CN108975377B - Preparation method of porous lanthanum oxide - Google Patents
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 239000002608 ionic liquid Substances 0.000 claims abstract description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 150000002603 lanthanum Chemical class 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 5
- 238000009841 combustion method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 45
- 238000001179 sorption measurement Methods 0.000 description 32
- 238000001354 calcination Methods 0.000 description 26
- 238000012512 characterization method Methods 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 238000009826 distribution Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000002336 sorption--desorption measurement Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000013335 mesoporous material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 5
- 229960001633 lanthanum carbonate Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- -1 rare earth chloride Chemical class 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000005653 Brownian motion process Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005537 brownian motion Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000486761 Chilobrachys Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of porous lanthanum oxide, which respectively weighs La (NO) with corresponding mass3)·6H2Preparing O and glycerol into solution with certain concentration with distilled water, and adding into the solutionAdding a certain amount of N-methyl-N-ethyl morpholine ionic liquid into a glycerol solution before mixing the two solutions, then adjusting the concentration, PH, heating time, heating temperature and other conditions of the added ionic liquid, and synthesizing the porous lanthanum oxide by a low-temperature combustion method. The preparation method is simple and easy to operate, the conditions are mild, and the prepared lanthanum oxide is superfine powder which is loose in texture, free of agglomeration and easy to crush, so that a new method is provided for preparing the porous lanthanum oxide.
Description
Technical Field
The invention relates to preparation of inorganic non-metallic materials, in particular to a preparation method of porous lanthanum oxide.
Background
Rare earth oxides are increasingly used in a variety of fields. The porous rare earth oxide material has the characteristics of high chemical activity, strong redox capability, variable coordination number and the like. Lanthanum oxide is an important rare earth oxide and has wide application in the aspects of catalysts, solid electrolytes and the like. In particular, the catalyst is widely used as a base catalyst in hydrogenation, isomerization, dehydration and dehydrogenation reactions. Porous La2O3Small particle, large specific surface area, high activity and micron-sized La2O3Has no performance, and plays an important role in various fields such as hydrogen storage materials, luminescent materials, ceramic materials, magnetic materials, catalysts and the like. La2O3The application of the catalyst comprises two main types of catalysts for purifying petrochemical engineering and automobile exhaust. The former as in MgO + SiO2Less than 10% of La is added into the catalyst2O3Can improve the octane number of the oil product by 110 times, and is beneficial to the use of the oil product. In the refining of crude oil into gasoline, La is adopted2O3When 28% mixed rare earth chloride is used as catalyst, the production capacity of oil refining and the quality of oil products can be improved. In the latter case, for example, La is added to the three-element noble metal catalyst2O3As an active component, the catalyst can improve the activity of the catalyst, has better catalytic performance, is beneficial to the conversion of hydrocarbon, carbon oxygen and nitrogen oxides in automobile exhaust, and has better purification effect, thereby protecting the living environment of people.
Porous La reported in the literature at present2O3The synthesis method is more, most of the synthesis methods are based on laboratory synthesis, and the synthesis methods are commonly a sol-gel method, a urea hydrolysis method, a micro-emulsion method, a solid-phase ball milling method, a hydrothermal method and the like, and the synthesis methods are represented by La (rare metal materials and engineering, 2005, 34 (2): 24-29)2O3Nitric acid and polyethylene glycol are used as raw materials, and a sol-gel method is utilized to prepare porous La2O3The experimental result shows that the La with the average grain diameter less than 50nm can be prepared under the proper technological parameters2O3And (3) powder. The literature (massive Salavati niaaria, Ghader hossei zadeha, Fatemeh Davara, Journal of Alloys and Compounds 2010, 56, 5952) uses lanthanum acetate and sodium carbonate as raw materials, reacts at 110 ℃ for 24h to give a lanthanum carbonate precipitate, which is then calcined at 700 ℃ to give porous lanthanum oxide. The document (Zhang. Y, Han. K, Cheng. T, Fang. Z, Inorg. chem.2007, 46, 4713) adopts a hydrothermal method, lanthanum salt and urea are used as raw materials, the temperature is controlled within the range of 210-270 ℃, the constant temperature is kept for 12-19 h, the precipitate obtained by the reaction is centrifugally washed, dried at 80 ℃ for 6h, and then the white powder is roasted at 750 ℃ for 3h, so that the white lanthanum oxide powder is obtained. CTAB/n-butanol/n-octane/La (NO) is adopted in Zhuwenqing, Zhang Chilobrachys, Soochet and the like (college basic science, 2010, 24 (9): 83-86)3)3Synthesis of porous La (OH) from the inverse microemulsion system formed by the aqueous solution3And then obtaining the porous lanthanum oxide. The methods or raw materials are expensive and high in cost, or the processes are complex, the conditions are harsh, the operation and control are not easy, or the large-scale and industrial production is not suitable to realize.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing porous lanthanum oxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of porous lanthanum oxide comprises the following steps:
(1) dissolving lanthanum salt in a solvent, and then dropwise adding a dispersing agent to obtain a lanthanum salt solution for later use;
(2) dissolving an organic fuel in a solvent, then dripping a dispersing agent, uniformly stirring, and adding an ionic liquid to obtain an organic fuel solution;
(3) mixing a lanthanum salt solution and an organic fuel solution until the molar ratio of the lanthanum salt to the organic fuel is 1:0.8-1.5, preferably 14:15, adjusting the pH value to 1-5, and uniformly stirring to obtain a mixed solution;
(4) and heating the mixed solution in a muffle furnace for reaction to obtain the porous lanthanum oxide.
