CN111020239A - Method for recovering rare earth and energy substances from rare earth hyper-enrichment plants - Google Patents
Method for recovering rare earth and energy substances from rare earth hyper-enrichment plants Download PDFInfo
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Abstract
The invention discloses a method for recovering rare earth and energy substances from rare earth hyperaccumulation plants, which combines the technologies of mechanical crushing, vacuum pyrolysis sectional condensation and rare earth leaching precipitation, and recovers pyrolysis oil and pyrolysis gas generated by pyrolysis of biomass of rare earth hyperaccumulation plant harvest through the technology of vacuum pyrolysis sectional condensation; processing the residue rich in rare earth elements by adopting a leaching precipitation technology to obtain mixed rare earth oxides; the residue after leaching the rare earth can be reused as a porous adsorption carbon material. The invention realizes high-value resource recovery of the rare earth hyper-enrichment plant harvest, converts the rare earth hyper-enrichment plant biomass into energy substances, recovers the rare earth elements rich in the plant body, avoids the harm of the rare earth hyper-enrichment plant to the environment, has clean and environment-friendly whole process, no secondary pollution, simple process and high recovery efficiency, and has obvious economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to a method for recovering rare earth and energy substances from rare earth hyperaccumulation plants.
Background
China is the country with the most rare earth reserves and is used as a strategic resource, and the rare earth is widely applied to the fields of military affairs, metallurgy, petrochemical industry and the like. However, since the environment is not properly managed during the rare earth mining process, the ecology in the regions around the rare earth producing area is seriously damaged, which has a serious impact on the health of human body. Therefore, some methods for treating rare earth pollution have been developed at present, and among them, phytoremediation is widely used in rare earth pollution treatment because of its low cost, and has the advantages of protecting surface soil, reducing erosion and reducing water and soil loss after vegetation is formed. However, the repaired super-enriched rare earth plant is rich in rare earth elements, and can also become a dangerous waste rich in rare earth if the plant is not reasonably disposed. On the other hand, the rare earth hyper-enrichment plant is a resource, the hyper-enrichment plant has higher recovery value, if the rare earth can be recovered from the rare earth hyper-enrichment plant harvest, the problem of environmental pollution can be solved, certain economic value can be brought, and both environmental and economic benefits can be achieved.
At present, no green treatment method aiming at the rare earth super-enriched plants exists, and full-value green recovery of the rare earth super-enriched plants is not performed. The patent CN108485692A discloses that the super-enriched plant harvest is prepared into biochar and generates hydrogen-rich gas by technical methods such as crushing, sorting, carbonization, and activation, but the technical method does not recover and treat the metal elements in the super-enriched plant harvest, which causes waste of resources. Patent CN109794262A burns cadmium-containing biochar from cadmium-hyper-enrichment plant harvest in a protective gas atmosphere through a tube furnace, and prepares the cadmium-containing biochar into a carbon-loaded cadmium sulfide photocatalytic material through a vulcanization reaction, but pyrolysis oil and pyrolysis gas generated in the pyrolysis process are not effectively treated and recovered, and are exposed to the environment to cause environmental pollution, thus causing harm to human bodies and being a waste of resources. Patent CN110145749A adopts safe incineration device to carry out incineration disposal with super enrichment plant results to subsequently handle harmful substance such as heavy metal tail gas and dust, sulphide that form burning, realized the safety minimizing of super enrichment plant, but the biomass resource of super enrichment plant results self and the heavy metal resource that is rich in vivo all not obtained effectual recovery. The technology of patent CN206966296U pyrolysis, leaching, purification, electrochemical deposition, oil-gas separation and the like converts pyrolysis oil generated by the pyrolysis of hyper-enriched plants into gasified coal gas, and recovers heavy metals in the hyper-enriched plants, but pyrolysis gas generated in the pyrolysis process is not properly treated, and environmental pollution can be caused when the pyrolysis gas is exposed in the environment.
The rare earth super-enriched plant harvest has high pollution and high resource, so that the treatment and disposal process of the rare earth super-enriched plant harvest has harmlessness, recycling and reduction, and the full-value recycling of the rare earth super-enriched plant harvest is realized. Therefore, a method for recycling the rare earth super-enriched plants in full value, which is green, safe, efficient, free from secondary pollution and free from secondary pollution, is urgently needed to be found.
