CN114921667A - Method for recovering rare earth and biomass high value-added products from hyper-enriched plants - Google Patents
Method for recovering rare earth and biomass high value-added products from hyper-enriched plants Download PDFInfo
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Abstract
The invention belongs to the technical field of solid waste recycling, and particularly relates to a method for recovering rare earth and biomass high-value-added products from hyper-enriched plants. The method adopts the solvent heat treatment, fast pyrolysis and rare earth separation and purification technologies, realizes simultaneous recycling of rare earth elements and biomass components in the harvested products of the rare earth super-enriched plants, selectively separates and recycles the rare earth elements in the plants, converts the rare earth super-enriched plant biomass into products with high added values such as lignin and phenols, is environment-friendly, clean and efficient in the whole process, has high recovery rate and purity of the obtained products, and has wide application prospects in the field of comprehensive recycling of the rare earth super-enriched plants.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling. More particularly, it relates to a method for recovering rare earth and biomass high value-added products from super-enriched plants.
Background
Rare earth is an important strategic resource and plays an important role in the fields of agriculture, industry, aerospace, medical treatment and the like. Along with the increase of rare earth demand, the development of rare earth mines is intensified, large areas of rare earth waste tailings land and waste materials are generated, the waste tailings land and the waste materials flow into land and water flow to pollute farmlands, and the ecological environment is damaged. In order to repair the soil polluted by the rare earth, the hyper-enrichment plants are planted in the rare earth polluted area, and the hyper-enrichment plants can absorb, transport and enrich the rare earth in the soil and water, so as to better recover the vegetation and repair the polluted soil. However, at the same time, how to perform green, environment-friendly and resource treatment and disposal on the polluted rare earth hyperaccumulator plants becomes an important problem in the industrial and large-scale application of the soil phytoremediation technology.
The rare earth hyper-enrichment plant after soil remediation is mainly rich in rare earth elements such as lanthanum, cerium, praseodymium and neodymium, and simultaneously rich in metal elements such as silicon, aluminum, calcium, manganese, magnesium and the like, and the separation and extraction of rare earth and non-rare earth metal is the key for recovering the rare earth elements from the hyper-enrichment plant. Moreover, the hyper-enriched plant is also rich in biomass components such as cellulose, lignin and the like, and has the potential of preparing fuels and chemicals. At present, the post-treatment methods of the hyper-enriched phytoremediation products mainly comprise incineration, pyrolysis, composting, compression landfill, liquid phase extraction and the like, and the key problem of limiting each treatment process is that the resource utilization and proper treatment of biomass components and metal elements are difficult to be considered simultaneously. For example, chinese patent application CN111020239A discloses a method for recovering rare earth and energy substances from rare earth super-enriched plants, which combines mechanical crushing, vacuum pyrolysis staged condensation and rare earth leaching precipitation technologies to recover mixed rare earth oxides, pyrolysis oil and gas products from rare earth super-enriched plants, but in the technology, the purity and recovery rate of rare earth products still need to be improved, and the components of pyrolysis oil and gas products are complex, and the value-added utilization needs to be improved, and biomass components such as cellulose, lignin and the like with higher added values in super-enriched plants are not fully utilized.
Therefore, a method for recovering rare earth and biomass high value-added products from hyper-enriched plants is urgently needed, high value-added resource utilization of biomass components and metal elements can be considered, and recovery rate is improved.
Disclosure of Invention
The invention aims to overcome the defects that the treatment of the existing rare earth hyper-enrichment plant cannot simultaneously consider the high value-added resource utilization of biomass components and metal elements, provides a method for recovering rare earth and biomass high value-added products from the hyper-enrichment plant, can simultaneously consider the high value-added resource utilization of the biomass components and the metal elements, and improves the recovery.
The above purpose of the invention is realized by the following technical scheme:
a method for recovering rare earth and biomass high value-added products from hyper-enriched plants specifically comprises the following steps:
s1, crushing the hyper-enriched plants, adding a sulfuric acid solution and absolute ethyl alcohol, carrying out complete thermal reaction on the solvents at 140-180 ℃ under a closed condition, cooling and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid phase product obtained in the step S1, adding water to completely precipitate, and filtering to obtain organic solvent lignin particles;
s3, completely pyrolyzing the solid-phase product obtained in the step S1 at 450-650 ℃ to obtain a phenol pyrolysis product (gas) and residues;
s4, ashing the residues obtained in the step S3, and leaching with a hydrochloric acid solution to obtain a leaching solution;
s5, adjusting the pH value of the leachate obtained in the step S4 to 1-3, adding ammonium sulfate and oxalic acid, completely precipitating, and filtering to obtain a precipitate and a filtrate;
s6, completely roasting the precipitate obtained in the step S5 at 800-900 ℃ to obtain the mixed rare earth oxide.