The preparation method is simple and easy to operate, the conditions are mild, and the prepared lanthanum oxide is superfine powder which is loose in texture, porous, free of agglomeration and easy to crush.
Further, 0.2 to 0.5g, preferably 0.22g, of lanthanum salt is dissolved in 1ml of solvent, the volume ratio of the dropwise added dispersant to the solvent is 1 to 1.5:10, preferably 1:10, 0.01 to 0.07g, preferably 0.05g, of the organic fuel is dissolved in 1ml of solvent, and the volume ratio of the dropwise added dispersant to the solvent is 1 to 1.5:10, preferably 1: 10.
Further, the solvent is distilled water; the lanthanum salt is lanthanum nitrate, preferably La (NO)3)3·6H2O; the organic fuel is any one of glycerol, urea, citric acid, ammonium citrate and glycine, and preferably glycerol; N-methyl-N-ethylmorpholine in an amount of 0.01 to 0.05g/ml, preferably 0.03g/ml, as ionic liquid; the dispersant is 0.01mol/L of polyethylene glycol.
Further, the pH value is adjusted to 1-5, preferably 3 by concentrated sulfuric acid and ammonia water; the heating reaction is carried out at 750-950 ℃ for 3-6h, preferably at 900 ℃ for 5 h.
Adopt above-mentioned further beneficial effect to lie in: the difference of reaction conditions can cause the crystallinity, the grain diameter, the pore diameter and the adsorbability of products to have great difference, and when the ionic liquid with the concentration of 0.03g/ml, the PH value of 3, the calcining temperature of 900 ℃ and the calcining time of 5 hours is added, the porous lanthanum oxide with uniform grains, higher crystallinity, uniform pore distribution and pure samples can be prepared.
Drawings
Figure 1 is an XRD characterization pattern of the concentration of ionic liquid of example 2 of the present invention;
FIG. 2 is an SEM image of samples prepared under different ionic liquid concentration conditions in example 2 of the present invention;
FIG. 3 is a STA curve for samples prepared in example 2 of the present invention at different ionic liquid concentrations;
FIG. 4 shows different concentrations of ionic liquid N in example 2 of the present invention2Adsorption-desorption curve and BJH adsorption aperture distribution diagram;
FIG. 5 is an XRD characterization of example 3 of the present invention at various pHs;
FIG. 6 is an SEM photograph of example 3 with different pH values;
FIG. 7 is a differential thermal-thermogravimetric curve at various pHs for example 3 of the present invention;
FIG. 8 shows N at different pH values in example 3 of the present invention2Adsorption-desorption curve and BJH adsorption aperture distribution diagram;
FIG. 9 is an XRD characterization of example 4 of the present invention for different heating times;
FIG. 10 is a SEM image of example 4 of the present invention with different heating times;
FIG. 11 is a differential thermal-thermogravimetric plot for different heating times for example 4 of the present invention;
FIG. 12 shows N at different heating times in example 4 of the present invention2Adsorption-desorption curve and BJH adsorption aperture distribution diagram;
FIG. 13 is an XRD characterization of different heating temperatures for example 5 of the present invention;
FIG. 14 is a SEM representation of different heating temperatures of example 5;
FIG. 15 is a differential thermal-thermogravimetric plot for different heating temperatures for example 5 of the present invention;
FIG. 16 shows N at different heating temperatures in example 5 of the present invention2Adsorption-desorption curve and BJH adsorption pore size distribution diagram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.1g of glycerol and 0.44gLa (NO) were weighed out3)3·6H2And O, respectively dissolving the components in 2ml of distilled water, dripping 0.21ml of 0.01mol/L polyethylene glycol into the two solutions, then adding a certain amount of ionic liquid into the glycerol solution, adjusting the pH of the mixed solution by using concentrated sulfuric acid and ammonia water, uniformly stirring the mixed solution by using a magnetic heating stirrer, and heating the mixed solution in a muffle furnace for a certain time to obtain the porous lanthanum oxide sample synthesized under the reaction condition.
