitrate, lithium chloride and lithium oxide.
Preferably, in the method of the present invention, the iron-containing compound is one or more of ferric nitrate, ferric chloride and ferric trioxide.
Preferably, in the method of the present invention, the vanadium-containing compound is VCl 3 And/or V 2 O 3 ;
Preferably, in the method of the present invention, the phosphorus-containing compound is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid.
Preferably, in the method of the present invention, the tin-containing compound is one or more of tin nitrate, tin tetrachloride and tin oxide.
Preferably, in the method of the present invention, the manganese-containing compound is one or more of manganese dioxide, manganese oxide and manganomanganic oxide.
Preferably, in the method of the present invention, the first firing in the step (1) is performed under the following conditions: the roasting temperature is 300-400 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the second firing in the step (1) is performed under the following conditions: the roasting temperature is 700-900 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the third firing in the step (2) is performed under the following conditions: the roasting temperature is 200-300 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the fourth firing in the step (2) is performed under the following conditions: the roasting temperature is 500-700 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the fifth roasting in the step (3) is performed under the following conditions: the roasting temperature is 300-400 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the sixth calcination in the step (3) is performed under the following conditions: the roasting temperature is 600-700 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the seventh firing in the step (5) is performed under the following conditions: the roasting temperature is 1000-1500 ℃, and the roasting time is 4-8h.
Preferably, in the method of the present invention, the seventh firing in the step (5) is performed under the following conditions: the roasting temperature is 1100-1200 ℃, and the roasting time is 6-8h.
Preferably, in the method of the present invention, the isostatic pressing treatment in step (4) is performed under the following conditions: treating for 4-8h under the pressure of 200-700 MPa.
Preferably, in the method of the present invention, the isostatic pressing treatment in step (4) is performed under the following conditions: treating for 4-5h under the pressure of 300-500 MPa.
Preferably, in the method of the present invention, the mechanical milling in the planetary ball mill in the steps (1), (2) and (3) is performed under the following conditions: ball specification: phi 6-10mm, the mass ratio of the ball material is 10-20:1, the rotating speed is 300-600rpm, and the ball milling time is 5-10h.
Preferably, in the method of the present invention, the Li obtained in step (1) 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 The LiSn prepared in the step (2) 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 The LiTi prepared in the step (3) 2 (PO 4 ) 3 The uniform mixing of (a) is carried out at the following ratio:
10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ,
10 to 30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And
40 to 80 parts by mass of LiTi 2 (PO 4 ) 3 。
In a third aspect, the present invention provides the use of a sodium ion adsorbent of the present invention or of a sodium ion adsorbent produced by a process of the present invention for removing sodium ions in a gas-solid phase, preferably at 300 to 600 ℃ and more preferably in a catalyst bed of a gas-solid phase reactor at 300 to 600 ℃.
The invention has the following beneficial effects:
li due to the different physical properties of the transition metal ions n M 2 (PO 4 ) 3 (wherein n =3 when the transition metal M has a valence of 3; and n =1 when the transition metal M has a valence of 4) the compound has a greatly changed conductive property. If the transition metal ion is not susceptible to valence change reaction and the resulting compound has a small electronic conductance, it can be used as a solid electrolyte. If the transition metal ions are easy to generate valence-change reaction, the material can be prepared into anode and cathode materials according to the potential. In the present invention, since Ti 4+ Is not easy to generate valence-change reaction, and LiTi 2 (PO 4 ) 3 Can be used as electrolyte. Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 Fe in (1) 3+ 、V 3+ Is easy to change from low price to high price and can be used as a positive electrode material. LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 Sn in (1) 4+ Or Mn 4+ Is easy to change from high price to low price and can be used as a cathode material. The inventor unexpectedly finds that after three different conductive materials are combined into a battery-like material combination of 'anode + electrolyte + cathode' according to a certain proportion, the adsorption capacity of the material on sodium ions is improved. Because the three materials have high heat stability and good structural strength after flaking molding, densification treatment and sintering, the material can be applied to a large-scale chemical reaction device to efficiently adsorb sodium ions in reaction raw materials when being in gas-solid phase contact at a high temperature of 300-600 ℃.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a schematic representation of the crystal structure of a NASICON type compound;
FIG. 2 is a diagram showing the effect of the sodium ion adsorbent prepared in example 3 of the present invention in the methanol conversion reaction.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Lithium carbonate (Li) 2 CO 3 ) Ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O), ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) The ingredients are weighed according to the Li: fe: P atomic ratio of 3 2 CO 3 808.04 g Fe (NO) 3 ) 3 ·9H 2 O, 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 6 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding ball: phi 10mm, ball mass ratio of 15, rotation speed of 500rpm, ball milling time: 6h; and roasting the ball-milled raw materials at 800 ℃ for 8 hours under the air atmosphere condition to obtain a sample, wherein the sample is reserved.
