Method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element

Abstract

The invention disclosed a method for recycling rare earth elements from waste light-emitting electronic components by pyrolysis and alkaline melting-acid leaching. Based on the pyrolysis properties of the organic polymer, through catalytic pyrolysis of the organic polymer material in electronic components and convert the carbon in the residue into water gas, realize high-efficient dismantling of waste electronic component packaging materials. The traditional problems that the compositions of waste light-emitting electronic components are difficult to disassemble are solved, the generated pyrolysis gas and water gas can continuously supply energy for the pyrolysis system and recover the heat in the flue gas to save energy. Meanwhile, based on the chemical dissolution reaction mechanism of phosphors, the combination process of alkali melting, and acid leaching is used to efficiently recover rare earth elements from the waste light-emitting electronic components, and the step leaching of rare earth elements is realized. The rare earth oxalate can be recovered by precipitation, which greatly reduces the difficulty of late separation and purification.

Claims

1. A method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element, comprising: step 1: using a steel belt continuous pyrolysis furnace to pyrolyze waste light-emitting electronic components, wherein N.sub.2 is introduced into the steel belt continuous pyrolysis furnace as a protective gas, oil-gas mixture and residue are obtained by heating and pyrolysis; initial temperature of the pyrolysis is 300-400 C., end temperature of the pyrolysis is 500-650 C.; 3-stage zone temperature control heating is adopted, temperature of zone 1 is 300-400 C., temperature of zone 2 is 400-550 C., temperature of zone 3 is 500-650 C., and pyrolysis time is 90-150 min; step 2: the residue with residual heat is sent, under protection of N.sub.2 atmosphere, to a gas generator, and high-temperature water vapor is introduced to convert carbon in the residue into water gas to obtain pyrolysis residue; temperature of the high-temperature water vapor is 750-900 C., reaction pressure is 2.3-3.2 MPa, and reaction time is 3-5 min; step 3: the oil-gas mixture is sent to a spray condensing tower, HBr is removed by lye spray and oil and gas are separated, pyrolysis oil, pyrolysis gas and NaBr are obtained; step 4: phosphor powder in the pyrolysis residue and metals in the pyrolysis residue are separated by eddy current separation, and acid leaching solvent and acid leaching auxiliary solvent are added to the phosphor powder to conduct acid leaching reaction; filtrate 1 and filter residue 1 are obtained by filtration; step 5: adding alkali melting agent to filter residue 1, performing an alkali melting process to obtain an alkali melting product; then adding acid leaching solvent and acid leaching auxiliary solvent to the alkali melting product to carry out acid leaching treatment, phosphor powder of nitrogen oxide system and phosphor powder of garnet system are leached, and filtrate 2 containing Eu.sup.3+, Tb.sup.3+ and Ce.sup.3+ is obtained by filtration; in the alkali melting process, a mass ratio of filter residue 1 to the alkali melting agent is 1:2-1:6, calcination temperature is 600-1000 C., and calcination time is 30-60 min; step 6: mixing filtrate 1 and filtrate 2 to obtain a mixed solution, adding a dispersant to the mixed solution, stirring and mixing; adding an oxalic acid solution to the mixed solution, then adding ammonia water to the mixed solution to obtain a final solution, wherein pH of the final solution is adjusted to 1.8-2.0 with the ammonia water, and the final solution is settled at 23-28 C. for 4-6 hours; after the settling of the final solution is complete, precipitation is filtered, washed, and dried by heat from a flue gas boiler to obtain rare earth oxalate.

2. The method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element according to claim 1, wherein: in step 3, the lye is a NaOH solution and a mass percentage concentration of the NaOH solution is 5-10%.

3. The method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element according to claim 1, wherein: in step 4, the acid leaching reaction is conducted at 30-50 C. for 40-80 min, the acid leaching solvent and the acid leaching auxiliary solvent are added at following ratios: every kilogram of the phosphor powder adds 3-8 L of the acid leaching solvent, and 2-4 L of the acid leaching auxiliary solvent.