In order to determine the optimal experimental conditions, an orthogonal experiment table is established on the premise of five factors and four levels, four levels are selected from the five factors to perform an orthogonal experiment by taking the pH value, the initial mass concentration, the addition amount, the temperature and the adsorption time as the five factors, the factors and the levels of the orthogonal experiment are shown in table 1, the factors and the levels of the orthogonal experiment are used for manufacturing the orthogonal experiment table, and the table is shown in table 2.
TABLE 1 factors and levels of orthogonal experiments
TABLE 2 results of orthogonal experiments
Calculation of mean value k from Table 1-2iCan know La2O3The best test conditions for adsorbing phosphate radicals are as follows: the initial mass concentration was 0.05mg/mL, the amount was 0.01g, the adsorption temperature was 55 ℃ and the adsorption time was 120min at pH 2. The ultimate difference analysis can show that the important sequence of factors influencing the adsorption quantity is as follows: b is>C>A>E>D, i.e. the initial mass concentration effect is greatest, followed by the initial mass concentration, then PH, followed by the adsorption time, and finally the lanthana dosage.
Example 2
Effect of Ionic liquid concentration on product
Reaction conditions in example 1 were fixed: the other conditions were unchanged, with the solution pH 2, the calcination temperature 750 ℃, the calcination time 1.5h, and the effect of the ionic liquid concentration on the porous lanthanum oxide preparation was examined.
XRD characterization is as shown in figure 1, and the concentrations in figure 1 are respectively (a)0.01 g/ml; (b)0.02 g/ml; (c)0.03 g/ml; (d)0.04 g/ml; (e)0.05g/ml by reacting with La2O3After comparison of the standard cards, we can see that the prepared porous lanthanum oxide is in a hexagonal crystal form. As can be seen from FIG. 1, when the ionic liquid concentration was 0.03g/ml, the prepared sample had the best crystallinity and the highest purity. Therefore, an ionic liquid concentration of 0.03g/ml was chosen as a suitable concentration for preparing the product. The average size of the product prepared at this ionic liquid concentration was 20.8nm as estimated by the scherrer equation D ═ K λ/Bcos θ.
SEM representation is shown in figure 2, wherein the concentration is 0.01g/ml in sequence; 0.02 g/ml; 0.03 g/ml; 0.04 g/ml; 0.05g/ml, as can be seen from FIG. 2, lanthanum oxide was prepared as a porous material. When the ionic liquid concentration is 0.01g/ml, 0.04g/ml and 0.05g/ml, the pore diameter of the sample is smaller, and as can be seen from the combination of figure 2, the three products are mesoporous lanthanum oxide, and when the ionic liquid concentration is 0.02g/ml and 0.03g/ml, the pore diameter of the prepared sample is larger and is a macroporous material, which is consistent with the BET pore diameter distribution test result. Therefore, the pore diameter regulation and synthesis of the porous lanthanum oxide can be realized by changing the concentration of the ionic liquid.
STA characterization As shown in FIG. 3, it can be seen that the weight loss of the prepared samples mainly occurs in the two temperature ranges of 150 ℃ to 400 ℃ and 600 ℃ to 800 ℃. The former is mainly caused by desorption of water adsorbed by the sample and loss of crystal water contained in the sample, and the latter is caused by decomposition of a small amount of lanthanum carbonate and lanthanum hydroxide in the sample. It can be seen from table 3 that the total weight loss of the sample at 1000 ℃ decreases with the increase of the concentration of the ionic liquid, indicating that the thermal stability of the sample increases with the increase of the concentration of the ionic liquid.