(2) Lithium carbonate (Li) 2 CO 3 ) Of, diManganese sulfide (MnO) 2 ) Ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) The materials are weighed according to the atomic ratio of Li to Mn to P of 1 2 CO 3 、
173.88 g MnO 2 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 5 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding balls: phi 10mm, ball mass ratio of 15, rotation speed of 500rpm, ball milling time: 6h; and roasting the ball-milled raw materials at 800 ℃ for 8 hours under the air atmosphere condition to obtain a sample for later use.
(3) Lithium carbonate (Li) 2 CO 3 ) Titanium dioxide (TiO) 2 ) Ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) The materials are weighed according to the atomic ratio of Li to Ti to P of 1 2 CO 3 159.76 g of TiO 2 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 6 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding balls: phi 10mm, ball mass ratio of 15, rotation speed of 500rpm, ball milling time: 6h; and roasting the ball-milled raw materials at 800 ℃ for 8 hours under the air atmosphere condition to obtain a sample for later use.
(4) Uniformly mixing the samples obtained in the steps (1), (2) and (3) according to a mass ratio of 1;
(5) And (5) baking the sample obtained in the step (4) at 1200 ℃ for 5 hours to obtain a final product.
Example 2
(1) The lithium carbonate in step (1) of example 1 was replaced with lithium chloride, ferric nitrate with vanadium trioxide, and ammonium dihydrogen phosphate with ammonium phosphate, and the other experimental conditions were the same as in step (1) of example 1;
(2) Replacement of manganese oxide in step (2) of example 1 with SnO 2 Replacement of ammonium dihydrogen phosphate by phosphoric acid, othersThe experimental conditions were the same as in step (2) of example 1;
(3) The ammonium dihydrogen phosphate in step (3) of example 1 was replaced with ammonium monohydrogen phosphate, and the other experimental conditions were the same as in step (3) of example 1;
(4) Uniformly mixing the samples obtained in the steps (1), (2) and (3) according to a weight ratio of 1;
(5) And (5) baking the sample obtained in the step (4) at 1400 ℃ for 6 hours to obtain a final product.
Example 3
(1) The other experimental conditions were the same as in step (1) of example 1 except that lithium carbonate in step (1) of example 1 was replaced with lithium chloride, ferric nitrate was replaced with ferric oxide, and ammonium dihydrogen phosphate was replaced with phosphoric acid;
(2) The manganese oxide in step (2) of example 1 was replaced with trimanganese tetroxide and ammonium dihydrogen phosphate was replaced with phosphoric acid, and the other experimental conditions were the same as in step (2) of example 1;
(3) The ammonium dihydrogen phosphate in step (3) of example 1 was replaced with phosphoric acid, and the other experimental conditions were the same as in step (3) of example 1;
(4) The same experimental conditions as in example 1;
(5) The same experimental conditions as in example 1 were used.
Comparative example 1
Lithium carbonate (Li) 2 CO 3 ) Ferric nitrate (Fe (NO) 3 ) 3 ·9H 2 O), ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) According to the Li/Fe/P atomic ratio of 3:2:3, respectively weighing 110.84 g of Li 2 CO 3 808.04 g Fe (NO) 3 ) 3 ·9H 2 O, 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 6 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding ball: phi 10mm, ball mass ratio of 15, rotation speed of 500rpm, ball milling time: 6h; ball for gameRoasting the ground raw materials at 800 ℃ for 8h under the air atmosphere condition to obtain a sample, and performing densification treatment on the sample, wherein the treatment conditions are as follows: tabletting under 10MPa to obtain 5mm phi and 5mm phi circular sheets, and isostatic pressing under 400MPa for 8h; and finally baking the sample at 1200 ℃ for 5h to obtain a final product.
Comparative example 2
Lithium carbonate (Li) 2 CO 3 ) Manganese dioxide (MnO) 2 ) Ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) The materials are weighed according to the atomic ratio of Li to Mn to P of 1 2 CO 3 173.88 g MnO 2 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 5 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding ball: phi 10mm, ball-to-material ratio 15, rotation speed 500rpm, ball milling time: 6h; roasting the ball-milled raw materials at 800 ℃ for 8h under the air atmosphere condition to obtain a sample, and performing densification treatment on the sample, wherein the treatment conditions are as follows: tabletting under 10MPa to obtain 5mm phi and 5mm phi circular sheets, and isostatic pressing under 400MPa for 8h; and finally baking the sample at 1200 ℃ for 5h to obtain a final product.