Disclosure of Invention
The invention provides a method for recovering rare earth and energy oil gas from rare earth super-enriched plants aiming at the defects of the conventional method for recovering rare earth super-enriched plant resources, and the method is used for respectively recovering rare earth super-enriched plant harvest in the forms of pyrolysis oil, pyrolysis gas and rare earth oxide by mechanical crushing, vacuum pyrolysis sectional condensation and rare earth leaching precipitation technologies. The whole process is green and efficient, and the complete recovery of the rare earth hyper-enrichment plant harvest is carried out, so that the method has certain economic value.
Accordingly, it is a first object of the present invention to provide a method for recovering rare earth and energy substances from a rare earth hyperaccumulation plant.
The invention further aims to provide application of the method in resource utilization of the rare earth hyper-enriched plants.
The invention further aims to provide application of the leached residue obtained by the method in preparation or as a porous adsorption carbon material.
In order to achieve the purpose, the invention is realized by the following scheme:
a method for recovering rare earth and energy substances from rare earth super-enriched plants (such as dicranopteris pedata, pokeberry root and crescent brake) is characterized in that the recovery of rare earth and energy oil gas in the rare earth super-enriched plants is realized by mechanical crushing, vacuum pyrolysis, sectional condensation and leaching precipitation technologies.
Specifically, the method comprises the following steps:
s1, drying and crushing rare earth hyper-enrichment plants to obtain uniform rare earth hyper-enrichment plant powder;
s2, placing the rare earth hyper-enriched plant powder in a vacuum pyrolysis sectional condensation device for vacuum pyrolysis condensation treatment;
s3, collecting the pyrolysis oil, the pyrolysis gas and the pyrolysis rare earth-rich residue obtained in the step S2;
s4, adding HCl and HNO into the rare earth-rich residue3Leaching the mixed acid, and filtering to obtain a rare earth leaching solution and leached residues;
s5, adding oxalic acid into the obtained rare earth leachate for precipitation to obtain a rare earth precipitate;
s6, placing the rare earth precipitate in a muffle furnace to be roasted to obtain rare earth oxide.
The invention adopts vacuum pyrolysis and sectional condensation, the pyrolysis degree is complete, and the rare earth hyper-enrichment plant harvest is pyrolyzed to generate energy substances such as pyrolysis oil, pyrolysis gas and the like. Meanwhile, rare earth elements in the residue are extracted by adopting a rare earth leaching precipitation technology, and the residual residue can be recycled as a porous adsorption carbon material. The whole method for recovering the super-enriched plant harvest combines vacuum pyrolysis condensation and rare earth leaching precipitation technologies, realizes the recovery of pyrolysis oil, pyrolysis gas and rare earth elements and the recycling of residues, realizes high-value recycling, is green and efficient in the whole process, and has important application value in the field of recycling of the rare earth super-enriched plants.
Preferably, the vacuum pyrolysis sectional condensation device is a three-section vacuum pyrolysis condensation device, the first section is a pyrolysis zone, and the second section and the third section are condensation zones.
Preferably, the first-stage pyrolysis temperature is 650-750 ℃, the heating rate is 20-30 ℃/min, and the retention time is 30-45 min; the condensation temperature of the second section is 160-180 ℃; the condensation temperature of the third section is 60-80 ℃.
Most preferably, the first-stage pyrolysis temperature is 700 ℃, the heating rate is 30 ℃/min, and the retention time is 30 min; the condensation temperature of the second section is 180 ℃; the condensation temperature in the third stage was 80 ℃.
Preferably, the HCl and HNO are in step S43The volume ratio is 1: 3-4; the HCl and HNO3The concentration of (a) is 2-3 mol/L; the volume ratio of the rare earth-rich residue to the mixed acid is 1: 3-4; the leaching treatment temperature is 75-85 ℃, and the leaching treatment time is 7-9 hours.
Most preferably, the HCl and HNO of step S43The volume ratio is 1: 3; the concentration of the HCl is 3 mol/L; the HNO3The concentration of (A) is 2 mol/L; the volume ratio of the rare earth-rich residue to the mixed acid is 1: 3; the leaching treatment temperature is 80 ℃, and the leaching treatment time is 8 hours.