TABLE 3 weight loss comparison of samples prepared at different ionic liquid concentrations
Ionic liquid N with different concentrations2The adsorption-desorption curves are shown in the figure, the distribution diagrams of the adsorption pore diameters of 4(A) and BJH are shown in the figure 4(B), and the isotherms of the five samples belong to a III-type adsorption isotherm in an IUPAC physical adsorption isotherm, mainly comprise mesoporous and macroporous structures, and weak gas-solid phase interaction occurs on non-porous or macroporous solids by the isotherm. We can see that this type of curve does not show inflection point B and no discernible monolayer is present. Following P/P0The adsorption amount gradually increases with the increase in the number of adsorbed layers. When P/P is present0After 0.9, the isotherm at which the ionic liquid was added at a concentration of 0.03g/ml began to become relatively steep, indicating that the air distribution of the adsorbent was relatively narrow and the size of the mesopores was relatively uniform. The low-pressure end of which is biased to the X axis to illustrate N2The acting force with the sample is weak, and the mesoporous material belongs to a typical mesoporous material.
From fig. 4(B) we can see that pore volume decreases slowly with increasing pore diameter. In the pore diameter range of less than 25nm, the pore volume is reduced in turn when the ionic liquid concentration is 0.01-0.02 g/ml. And when the concentration of the ionic liquid is increased to 0.03g/ml, the pore volume is suddenly increased, and then gradually reduced at 0.04-0.05g/ml along with the increase of the concentration of the ionic liquid. Therefore, in this range of pore sizes, the same pore size, 0.03g/ml ionic liquid corresponds to the largest pore volume, which indicates that the concentration of added ionic liquid has a certain influence on the pore volume. When the concentration of the ionic liquid is 0.03g/ml, the corresponding specific surface area is the largest, which indicates that the porous lanthanum oxide prepared by the ionic liquid with the concentration has the best adsorption performance.
Example 3
Effect of pH on the product
Five groups of comparative experiments are carried out, the pH values of the five experiments are respectively 1, 2, 3, 4 and 5, the reaction steps are as in example 1, the concentration of the fixed ionic liquid is 0.03, the heating temperature is 750 ℃, the heating time is 1.5h, other reaction conditions are unchanged, porous lanthanum oxide samples prepared in the pH environment are respectively synthesized through experiments, the influence of different pH values on the reaction is researched through characterization, and the optimal pH value is selected. The difference of the PH values in the solution directly influences the particle size of the product, in the reaction of preparing the porous lanthanum oxide by a combustion method, glycerin plays a role in complexing metal ions while playing a role in a combustion agent, the metal ions can be uniformly distributed in a complex at a proper PH value, and when the PH value is small, the complexing effect on the lanthanum ions is not strong enough due to insufficient ionization in the solution, so that the particle size of the synthesized porous lanthanum oxide is large. When the pH is too high, a large number of crystal nuclei are generated to increase the collision frequency between the crystal nuclei, resulting in the formation of an agglomeration phenomenon.
The XRD characterization is as in fig. 5, where (a) PH 1; (b) PH is 2; (c) PH is 3; (d) PH is 4; (e) PH 5, by reaction with La2O3After comparison of the standard cards, we can see that the prepared porous lanthanum oxide is in a hexagonal crystal form. When PH is 1, the lower height of the diffraction peak indicates that the crystallinity of the ion synthesized in the PH environment is low, and when PH is increased to 2 and 3, the height of the diffraction peak is significantly increased, indicating that the crystallinity of the ion in the reaction system is also increased successively. While as the pH continued to rise, the height of the diffraction peak decreased again, and La2O3The diffraction peak intensity of (2) is decreased, and the diffraction peak intensity of the impurity peak is increased. La corresponding to pH value of 1, 2, 3, 4, 52O3The average particle diameters were 26.3nm, 23.2nm, 21.8nm, 22.4nm and 28.9nm, respectively. Therefore, as the pH increases, La2O3The particle size of (a) is first reduced and then increased. La at pH 32O3The particle size of (a) is relatively small.