The invention adopts sulfuric acid solution to assist ethanol to carry out solvent heat treatment, primarily separates the harvest of the rare earth super-enrichment plant to obtain a solid phase product enriched with rare earth and calcium and a liquid phase product dissolved with lignin; removing ethanol from the liquid phase product, adding water for precipitation to obtain a lignin product, rapidly pyrolyzing the solid phase component to obtain a phenol product and residues, and further separating and purifying the residues by adopting ashing-hydrochloric acid leaching-ammonium sulfate/oxalic acid combined precipitation technology to obtain the mixed rare earth oxide with higher purity. The whole comprehensive resource recovery process of the super-enriched plants combines the solvent heat treatment, the fast pyrolysis and the rare earth separation and purification technology, realizes the simultaneous resource recovery and utilization of rare earth elements and biomass components in the harvested products of the rare earth super-enriched plants, selectively separates and recovers the rare earth elements in the plants, converts the biomass of the rare earth super-enriched plants into lignin, phenols and other products with high added value, is clean and efficient in the whole process, has high recovery rate and purity of the obtained products, and has wide application prospect in the field of comprehensive resource utilization of the rare earth super-enriched plants.
Further, in step S1, the concentration of the sulfuric acid solution is 0.1-0.5 mol/L.
Preferably, in the step S1, the solvothermal reaction time is 1-3 h.
Preferably, in step S1, the absolute ethyl alcohol is added in an amount of 75-97.83% (volume concentration).
Further, in step S3, the pyrolysis is performed in an inert gas atmosphere.
Preferably, in the step S3, the pyrolysis time is 20-30S.
Further, in step S4, the ashing temperature is 500-600 ℃.
Preferably, in the step S4, the ashing time is 1-3 h.
Preferably, in the step S4, the concentration of the hydrochloric acid solution is 0.1-0.5 mol/L.
Preferably, in step S4, the solid-to-liquid ratio of the hydrochloric acid solution added is (10-30) mL: 1g of the total weight of the composition.
Preferably, in the step S4, the leaching time is 1-4 h.
Preferably, in the step S4, the leaching temperature is 35-85 ℃.
Further, in step S5, the amount of ammonium sulfate added is 0.8 to 4.0 g/L.
Preferably, in step S5, the temperature of the precipitation is 30-80 ℃.
Preferably, in step S5, the addition amount of oxalic acid is 1 to 5 times the theoretical addition amount.
Further, in the step S6, the roasting time is 1-3 h.
Furthermore, the hyper-enriched plants include common hyper-enriched plants in the field such as dicranopteris pedata, pokeberry root, crescent fern, hickory nut, dryopteris fragrans and the like.
In addition, the invention also claims application of the method for recovering rare earth and biomass high value-added products from the super-enriched plants in comprehensive resource utilization of the rare earth super-enriched plants. Specifically, the comprehensive resource utilization of the rare earth hyper-enriched plant refers to the recovery of biomass high value-added products such as rare earth and/or lignin, phenols and the like from the hyper-enriched plant.
The invention has the following beneficial effects:
the invention relates to a method for recovering rare earth and biomass high-added-value products from hyper-enriched plants, which adopts the technologies of solvent heat treatment, fast pyrolysis and rare earth separation and purification, realizes the simultaneous recovery and resource utilization of rare earth elements and biomass components in harvested products of the hyper-enriched rare earth plants, selectively separates and recovers the rare earth elements in plant bodies, converts the hyper-enriched rare earth plant biomass into lignin, phenol and other products with high added values, is environment-friendly, clean and efficient in the whole process, has high recovery rate and purity of the obtained products, and has wide application prospect in the field of comprehensive resource utilization of the hyper-enriched rare earth plants.
Drawings
Fig. 1 is a flow chart of a method for recovering rare earth and biomass high value-added products from hyper-enriched plant dicranopteris pedata in example 1 of the present application.
FIG. 2 is an SEM image of a mixed rare earth oxide product recovered from Dicranopteris pedata of the hyper-enrichment plant of example 1.