Preferably, the temperature for adding oxalic acid for precipitation in the step S5 is 75-85 ℃, and the volume ratio of the rare earth leaching solution to the oxalic acid is 1: 1-1.5.
Most preferably, the temperature for adding oxalic acid for precipitation in the step S5 is 80 ℃, and the volume ratio of the rare earth leaching solution to the oxalic acid is 1:1.
Preferably, the roasting in the step S6 is carried out at 750-850 ℃ for 1-1.5 h.
Most preferably, the firing of step S6 is firing at 800 ℃ for 1 h.
Preferably, the vacuum degree of the vacuum pyrolysis sectional condensation device is 10-100 Pa.
Most preferably, the vacuum degree of the vacuum pyrolysis sectional condensation device is 10Pa
Preferably, the rare earth oxide is a mixed rare earth oxide with the purity of more than or equal to 90 percent.
The application of the method in the aspect of resource utilization of the rare earth super-enriched plants is also within the protection scope of the invention. Specifically, the resource utilization of the rare earth super-enriched plant refers to the recovery of rare earth and/or energy oil gas from the super-enriched plant.
In addition, the leached residue obtained in the method can be used for preparing or serving as a porous adsorption carbon material.
In addition, as an optional specific scheme, the structure of the vacuum pyrolysis sectional condensation device is as follows:
the device consists of a vacuum pyrolysis condensing system, a vacuum pumping system and a pyrolysis gas collecting system; the vacuum pyrolysis condensing system is connected with the pyrolysis gas collecting system through a vent pipeline, a gas outlet valve is arranged at the end of the vacuum pyrolysis condensing system, and a pyrolysis gas collecting system valve is arranged at the end of the pyrolysis gas collecting system; the vacuum pumping system consists of a backing pump and a diffusion pump, wherein the backing pump is connected with the vent pipeline and a backing pump valve is arranged between the backing pump and the vent pipeline, and the diffusion pump is connected with the vent pipeline and a diffusion pump valve is arranged between the diffusion pump and the vent pipeline; a vacuum pyrolysis condensing assembly is arranged in the vacuum pyrolysis condensing system; three temperature zones are arranged in the vacuum pyrolysis condensation assembly, the first temperature zone is a pyrolysis zone, the second temperature zone and the third temperature zone are condensation zones, each temperature zone is provided with a treatment object container and a heating element, and each heating element is connected with a temperature regulator; the vacuum pumping system is provided with a vacuum pumping system main switch and a vacuum instrument meter, the backing pump is provided with a backing pump switch, and the diffusion pump is provided with a diffusion pump switch; the vacuum pyrolysis condensing system is provided with an air inlet valve.
The method for recovering the energy substances from the rare earth super-enriched plant harvest by using the device can be carried out according to the following steps:
(1) the method comprises the steps of crushing rare earth hyper-enrichment plants into uniform powder by a shear type crusher, placing the crushed plants in a corundum crucible I, closing an air inlet valve, connecting all parts, and ensuring the sealing performance of a system.
(2) And opening a main switch of the vacuum pumping system, simultaneously opening a backing pump switch and a diffusion pump switch, opening a backing pump valve, and simultaneously ensuring that the diffusion pump valve is in a closed state, namely starting to pump the vacuum of the system. And when the vacuum degree of the system is 10-100 Pa and the diffusion pump is preheated for 40-50 min as shown by the vacuum instrument, closing the valve of the backing pump and opening the valve of the diffusion pump.
(3) And starting a main switch of the vacuum pyrolysis condensation assembly, adjusting a temperature regulator I, setting the pyrolysis final temperature to be 500-600 ℃, the heating rate to be 20-30 ℃/min, and the retention time to be 30-45 min. And simultaneously adjusting a temperature regulator II and a temperature regulator III, setting the condensation temperatures of the two sections of condensation zones to be 150-180 ℃ and 50-80 ℃, and starting to operate. And simultaneously opening a valve of the pyrolysis gas collection system.
(4) And after pyrolysis is finished and the temperature of the pyrolysis zone is reduced to be below 300 ℃, the vacuumizing system can be closed. And firstly closing a diffusion pump valve, waiting for 1h, closing a backing pump switch and a diffusion pump switch when the diffusion pump oil is cooled down, and simultaneously closing a vacuum pyrolysis condensation assembly main switch and a vacuumizing system main switch.