The porous lanthanum oxide samples prepared under the reaction conditions of PH 1, PH 2, PH 3, PH 4 and PH 5 (0.03 g/ml of ionic liquid; 750 degrees of calcination temperature; 1.5h of calcination time) are subjected to differential thermal-thermogravimetric characterization, and the generated differential thermal-thermogravimetric curves are analyzed, wherein the SEM characterization is as shown in FIG. 6, and the STA characterization is as shown in FIG. 7.
As shown in fig. 6, it can be seen from the figure that the morphology of the sample changes due to the change of PH, and when PH is 1, the morphology of the sample is a fine mesh porous structure, and the distribution of mesopores and macropores is not uniform. When PH is 2, a layered structure appears on a finer network structure, the number of mesopores is reduced and the distribution is uneven. At PH 3 and PH 4, the morphology of the sample becomes a lamellar structure, and in contrast, at PH 3 there are fewer mesopores and a more uniform distribution. At PH 5, the morphology of the sample changed to a network structure. Thus, the difference of pH has a great influence on the appearance of the porous lanthanum oxide.
From fig. 7 we can see that there is some mass loss below 150 ℃, mainly the desorption process of the physically adsorbed water. The mass loss is larger at the temperature of 150 ℃ and 400 ℃, and the corresponding DTA curve has a smaller endothermic peak, which is probably the desorption process of the combined water in the sample. The mass loss is large at the temperature of 400-800 ℃, and the corresponding DSC curve in the range has an obvious endothermic peak which is probably an endothermic process generated by decomposition of certain carbonate of lanthanum generated in the sample. Under the environment of the five pH values, obvious heat absorption phenomenon exists after 600 ℃. However, only at PH 3, the DSC curve slowly flattens at 900 ℃, while other PHs show a constant endotherm after 600 ℃ and do not have a gradual trend. This indicates that, when PH is 3, all impurities are completely decomposed after 900 ℃, and pure porous lanthanum oxide is obtained. Therefore, in order to obtain pure porous lanthanum oxide, the porous lanthanum oxide can be calcined at a constant temperature of 900 ℃, and the particle size can be controlled by controlling the heating time.
The porous lanthanum oxides prepared at different PHs were subjected to BET characterization, and the resulting nitrogen adsorption-desorption isotherm curve is shown in fig. 8 (a). From the curves in the figure, we can judge that the isothermal curves of the five samples belong to the III-class adsorption isotherm in the IUPAC physical adsorption isotherm, the isothermal curves mainly comprise mesoporous and macroporous structures, and we can see that inflection points B do not appear on the curves, so that no identifiable monomolecular layer exists. This isotherm results in weak gas-solid phase interactions on non-porous or macroporous solids. The low-pressure end of which is biased to the X axis to illustrate N2Has weak acting force with a sample, belongs to a typical mesoporous material, and is characterized in thatIn the whole pressure variation range, in the latter half N2The adsorption quantity of the adsorbent is increased at a very high speed, the capillary condensation phenomenon is generated, and the adsorption-desorption isothermal curves with different pH values do not have hysteresis loops. Therefore, the sample internal pore prepared under this condition is of a type that is closed at one end or open at both ends. The shape of the curve was not changed, and the amount of nitrogen adsorbed decreased at PH 1-2, increased at PH 3, and then gradually decreased with increasing PH.
The data of the porous lanthanum oxide prepared by ionic liquid with different concentrations characterized by BET show that the specific surface area can be used for evaluating the adsorption performance of a sample, and the larger the value of the specific surface area is, the better the adsorption performance of the sample is. The specific surface area is the largest when PH is 1, but the relative pore size and micropore volume are the smallest. To further investigate the pore volume of the samples as a function of pore diameter, the calculated BJH desorption integrated pore volume data was characterized by BET and pore volume as a function of pore diameter was plotted by origin, as shown in fig. 8 (B). From the figure, it can be seen that the micropore volume corresponding to pH 2 or pH 3 is the largest at the same particle size. In contrast, when PH is 3, the corresponding specific surface area is relatively large. Therefore, porous lanthanum oxide with strong adsorption performance and large pore diameter and micropore volume can be prepared by selecting PH 3.