Detailed Description
The invention is further described with reference to the drawings and specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 method for recovering rare earth and biomass high value-added product from ultra-enriched plant dicranopteris pedata
The method for recovering rare earth and biomass high-value-added products from the ultra-enriched plant dicranopteris pedata specifically comprises the following steps (see a flow chart in figure 1):
s1, drying and crushing dicranopteris pedata leaf serving as a harvested product of the rare earth hyper-enrichment plant into uniform powder by a crusher, taking 2g of the powder sample, placing the powder sample in an inner liner of a hydrothermal reaction kettle, adding 5mL of 0.4mol/L sulfuric acid and 35mL of ethanol, placing the closed reaction kettle in an oven for solvothermal reaction at 160 ℃ for 2h, cooling to room temperature, collecting and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid phase product obtained in the step S1 by rotary evaporation, adding 500mL of deionized water, standing and precipitating for 24h, filtering to obtain 0.14g of a precipitated product, and analyzing by 2D HSQC NMR to show that the product is organic solvent lignin particles;
s3, analyzing the metal content of 1.13g of the solid-phase product obtained in the step S1 by ICP-OES and ICP-MS, and finding that 94.52% of rare earth and 87.42% of calcium are still remained in the solid-phase product, and most of impurity metals of aluminum, iron, magnesium and manganese are dissolved in the liquid-phase product; rapidly heating the solid-phase product to 550 ℃ by adopting py-GC/MS (pyro-GC/MS), and pyrolyzing for 24s to obtain a phenolic pyrolysis product (gas) and residues;
s4, performing an ashing experiment on the residue obtained in the step S3 at 550 ℃ for 3 hours, leaching the residue after the reaction is completed by using hydrochloric acid with the concentration of 0.4mol/L, wherein the liquid-solid ratio is 25 mL: 1g, leaching time of 2h and temperature of 35 ℃ to obtain a leaching solution, analyzing the metal content by adopting ICP-OES and ICP-MS, and finding that the rare earth concentration in the leaching solution is 1.640g/L and the leaching concentration of calcium is 0.852 g/L;
s5, adding ammonia water dropwise into the leachate obtained in the step S4 to adjust the pH value to 2, adding 1.6g/L of ammonium sulfate and 3 times of theoretically-added amount of oxalic acid, precipitating at the temperature of 30 ℃, filtering to obtain a precipitate and a filtrate, analyzing the metal content by adopting ICP-OES and ICP-MS, and finding that 97.93% of rare earth is recovered through precipitation, and 99.96% of calcium is remained in the filtrate;
s6, placing the precipitate obtained in the step S5 in a muffle furnace to roast for 1h at 900 ℃, and obtaining the mixed rare earth oxide with the purity of 97.12 percent and the recovery rate of 88.89 percent.
Example 2A method for recovering rare earth and biomass high value-added products from the hyper-enriched plant Phytolacca americana
The method for recovering rare earth and biomass high value-added products from the super-enriched plant pokeweed specifically comprises the following steps:
s1, airing leaves of the rare earth hyper-enriched plant harvested material pokeberry by using a crusher, crushing the leaves into uniform powder, taking 2g of the powder sample, placing the powder sample into an inner liner of a hydrothermal reaction kettle, adding 5mL of 0.4mol/L sulfuric acid and 35mL of ethanol, placing the closed reaction kettle in an oven for solvothermal reaction for 2 hours at 160 ℃, cooling to room temperature, collecting and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid phase product obtained in the step S1 by rotary evaporation, adding 500mL of deionized water, standing and precipitating for 24h, filtering to obtain 0.25g of a precipitated product, and analyzing by 2D HSQC NMR to show that the product is organic solvent lignin particles;
s3, analyzing the metal content of 1.16g of the solid-phase product obtained in the step S1 by ICP-OES and ICP-MS, and finding that 91.49% of rare earth and 90.25% of calcium remain in the solid-phase product, and most of impurity metals of aluminum, iron, magnesium and manganese are dissolved in the liquid-phase product; rapidly heating the solid phase product to 550 ℃ by adopting py-GC/MS (pyro-GC/MS), and pyrolyzing for 24s to obtain a phenol pyrolysis product (gas) and residue;
s4, performing an ashing experiment on the residue obtained in the step S3 at 550 ℃ for 3 hours, leaching the residue after the reaction is completed by using hydrochloric acid with the concentration of 0.4mol/L, wherein the liquid-solid ratio is 25 mL: 1g, leaching time of 2h and temperature of 35 ℃ to obtain a leaching solution, and analyzing the metal content by adopting ICP-OES and ICP-MS to find that the rare earth concentration in the leaching solution is 0.952g/L and the calcium leaching concentration is 0.531 g/L;
s5, adding ammonia water dropwise into the leachate obtained in the step S4 to adjust the pH value to 2, adding 1.6g/L of ammonium sulfate and 3 times of the theoretical addition amount of oxalic acid, precipitating at the temperature of 30 ℃, filtering to obtain a precipitate and a filtrate, analyzing the metal content by adopting ICP-OES and ICP-MS, and finding that 95.63% of rare earth is recovered through precipitation, and 97.81% of calcium is remained in the filtrate;
s6, placing the precipitate obtained in the step S5 in a muffle furnace at 900 ℃ for roasting for 1h to obtain the mixed rare earth oxide with the purity of 98.05 percent and the recovery rate of 87.32 percent.