(5) And opening the air inlet valve, collecting pyrolysis products in the corundum crucible II and the corundum crucible III, and simultaneously collecting pyrolysis gas in the pyrolysis gas collecting system, so that the pyrolysis gas can be secondarily utilized as an energy substance.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the rare earth hyper-enriched plant is treated by adopting a vacuum pyrolysis sectional condensation technology, energy substances such as pyrolysis oil, pyrolysis gas and the like are recovered, and the waste of biomass resources of the rare earth hyper-enriched plant is avoided.
2. The method adopts the rare earth leaching precipitation technology to recover the rare earth elements in the residues, simultaneously furthest ensures that the structure of the leached residues is not damaged to a greater extent, and ensures the porous structure of the residues while recovering the rare earth elements, so that the residues can be subsequently used as porous adsorption carbon materials for recycling.
3. The method disclosed by the invention is green and efficient, simple to operate and high in recovery efficiency.
Drawings
FIG. 1 is a schematic structural diagram of a vacuum pyrolysis sectional condensation device;
1 is an air inlet valve; 2 is a vacuum pyrolysis condensation component; 3 is super-enriched plant harvest; 4 is a corundum crucible I; 5 is a vacuum pyrolysis condensing system; 6 is a corundum crucible II; 7 is a corundum tube; 8 is corundum crucible III; 9 is an air outlet valve; 10 is a main switch of the vacuum pumping system; 11 is a backing pump switch; 12 is a diffusion pump switch; 13 is a vacuum instrument meter; 14 is a pyrolysis gas collection system; 15 is a silicon molybdenum rod thermocouple heating element I; 16 is a silicon-molybdenum rod thermocouple heating element II; 17 is a main switch of the vacuum pyrolysis condensation component; 18 is a temperature regulator I; 19 is a temperature regulator II; 20 is a temperature regulator III; 21 is a silicon-molybdenum rod thermocouple heating element III; 22 is a backing pump valve; 23 is a backing pump; 24 is a diffusion pump valve; 25 is a diffusion pump; 26 is a vacuum-pumping system; 27 is a valve of a pyrolysis gas collection system;
FIG. 2 is a basic process for recovering rare earth and energy substances from the rare earth hyperaccumulation plant according to the present invention.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, 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.
Embodiment 1 method for recovering energy substances from rare earth hyper-enriched plant dicranopteris pedata by utilizing vacuum pyrolysis sectional condensation device
1. Vacuum pyrolysis sectional condensing device
The structure of the vacuum pyrolysis sectional condensation device is shown in fig. 1, and comprises a vacuum pyrolysis condensation system 5, a vacuum pumping system 26 and a pyrolysis gas collection system 14. The vacuum pyrolysis condensing system 5 is respectively provided with an air inlet valve 1 and an air outlet valve 9, a corundum tube 7 is arranged in the vacuum pyrolysis condensing assembly 2, a first temperature zone in the corundum tube is a pyrolysis zone, a corundum crucible I4 is arranged for containing the super-enriched plant harvest 3, and the temperature of the first temperature zone is controlled by controlling a silicon-molybdenum rod thermocouple heating element I15 through a temperature regulator I18; the second temperature zone is a condensation zone, a corundum crucible II 6 is placed to collect pyrolysis products generated by pyrolysis of the super-enriched plants in the first temperature zone, and the condensation temperature is controlled by controlling a silicon-molybdenum rod thermocouple heating element II 16 through a temperature regulator II 19; the third temperature zone is a condensation zone, a corundum crucible III 8 is placed to collect pyrolysis products which are not collected in the second temperature zone, and the temperature of the third temperature zone is controlled by controlling a silicon-molybdenum rod thermocouple heating element III 21 through a temperature regulator III 20; the main power supply of the vacuum pyrolysis condensation system 5 is controlled by a main switch 17 of the vacuum pyrolysis condensation component; the vacuum pumping system 26 consists of a backing pump 23 and a diffusion pump 25, wherein the backing pump 23 plays a role in vacuum pumping, the diffusion pump 25 plays a role in strengthening vacuum pumping, the vacuum degree of the system can be seen on a vacuum instrument table 13, a backing pump valve 22 controls the gas inlet and outlet of the backing pump 23, a diffusion pump valve 24 controls the gas inlet and outlet of the diffusion pump 25, and the vacuum pumping condition of the system is controlled by adjusting different valves, a backing pump switch 11 and a diffusion pump switch 12; the main power supply of the vacuum-pumping system 26 is controlled by a main switch 10 of the vacuum-pumping system; the pyrolysis gas collection system 14 is a gas collection tank, and controls the valve 27 of the pyrolysis gas collection system to be opened and closed, so that the function of collecting and decomposing the heat can be achieved.