Comparative example 3
Lithium carbonate (Li) 2 CO 3 ) Titanium dioxide (TiO) 2 ) Ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) According to the atomic ratio of Li to Ti to P of 1:2:3, weighing and proportioning, respectively weighing 36.95 g of Li 2 CO 3 159.76 g of TiO 2 345.09 g NH 4 H 2 PO 4 Placing the mixture into a vibrating disk type grinder, uniformly grinding the mixture, roasting the mixture for 6 hours at 300 ℃, and then placing the mixture into a planetary ball mill for mechanical grinding under the grinding conditions: specification of grinding ball: phi 10mm, ball-to-material ratio 15, rotation speed 500rpm, ball milling time: 6h; roasting the ball-milled raw materials at 800 ℃ for 8h under the air atmosphere condition to obtain a sample, and performing densification treatment on the sample, wherein the treatment conditions are as follows: tabletting under 10MPa to obtain 5mm phi and 5mm phi circular sheets, and isostatic pressing under 400MPa for 8h; finally, the sample is heated to 1200 DEG CBaking for 5h to obtain the final product.
Example 4
The samples obtained in comparative examples 1, 2, 3, 1, 2 and 3 were crushed and sieved through 20 to 40 mesh sieves for future use.
In order to evaluate the adsorption effect of the adsorbent, a fixed bed continuous flow reactor is adopted to evaluate the adsorption performance of the sodium ion adsorbent, the loading amount of the 20-40-mesh adsorbent is 10g each time, a sodium hydroxide solution with the mass concentration of 100mg/L is pumped into the reactor through a trace feed pump, and the solution is vaporized through a preheater at 200 ℃. Adsorption conditions under gas-solid conditions: the temperature is 400 ℃, and the liquid air speed is 0.3h -1 The system pressure is 0.05MPa, the time of each adsorption is 72h, and the effluent after passing through the adsorbent is collected after being condensed. Na in condensate is measured by adopting Thermo 3300 graphite furnace flame atomic absorption spectrometer + The wavelength of the sodium lamp is 589.6nm. The results of testing the samples of comparative example 1, comparative example 2, comparative example 3, example 1, example 2, and example 3 are shown in table 1.
TABLE 1
Table 1 shows Li obtained in comparative examples 1, 2 and 3 3 Fe 2 (PO 4 ) 3 、LiMn 2 (PO 4 ) 3 、LiTi 2 (PO 4 ) 3 While the sodium ion concentrations in the condensate of the single-component adsorbents of examples 1, 2 and 3 are respectively 92.3mg/L, 87.6mg/L and 75.4mg/L, the sodium ion concentrations in the condensate of examples 1, 2 and 3 are obviously reduced to 4.3mg/L, 3.2mg/L and 1.5mg/L, which shows that the sodium ion adsorbents prepared by the three-component NASICON type compounds have higher sodium ion adsorption performance under gas-solid phase conditions.
Example 5
This example illustrates the use of the sodium sorbent of the present invention in an acid catalyst reaction. 1.0g of the sodium ion adsorbent obtained in example 3 was loaded on 3.0g of MTP catalyst (ZSM-5 type catalyst, shanghai)Zhuyue chemical technology limited, 20-40 mesh) upper layer. The evaluation device adopts a fixed bed flow reactor, 10mg/L sodium hydroxide is added into 50wt% methanol water solution as reaction raw material, and the reaction conditions are as follows: liquid hourly space velocity of 1h -1 The reaction temperature is 480 ℃, and the total pressure of the system is less than 0.05MPa. The reaction products were analyzed by Flame Ionization Detector (FID), and the reference experiment, without sodium adsorbent, showed the different effects of the two scenarios in terms of the length of time for methanol conversion to drop to 90%, with the results shown in fig. 2.
Figure 2 shows that sodium ion is a poison for ZSM-5 molecular sieve catalysts. The time without sodium ion adsorbent is 530h, while the time after adding the adsorbent prepared by the invention is increased to 850h. This shows that the sodium ion adsorbent of the present invention effectively adsorbs sodium ions in the reaction under the gas-solid phase condition, and greatly improves the stability of the acid catalyst.