Example 3A method for recovering rare earth and biomass high value-added products from hyper-enriched plant crescent moon fern
The method for recovering rare earth and biomass high value-added products from the hyper-enriched plant crescent pteris specifically comprises the following steps:
s1, drying and crushing the single-leaf crescent moon fern leaves of the rare earth hyper-enrichment plant harvest into uniform powder by adopting a crusher, taking 2g of a powdery sample, placing the powdery sample in an inner liner of a hydrothermal reaction kettle, adding 5mL of 0.4mol/L sulfuric acid and 35mL of ethanol, placing the closed reaction kettle in an oven for carrying out solvothermal reaction for 2 hours at 160 ℃, cooling to room temperature, collecting and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid phase product obtained in the step S1 by rotary evaporation, adding 500mL of deionized water, standing and precipitating for 24h, filtering to obtain 0.21g of a precipitated product, and analyzing by 2D HSQC NMR to show that the product is organic solvent lignin particles;
s3, analyzing the metal content of 1.08g of the solid-phase product obtained in the step S1 by ICP-OES and ICP-MS, and finding that 93.26% of rare earth and 86.15% of calcium remain in the solid-phase product, and most of the impurity metals of aluminum, iron, magnesium and manganese are dissolved in the liquid-phase product; rapidly heating the solid phase product to 550 ℃ by adopting py-GC/MS (pyro-GC/MS), and pyrolyzing for 24s to obtain a phenol pyrolysis product and residues;
s4, performing an ashing experiment on the residue obtained in the step S3 at 550 ℃ for 3 hours, leaching the residue after the reaction is completed by using hydrochloric acid with the concentration of 0.4mol/L, wherein the liquid-solid ratio is 25 mL: 1g, leaching time of 2h and temperature of 35 ℃ to obtain a leaching solution, analyzing the metal content by adopting ICP-OES and ICP-MS, and finding that the rare earth concentration in the leaching solution is 0.769g/L and the leaching concentration of calcium is 0.683 g/L;
s5, adding ammonia water dropwise into the leachate obtained in the step S4 to adjust the pH value to 2, adding 1.6g/L of ammonium sulfate and 3 times of theoretically-added amount of oxalic acid, precipitating at the temperature of 30 ℃, filtering to obtain a precipitate and a filtrate, analyzing the metal content by adopting ICP-OES and ICP-MS, and finding that 96.25% of rare earth is recovered through precipitation, and 96.72% of calcium is remained in the filtrate;
s6, placing the precipitate obtained in the step S5 in a muffle furnace to roast for 1h at 900 ℃, and obtaining the mixed rare earth oxide with the purity of 96.95 percent and the recovery rate of 85.73 percent.
Comparative example 1 treatment method of hyper-enriched plant
S1, drying and crushing the dicranopteris pedata leaf serving as a harvested product of the rare earth super-enriched plant into uniform powder by using a crusher, taking 2g of the powder sample, placing the powder sample into an inner liner of a hydrothermal reaction kettle, adding 40mL of 0.4mol/L sulfuric acid, placing the closed reaction kettle into an oven, carrying out solvent thermal reaction for 2 hours at 160 ℃, cooling to room temperature, collecting and separating to obtain a liquid-phase product and a solid-phase product;
s2, the liquid phase product obtained in the step S1 does not dissolve the plant endophyte component, and the step does not obtain a lignin product;
s3, analyzing the metal content of 1.18g of the solid-phase product obtained in the step S1 by ICP-OES and ICP-MS, and finding that the fixation rates of rare earth, calcium, aluminum, iron and magnesium in the solid-phase component are 1.12%, 2.00%, 6.16%, 0.35% and 0.55% respectively, and the manganese content is not detected, which indicates that the rare earth and impurity metals are basically dissolved in the solution, and the process cannot realize the primary separation of the rare earth and other impurity metals.