Example 4
Effect of calcination time on the product
Seven groups of comparative experiments are carried out, so that the heating time of the seven groups of experiments is respectively t-1.5 h, t-2 h, t-3 h, t-4 h, t-5 h, t-6 h and t-7 h, the experimental procedure is the same as that of example 1, the concentration of the fixed ionic liquid is 0.03g/ml, the pH value is 3, the heating temperature is 750 degrees, other conditions are not changed, the porous lanthanum oxide samples prepared by the seven heating times are respectively synthesized by the experiments, the influence of the heating time on the reaction is researched by characterization, and the optimal heating time is selected.
The XRD characterization is as shown in fig. 9, wherein (a) t is 1.5 h; (b) t is 2 h; (c) t is 3 h; (d) t is 4 h; (e) t is 5 h; (d) t is 4 h; (e) t is 7h, and as can be seen from the figure, under different heating times, the morphology of the diffraction peak is not greatly changed and is changedOnly the height of the diffraction peak, and La was simultaneously produced while synthesizing lanthanum oxide2CO5And La (OH)3Impurities, and we can conclude that this phenomenon occurs because the calcination temperature is too low to complete the reaction, resulting in La2CO5The lanthanum ions are partially complexed to form La (OH) without complete decomposition3A complex compound. As the heating time increases, the height of the diffraction peak increases and then decreases. From this, it can be judged that the crystallinity is large first and small second. When the calcination time t is 5h, the height of the diffraction peak is the highest, so that the crystallinity of the obtained product is the highest when t is 5h, and the average particle size of the obtained porous lanthanum oxide is 22.3 nm.
Fig. 10 is SEM images of samples prepared at different heating times, wherein t is 1.5 h; t is 3 h; t is 4 h; t is 5 h; t is 6h, and as can be seen from the figure, the porous lanthanum oxide prepared when the calcination time is 1.5h is a blocky porous structure with small particles, and the mesopores on the surface of the sample are not uniformly distributed. When the heating time is 3 hours, the shape of the material is a flaky porous structure, the quantity of mesopores is small, and the distribution is uniform. The samples prepared by calcining for 4h, 5h and 6h are all flocculent structures, the appearance of the samples is not changed under the calcining time, the change is only the size of the pore diameter, and the mesopores on the surface of the sample are less and are not uniformly distributed. Therefore, the calcination time within a certain range has an influence on the appearance of the sample, and the appearance of the sample does not change beyond the time.
Fig. 11 is a differential thermal-thermogravimetric curve of different heating times, and TG curve shows that there is some mass loss below 150 ℃, mainly desorption process of physically adsorbed water. The mass loss is obvious at the temperature of 100 ℃ and 400 ℃, and the weight loss rates of heating time of 1.5h, 3h, 4h, 5h and 6h in the temperature range are respectively 3%, 6%, 7%, 11% and 5%. And the DSC curve has a stronger endothermic peak in the temperature range, the phase is a desorption process of the combined water, and obvious mass loss also occurs at 800 ℃ of 400-. And the DSC curve has one in the temperature rangeA strong endothermic peak, which may be the endotherm generated by the decomposition of lanthanum carbonate. After 800 ℃, the DSC curve still has the tendency of generating endothermic peak, and the stage may be the process that lanthanum hydroxide is slowly calcined into lanthanum oxide, and the following reaction occurs, 2La (OH)3—2LaO(OH)+2H 20—La 203+H 20。
The porous lanthanum oxide prepared by different heating times is subjected to BET characterization, and the obtained nitrogen adsorption-desorption curve is shown in FIG. 12 (A). From the curves in the figure we can judge that the isotherm curves of these five samples also belong to the class iii adsorption isotherm in the IUPAC physisorption isotherm, we can see that this type of curve does not present inflection point B, so we can judge that it does not have a discernible monolayer. The low-pressure end of which is biased to the X axis to illustrate N2The acting force with the sample is weak, and the mesoporous material belongs to a typical mesoporous material. From the figure we can see that for N2The adsorption performance of (a) is small first and then large, and the adsorption performance is related to the pore diameter and the pore volume of the sample, so in order to further study the influence of heating time on the adsorption performance of the sample, BJH desorption integral pore volume data obtained by using BET characterization is used, origin is used for drawing a pore volume change curve along with the pore diameter, as shown in figure 12(B), as can be seen from the figure, in a certain pore diameter range, the pore volume is gradually increased along with the increase of heating time, when the heating time is 5h, the pore volume is suddenly reduced, and when the heating time is 6h, the pore volume is suddenly increased. This indicates that the heating time has some effect on the pore volume.