2. Method for recovering energy substances from rare earth hyper-enriched plant dicranopteris pedata by utilizing vacuum pyrolysis sectional condensation device
(1) Crushing the rare earth hyper-enrichment plant dicranopteris pedata into uniform powder by adopting a shear type crusher, putting the crushed plant in a corundum crucible I, closing an air inlet valve, and connecting all parts to ensure the sealing property of the system.
(2) And opening a main switch of the vacuum pumping system, simultaneously opening a backing pump switch and a diffusion pump switch, opening a backing pump valve, and simultaneously ensuring that the diffusion pump valve is in a closed state, namely starting to pump the vacuum of the system. And when the vacuum degree of the system is 10Pa and the diffusion pump is preheated for 40min as shown by the vacuum instrument, closing the valve of the pre-pump and opening the valve of the diffusion pump.
(3) And starting a main switch of the vacuum pyrolysis condensation assembly, adjusting a temperature regulator I, setting the pyrolysis final temperature to be 700 ℃, the heating rate to be 30 ℃/min and the retention time to be 30 min. And simultaneously adjusting a temperature regulator II and a temperature regulator III, setting the condensation temperatures of the two sections of condensation zones to be 180 ℃ and 80 ℃, and starting to operate. And simultaneously opening a valve of the pyrolysis gas collection system.
(4) And after pyrolysis is finished and the temperature of the pyrolysis zone is reduced to be below 300 ℃, the vacuumizing system can be closed. And firstly closing a diffusion pump valve, waiting for 1h, closing a backing pump switch and a diffusion pump switch when the diffusion pump oil is cooled down, and simultaneously closing a vacuum pyrolysis condensation assembly main switch and a vacuumizing system main switch.
(5) And opening the air inlet valve, collecting pyrolysis products in the corundum crucible II and the corundum crucible III, and simultaneously collecting pyrolysis gas in the pyrolysis gas collecting system, so that the pyrolysis gas can be secondarily utilized as an energy substance.
Example 2 method for recovering rare earth and energy substances from rare earth super-enriched plant dicranopteris pedata
(1) Drying the dicranopteris pedata plant, and crushing the dried plant in a shear type crusher to obtain uniform dicranopteris pedata powder;
(2) weighing 40g of dicranopteris pedata powder, and performing pyrolysis and condensation treatment in a vacuum pyrolysis sectional condensation device. Setting the vacuum degree of a first stage pyrolysis area to be 10Pa, the pyrolysis final temperature to be 700 ℃, the heating rate to be 30 ℃/min and the retention time to be 30 min. Setting the condensation temperature of a second section of condensation area to be 180 ℃ and the condensation temperature of a third section of condensation area to be 80 ℃;
(3) after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 27.666g of pyrolysis oil and pyrolysis gas in total, analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), finding that pyrolysis oil gas mainly comprises ethylene oxide and acetaldehyde, and can be recycled as energy substances, collecting pyrolysis residues to be subjected to subsequent treatment;
(4) ICP-MS is adopted to measure the total content of rare earth in the pyrolysis residue, and the total content is 6160mg kg-1. Taking 3mol/LHCl and 2mol/LHNO3The mixed acid (volume ratio is 1: 3) is used for leaching the residue, and the volume ratio of the mixed acid to the residue is 3: 1, setting the leaching temperature to 80 ℃, completely reacting for about 8 hours, filtering to obtain rare earth leachate,the residual residue can be recycled as porous adsorption carbon material;
(5) adding oxalic acid into the rare earth leachate, and setting the temperature to be 80 ℃, wherein the volume ratio of the rare earth leachate to the oxalic acid is 1:1, so as to obtain a rare earth precipitate;
(6) and (3) placing the rare earth precipitate in a muffle furnace, and roasting for 1h at the temperature of 800 ℃ to obtain the mixed rare earth oxide of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide with the purity of 94.08%.