Comparative example 2 treatment method of hyper-enriched plant
S1, drying and crushing the dicranopteris pedata leaf serving as a harvested product of the rare earth super-enrichment plant into uniform powder by using a crusher, taking 2g of the powder sample, placing the powder sample in an inner liner of a hydrothermal reaction kettle, adding 30mL of 0.4mol/L sulfuric acid and 10mL of ethanol, placing the closed reaction kettle in an oven for solvothermal reaction at 160 ℃ for 2 hours, cooling to room temperature, collecting and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid-phase product obtained in the step S1 by rotary evaporation, adding 500mL of deionized water, standing and precipitating for 24 hours, and filtering to obtain only 0.0007g of a precipitation product;
s3, analyzing the metal content of 1.19g of the solid-phase product obtained in the step S1 by ICP-OES and ICP-MS, and finding that the fixation rates of rare earth, calcium, aluminum, iron and magnesium in the solid-phase component are 4.93%, 4.02%, 6.21%, 1.75% and 0.51% respectively, and the manganese content is not detected, which indicates that most of rare earth and impurity metals are dissolved in the solution, and the process cannot realize the primary separation of the rare earth and other impurity metals.
Measurement of Properties
The SEM image (500 × magnification) of the mixed rare earth oxide obtained in example 1 was measured, and the results are shown in fig. 2, in which the full scan image, the alignment mark image of element O, the alignment mark image of element La, the alignment mark image of element Ce, the alignment mark image of element Pr, and the alignment mark image of element Nd are shown in this order from left to right. As can be seen from the figure, the mixed rare earth oxide obtained by the invention has the rare earth elements of La, Ce, Pr, Nd and O, and the main structure of the mixed rare earth oxide is combined by the elements.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for recovering rare earth and biomass high value-added products from hyper-enriched plants is characterized by comprising the following steps:
s1, crushing the hyper-enriched plants, adding a sulfuric acid solution and absolute ethyl alcohol, carrying out complete thermal reaction on the solvents at 140-180 ℃ under a closed condition, cooling and separating to obtain a liquid-phase product and a solid-phase product;
s2, removing ethanol from the liquid phase product obtained in the step S1, adding water to completely precipitate, and filtering to obtain lignin particles;
s3, completely pyrolyzing the solid-phase product obtained in the step S1 at 450-650 ℃ to obtain a phenol pyrolysis product and residues;
s4, ashing the residues obtained in the step S3, and leaching with a hydrochloric acid solution to obtain a leaching solution;
s5, adjusting the pH of the leachate obtained in the step S4 to 1-3, adding ammonium sulfate and oxalic acid, completely precipitating, and filtering to obtain a precipitate and a filtrate;
s6, completely roasting the precipitate obtained in the step S5 at 800-900 ℃ to obtain the mixed rare earth oxide.
2. The method according to claim 1, wherein in step S1, the concentration of the sulfuric acid solution is 0.1-0.5 mol/L.
3. The method of claim 1, wherein in step S3, the pyrolysis is performed in an inert gas atmosphere.
4. The method according to claim 1, wherein the ashing temperature in step S4 is 500 to 600 ℃.
5. The method according to claim 1, wherein in step S4, the concentration of the hydrochloric acid solution is 0.1-0.5 mol/L.
6. The method according to claim 1, wherein in step S4, the solid-to-liquid ratio of the hydrochloric acid solution is (10-30) mL: 1g of the total weight of the composition.
7. The method as claimed in claim 1, wherein the ammonium sulfate is added in an amount of (0.8-4.0) g/L in step S5.
8. The method according to claim 1, wherein the temperature of the precipitation in step S5 is 30-80 ℃.
9. The method according to any one of claims 1 to 8, wherein the hyper-enriched plant comprises dicranopteris pedata, pokeberry root, crescent fern, hickory nut, pecan and dryopteris fragrans.
10. The use of the method for recovering rare earth and biomass high value-added products from hyper-enriched plants as claimed in any of claims 1 to 9 in the comprehensive resource utilization of rare earth hyper-enriched plants.
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| CN111111660A (en) * | 2020-01-17 | 2020-05-08 | 中山大学 | Method for preparing carbon dioxide reduction photocatalyst by utilizing hyper-enriched plants |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117701273A (en) * | 2023-12-12 | 2024-03-15 | 中山大学 | Photoluminescent material based on rare earth super-enriched plants and preparation method and application thereof |
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