The data relating to the porous lanthanum oxide prepared by different heating times characterized by BET show that the specific surface area can be used for evaluating the adsorption performance of the sample, and the larger the value of the specific surface area, the better the adsorption performance of the sample is. As can be seen from the table, the specific surface area is the largest when the heating time is 5 hours, and N is2In the adsorption-desorption curve, it can be seen that the adsorption is minimal, and correspondingly the average pore size and micropore volume of the lanthanum oxide produced during this heating period are minimal, possibly its pore size and pore volume versus its N2The adsorptivity has an influence.
Example 5
Effect of calcination temperature on the product
Five comparative tests are carried out, so that the calcination temperatures of the five tests are respectively 750 degrees, 800 degrees, 850 degrees, 900 degrees and 950 degrees, the experimental procedure is the same as that of example 1, the concentration of the fixed ionic liquid is 0.03g/ml, the pH value is 3, the heating time is 5 hours, other conditions are not changed, the porous lanthanum oxide samples prepared by the five calcination times are respectively synthesized through the experiments, the influence of the calcination temperature on the reaction is researched through characterization, and the optimal calcination temperature is selected. The calcination temperature plays an important role in this experiment, when the calcination temperature is too low, the reaction is incomplete, some impurities are generated, the particle size is too large due to agglomeration of the product caused by slow growth speed of the particle size, and when the reaction temperature reaches the optimal temperature of the reaction, the particle size of the obtained product is slowly increased along with the continuous increase of the temperature. This is because when the temperature is relatively high, brownian motion formed by hydrolysis is accelerated, collision kinetic energy and collision frequency between ions are increased, and thus it tends to be more likely to be aggregated into large particles.
Fig. 13 is an XRD characterization pattern of the porous lanthanum oxide synthesized at different calcination temperatures, where (a) T is 750 ℃; (b) t is 800 ℃; (c) t is 850 ℃; (d) t is 900 ℃; (e) when the temperature reaches 800 degrees and 850 degrees, although the diffraction peak of the impurity still exists, the intensity of the diffraction peak is obviously weakened. When the temperature reaches 900 ℃ and 950 ℃, the impurity peaks of the prepared product completely disappear, and only the diffraction peaks of the porous lanthanum oxide exist. Through La2O3After comparison of the standard cards, we can see that the prepared porous lanthanum oxide is in a hexagonal crystal form. The particle sizes of the porous lanthanum oxide prepared at 900 ℃ and 950 ℃ are respectively 34.4nm and 41.4nm estimated by a Sherrer formula D ═ K lambda/Bcos theta, and the porous lanthanum oxide with smaller particle size can be obtained at 900 ℃.
Fig. 14 is an SEM characterization of porous lanthanum oxide prepared at different heating temperatures, where the temperature is, in order, T750 ℃; t is 800 ℃; t is 850 ℃; t is 900 ℃; t is 950 ℃, from the figureAs can be seen from the above, the porous lanthanum oxide prepared at the calcination temperature of 750 ℃ has a flocculent structure and non-uniform mesopore distribution. When the heating temperature reaches 800-850 ℃, a blocky structure is generated on the flocculent structure, and the number of mesopores is also reduced. When the calcining temperature reaches 900 ℃, the shape of the material is changed into a thin rod-shaped structure, and only a small amount of mesopores are arranged on the surface of the material. When the calcination temperature reaches 950 ℃, the morphology of the material is changed into a coarse rod-shaped structure, and almost no mesopores exist on the surface of the material, which is compared with the judgment of N at the temperature when BET representation is carried out2The adsorbability is the least fit. It can be seen from the figure that at this temperature, significant agglomeration occurs, and when the temperature is relatively high, brownian motion due to hydrolysis is accelerated, and collision kinetic energy and collision frequency between ions are increased, so that it tends to be more prone to agglomerate into large particles. Therefore, the difference of the calcination temperature has a certain influence on the appearance of the sample.