The whole process is as shown in figure 2, the green resource recovery of the rare earth super-enriched plant harvest is realized through the treatment of the whole system, and the energy substance pyrolysis oil gas, the mixed rare earth oxide and the porous residue with adsorbability are respectively recovered from the rare earth super-enriched plant harvest. The whole process is simple in process, green and efficient, secondary pollution cannot be caused, and high economic benefits are achieved while environmental pollution is avoided.
Example 3A method for recovering rare earth and energy substances from the rare earth super-enriched plant Phytolacca americana
(1) Drying the rare earth hyper-enriched pokeberry plants, and crushing the dried plants in a shear type crusher to obtain uniform pokeberry powder;
(2) weighing 40g of the pokeberry root powder, and carrying out pyrolysis condensation treatment on the pokeberry root powder in a vacuum pyrolysis sectional condensation device. Setting the vacuum degree of the first stage pyrolysis area to be 50Pa, the pyrolysis final temperature to be 650 ℃, the heating rate to be 25 ℃/min and the retention time to be 30 min. Setting the condensation temperature of a second section of condensation area to be 160 ℃, and setting the condensation temperature of a third section of condensation area to be 70 ℃;
(3) after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 35.47g of pyrolysis oil and pyrolysis gas in total, analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), finding that pyrolysis oil gas mainly comprises ethylene oxide and acetaldehyde, and can be recycled as energy substances, collecting pyrolysis residues to be subjected to subsequent treatment;
(4) ICP-MS is adopted to measure the total content of rare earth in the pyrolysis residue, and the total content is 5971mg kg-1. Taking 3mol/LHCl and 2mol/LHNO3Mixed acid of (volume ratio is 1: 4)Leaching the residue, wherein the volume ratio of the mixed acid to the residue is 4: 1, setting the leaching temperature to be 75 ℃, completely reacting for about 9 hours, filtering to obtain a rare earth leaching solution, and recycling the residual residues to be used as a porous adsorption carbon material for reutilization;
(5) adding oxalic acid into the rare earth leachate, and setting the temperature to be 85 ℃, wherein the volume ratio of the rare earth leachate to the oxalic acid is 1:1.5, so as to obtain a rare earth precipitate;
(6) and (3) placing the rare earth precipitate in a muffle furnace, roasting for 1h at the temperature of 850 ℃, and finally obtaining the mixed rare earth oxide of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide with the purity of 91.71%.
The whole process is as shown in figure 2, the green resource recovery of the rare earth super-enriched plant harvest is realized through the treatment of the whole system, and the energy substance pyrolysis oil gas, the mixed rare earth oxide and the porous residue with adsorbability are respectively recovered from the rare earth super-enriched plant harvest. The whole process is simple in process, green and efficient, secondary pollution cannot be caused, and high economic benefits are achieved while environmental pollution is avoided.