Claims (23)
1. A sodium ion adsorbent comprising the following components:
10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ,
10 to 30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And
40-80 parts by mass of LiTi 2 (PO 4 ) 3 。
2. A method of making the sodium ion adsorbent of claim 1, comprising the steps of:
(1) Taking a lithium-containing compound, an iron-containing or vanadium-containing compound and a phosphorus-containing compound as raw materials, weighing and mixing the raw materials according to the atomic ratio of Li to Fe to P or Li to V to P of 3; mechanically grinding the product after the first roasting by a planet ball mill, and then carrying out second roasting to prepare Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ;
(2) With compounds containing lithiumAnd taking a tin-containing or manganese-containing compound and a phosphorus-containing compound as raw materials, weighing and mixing the raw materials according to the atomic ratio of Li to Sn to P or Li to Mn to P of 1 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 ;
(3) Lithium-containing compound, titanium dioxide and phosphorus-containing compound are used as raw materials, and the atomic ratio of Li to Ti to P is 1:2:3, grinding and uniformly mixing, performing fifth roasting, mechanically grinding a product obtained after the fifth roasting by using a planet ball mill, and performing sixth roasting to obtain the LiTi 2 (PO 4 ) 3 ;
(4) Li prepared in the step (1) 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 The LiSn prepared in the step (2) 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 The LiTi prepared in the step (3) 2 (PO 4 ) 3 Uniformly mixing, tabletting and forming, and then carrying out static pressure treatment;
(5) And (4) carrying out seventh roasting on the sample obtained in the step (4) to prepare the sodium ion adsorbent.
3. The method of claim 2, wherein the lithium-containing compound is one or more of lithium carbonate, lithium nitrate, lithium chloride, and lithium oxide.
4. The method of claim 2, wherein the iron-containing compound is one or more of ferric nitrate, ferric chloride, and ferric trioxide.
5. The method of claim 2, wherein the vanadium-containing compound is VCl 3 And/or V 2 O 3 。
6. The method of claim 2, wherein the phosphorus-containing compound is one or more of ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid.
7. The method according to claim 2, wherein the tin-containing compound is one or more of tin nitrate, tin tetrachloride and tin oxide.
8. The method of claim 2, wherein the manganese-containing compound is one or more of manganese dioxide, manganese oxide and trimanganese tetroxide.
9. The method as claimed in claim 2, wherein the first firing in the step (1) is performed under the following conditions: the roasting temperature is 300-400 ℃, and the roasting time is 4-8h.
10. The method as claimed in claim 2, wherein the second firing in the step (1) is performed under the following conditions: the roasting temperature is 700-900 ℃, and the roasting time is 4-8h.
11. The method as claimed in claim 2, wherein the third firing in the step (2) is performed under the following conditions: the roasting temperature is 200-300 ℃, and the roasting time is 4-8h.
12. The method as claimed in claim 2, wherein the fourth firing in the step (2) is performed under the following conditions: the roasting temperature is 500-700 ℃, and the roasting time is 4-8h.
13. The method as claimed in claim 2, wherein the fifth firing in the step (3) is performed under the following conditions: the roasting temperature is 300-400 ℃, and the roasting time is 4-8h.
14. The method as claimed in claim 2, wherein the sixth firing in the step (3) is performed under the following conditions: the roasting temperature is 600-700 ℃, and the roasting time is 4-8h.
15. The method as claimed in claim 2, wherein the seventh firing in the step (5) is performed under the following conditions: the roasting temperature is 1000-1500 ℃, and the roasting time is 4-8h.
16. The method as claimed in claim 15, wherein the seventh firing in the step (5) is performed under the following conditions: the roasting temperature is 1100-1200 ℃, and the roasting time is 6-8h.
17. The method according to claim 2, wherein the isostatic pressing treatment in step (4) is performed under the following conditions: treating for 4-8h under the pressure of 200-700 MPa.
18. The method as claimed in claim 17, wherein the isostatic pressing treatment in step (4) is performed under the following conditions: treating for 4-5h under the pressure of 300-500 MPa.
19. The method according to claim 2, wherein the mechanical milling of the planetary ball mill in the steps (1), (2) and (3) is carried out under the following conditions: ball specification: phi is 6-10mm, and the mass ratio of the ball material is 10-20:1, the rotating speed is 300-600rpm, and the ball milling time is 5-10h.
20. The method of claim 2, wherein the step (1) produces Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 The LiSn prepared in the step (2) 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 The LiTi prepared in the step (3) 2 (PO 4 ) 3 The uniform mixing of (a) is carried out at the following ratio:
10 to 30 parts by mass of Li 3 Fe 2 (PO 4 ) 3 Or Li 3 V 2 (PO 4 ) 3 ,
10-30 parts by mass of LiSn 2 (PO 4 ) 3 Or LiMn 2 (PO 4 ) 3 And
40-80 parts by mass of LiTi 2 (PO 4 ) 3 。
21. Use of the sodium ion adsorbent of claim 1 or the sodium ion adsorbent produced by the process of any one of claims 2 to 20 in a catalyst bed under gas-solid phase conditions to remove sodium ions.
22. Use according to claim 21, wherein the gas-solid phase conditions are those of 300-600 ℃.
23. Use according to claim 21, wherein the gas-solid phase conditions are a gas-solid phase reactor at 300-600 ℃.
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