The results of the thermal decomposition experiments of the porous lanthanum oxide prepared at different heating times are shown in fig. 11. As can be seen from fig. 15, the sample had a certain mass loss below 150 ℃, mainly the removal process of physically adsorbed water; the mass loss is large at the temperature of 150 ℃ and 400 ℃, and a weaker endothermic peak is simultaneously formed corresponding to a DSC curve, and the phase may be a removal process of the bound water; the mass loss at 400-550 ℃ and a strong endothermic peak corresponding to a DSC curve are also caused, probably because a certain lanthanum carbonate exists in a sample and an endothermic phenomenon is generated due to decomposition reaction; certain mass loss exists at the temperature of 550-800 ℃, and an endothermic peak is also generated by the decomposition reaction of lanthanum carbonate corresponding to a DSC curve; the mass loss after 800 ℃ is the process of slowly calcining lanthanum hydroxide into lanthanum oxide. When the lanthanum oxide is characterized by XRD, only the diffraction peaks of the lanthanum oxide are detected at 900 ℃ and 950 ℃, and no peaks of other impurities appear, so that the lanthanum oxide possibly reacts with water and carbon dioxide in the air to generate certain carbonate of the lanthanum after being left in the air for too long.
The porous lanthanum oxide prepared by different heating temperatures is subjected to BET characterization, and the obtained nitrogen adsorption-desorption curve is shown in figure 16 (A). From the curves in the figure we can judge that the isotherm curves of these five samples belong to the class iii adsorption isotherm in the IUPAC physisorption isotherm, and since we can see that this type of curve does not present inflection point B, it does not present a discernible monolayer. From the nitrogen adsorption-desorption curve we can see that the sample is for N2The adsorptivity increases and then decreases with increasing heating temperature. From FIG. 16(B), it can be seen that pore volume varies with pore diameter, and that in a certain pore diameter range, pore volume increases and decreases with increasing heating temperature, so that it can be judged that increasing heating temperature changes the pore volume of the sample to affect N2And (4) adsorption performance. Since the low-pressure end is biased toward the X axis in the nitrogen adsorption-desorption curve, N is indicated2The acting force with the sample is weak, and the mesoporous material belongs to a typical mesoporous material.
The data of the porous lanthanum oxide prepared by ionic liquid with different concentrations characterized by BET show that the specific surface area can be used for evaluating the adsorption performance of a sample, and the larger the value of the specific surface area is, the better the adsorption performance of the sample is. From the table, we can see that the values of the specific surface areas of the samples become smaller in order with the increase of the heating temperature. The adsorption performance thereof is slowly deteriorated with the increase of the temperature.
Claims (7)
1. A preparation method of porous lanthanum oxide is characterized by comprising the following steps:
(1) dissolving lanthanum salt in a solvent, and then dropwise adding a dispersing agent to obtain a lanthanum salt solution for later use;
(2) dissolving an organic fuel in a solvent, then dripping a dispersing agent, uniformly stirring, and adding an ionic liquid to obtain an organic fuel solution;
(3) mixing the lanthanum salt solution and the organic fuel solution, adjusting the pH value to 1-5, and uniformly stirring to obtain a mixed solution;
(4) heating the mixed solution in a muffle furnace for reaction to obtain porous lanthanum oxide;
the reaction in the step (4) is a heating reaction at 750-950 ℃ for 3-6 h;
the ionic liquid is N-methyl-N-ethyl morpholine;
the concentration of the ionic liquid is 0.01-0.05 g/ml.
2. The method as claimed in claim 1, wherein the lanthanum salt is dissolved in an amount of 0.2-0.5g per 1ml of the solvent in the step (1), the organic fuel is dissolved in an amount of 0.01-0.07g per 1ml of the solvent in the step (2), and the volume ratio of the dropwise added dispersant to the solvent is 1-1.5: 10.
3. The method as claimed in claim 1, wherein the mixing in step (3) is carried out until the molar ratio of lanthanum salt to organic fuel is 1: 0.8-1.5.
4. The method of claim 1, wherein the step (3) is performed by adjusting the pH of the mixed solution to 1-5 with concentrated sulfuric acid and ammonia water.
5. The method according to any one of claims 1 to 4, wherein the solvent is distilled water.
6. The method as claimed in any one of claims 1 to 4, wherein the lanthanum salt is lanthanum nitrate, and the organic fuel is any one of glycerol, urea, citric acid, ammonium citrate and glycine.
7. The method for preparing porous lanthanum oxide according to any one of claims 1 to 4, wherein the dispersant is 0.01mol/L polyethylene glycol.
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