Example 4A method for recovering rare earth and energy substances from rare earth hyperaccumulation plant crescent moon fern
(1) Drying rare earth hyper-enriched crescent moon fern plants, and crushing the dried plants in a shear type crusher to obtain uniform crescent moon fern powder;
(2) weighing 40g of the crescent moon fern powder, and performing pyrolysis condensation treatment in a vacuum pyrolysis sectional condensation device. Setting the vacuum degree of a first stage pyrolysis area as 100Pa, the pyrolysis final temperature as 700 ℃, the heating rate as 30 ℃/min and the retention time as 45 min. Setting the condensation temperature of a second section of condensation area to be 170 ℃ and the condensation temperature of a third section of condensation area to be 80 ℃;
(3) after pyrolysis is completed, collecting pyrolysis oil and pyrolysis gas to obtain 31.33g of pyrolysis oil and pyrolysis gas in total, analyzing the pyrolysis oil and pyrolysis gas by adopting GC-MS (gas chromatography-mass spectrometry), finding that the pyrolysis oil gas mainly comprises ethylene oxide and acetaldehyde, and can be recycled as energy substances, collecting pyrolysis residues for subsequent treatment;
(4) ICP-MS is adopted to measure the total content of rare earth in the pyrolysis residue, and the total content is 6015.41mg kg-1. Taking 2mol/LHCl and 2mol/LHNO3The mixed acid (volume ratio is 1: 3) is used for leaching the residue, and the volume ratio of the mixed acid to the residue is 3: 1, setting the leaching temperature to be 75 ℃, completely reacting for about 8 hours, filtering to obtain a rare earth leaching solution, and recycling the residual residues to be used as a porous adsorption carbon material for reutilization;
(5) adding oxalic acid into the rare earth leachate, and setting the temperature to be 75 ℃, wherein the volume ratio of the rare earth leachate to the oxalic acid is 1:1, so as to obtain a rare earth precipitate;
(6) and (3) placing the rare earth precipitate in a muffle furnace, roasting for 1h at the temperature of 750 ℃, and finally obtaining the mixed rare earth oxide of lanthanum oxide, neodymium oxide, cerium oxide and praseodymium oxide with the purity of 90.82%.
The whole process is as shown in figure 2, the green resource recovery of the rare earth super-enriched plant harvest is realized through the treatment of the whole system, and the energy substance pyrolysis oil gas, the mixed rare earth oxide and the porous residue with adsorbability are respectively recovered from the rare earth super-enriched plant harvest. The whole process is simple in process, green and efficient, secondary pollution cannot be caused, and high economic benefits are achieved while environmental pollution is avoided.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for recovering rare earth and energy substances from rare earth super-enriched plants is characterized in that the recovery of rare earth and energy oil gas in the rare earth super-enriched plants is realized by mechanical crushing, vacuum pyrolysis sectional condensation and leaching precipitation technologies.
2. The method of claim 1, comprising the steps of:
s1, drying and crushing rare earth hyper-enrichment plants to obtain uniform rare earth hyper-enrichment plant powder;
s2, placing the rare earth hyper-enriched plant powder in a vacuum pyrolysis sectional condensation device for vacuum pyrolysis condensation treatment;
s3, respectively collecting the pyrolysis oil, the pyrolysis gas and the rare earth-rich residues obtained in the step S2;
s4, adding HCl and HNO into the rare earth-rich residue3Leaching the mixed acid, and filtering to obtain a rare earth leaching solution and leached residues;
s5, adding oxalic acid into the obtained rare earth leachate for precipitation to obtain a rare earth precipitate;
s6, placing the rare earth precipitate in a muffle furnace to be roasted to obtain rare earth oxide.
3. The method according to claim 2, wherein the vacuum pyrolysis staged condensation device is a three-stage vacuum pyrolysis condensation device, the first stage is a pyrolysis zone, and the second stage and the third stage are condensation zones; the first-stage pyrolysis temperature is 650-700 ℃, the heating rate is 20-30 ℃/min, and the retention time is 30-45 min; the condensation temperature of the second section is 160-180 ℃; the condensation temperature of the third section is 60-80 ℃.
4. The method of claim 2, wherein the HCl and HNO are mixed in step S43The concentration of (a) is 2-3 mol/L, HCl and HNO3Is 1: 3-4; the volume ratio of the rare earth-rich residue to the mixed acid is 1: 3-4; the leaching treatment temperature is 75-85 ℃, and the leaching treatment time is 7-9 hours.
5. The method according to claim 2, wherein the temperature for adding oxalic acid for precipitation in the step S5 is 75-85 ℃, and the volume ratio of the rare earth leaching solution to oxalic acid is 1: 1-1.5.
6. The method of claim 2, wherein the roasting in step S6 is carried out at 750-850 ℃ for 1-1.5 h.
7. The method according to claim 2, wherein the vacuum degree of the vacuum pyrolysis sectional condensation device is 10-100 Pa.
8. The method according to any one of claims 2 to 7, wherein the rare earth oxide is a mixed rare earth oxide having a purity of 90% or more.
9. Rare earth oxides, pyrolysis oil or pyrolysis gas obtained by the process according to any one of claims 1 to 7.
10. The application of the method of any one of claims 1 to 7 in resource utilization of rare earth super-enriched plants.
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