4. The method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element according to claim 1, wherein: in step 5, the acid leaching treatment is carried out at 70-90 C. for 20-25 min, the acid leaching solvent and the acid leaching auxiliary solvent are added at ratios: every kilogram of the alkali melting product adds 3-8 L of the acid leaching solvent, and 2-4 L of the acid leaching auxiliary solvent.

5. The method of pyrolysis for waste light-emitting electronic components and recovery for rare-earth element according to claim 1, wherein: in step 6, the dispersing agent is Polyethylene Glycol (PEG) 20000 or Polyethyleneimine (PEI), and added in the amount of 3-5% (Wt) of the mixed solution, and the oxalic acid solution is added in the amount of 20-33% (wt) of the mixed solution.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows the flow chart of the invention

EMBODIMENTS

(2) In the embodiments: Acid leaching solventhydrochloric acid, mass fraction 38%; Acid leaching auxiliary solventhydrogen peroxide, mass fraction 30%; Precipitantoxalic acid solution, concentration 30 g/L;

Embodiment 1

(3) The waste light-emitting electronic components are sent to the steel strip continuous pyrolysis furnace for pyrolysis for 90 min, and N.sub.2 is introduced into the furnace as a protective gas, the initial pyrolysis temperature was set at 320 C. and the final pyrolysis temperature was set at 520 C. The temperature of zone 1 is 320 C., the temperature of zone 2 is 450 C., and the temperature of zone 3 is 520 C. to obtain oil and gas mixture and residue; under the protection of N.sub.2 atmosphere, the residue with residual heat is sent to the gas generator, and water vapor at 800 C. is introduced, the reaction was carried out under 3.0 MPa for 4 min to obtain pyrolysis residue and water gas; the oil and gas mixture is sent to the spray condensation tower, and the NaOH alkali solution with a mass percentage concentration of 6% is sprayed to obtain pyrolysis oil, pyrolysis gas and NaBr; eddy current was used to separate pyrolysis slag, and the phosphor powder is obtained by separation. Add 6 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% into each kilogram of phosphor powder for acid leaching treatment. The reaction temperature is set to 40 C. and the reaction time is 60 min. Filtrate 1 and filter residue 1 are obtained by filtration, the leaching efficiency of Y.sup.3+ is 99.95%; add Na.sub.2O.sub.2 alkali melting agent with a slag-alkali mass ratio of 1:2 in filter residue 1 for high-temperature alkali melting, set the calcination temperature at 700 C., calcination time 60 min, add 4 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% in every kilogram of filter residue 1 to carry out acid leaching treatment, set the reaction temperature to 75 C. and the reaction time to 25 min, and filter to obtain filtrate 2. The leaching efficiency of Eu.sup.3+, Tb.sup.3+ and Ce.sup.3+ is 99.50%; mix filtrate 1 and filtrate 2, add 2% mass of PEG 20000 dispersant of the mixed solution, stir and mix, add 25% mass of 30 g/L oxalic acid solution of the mixed solution, adjust the pH of the solution to 2.0 with ammonia, and settle for 4 hours at 25 C., after filtration, washing and drying, rare earth oxalate is obtained, and the total recovery rate of rare earth is 99.12%.

Embodiment 2

(4) The waste light-emitting electronic components are sent to the steel strip continuous pyrolysis furnace for pyrolysis for 90 min, and N.sub.2 is introduced into the furnace as a protective gas, the initial pyrolysis temperature was set at 330 C. and the final pyrolysis temperature was set at 560 C. The temperature of zone 1 is 330 C., the temperature of zone 2 is 480 C., and the temperature of zone 3 is 560 C. to obtain oil and gas mixture and residue; under the protection of N.sub.2 atmosphere, the residue with residual heat is sent to the gas generator, and water vapor at 800 C. is introduced, the reaction was carried out under 3.0 MPa for 4 min to obtain pyrolysis residue and water gas; the oil and gas mixture is sent to the spray condensation tower, and the NaOH alkali solution with a mass percentage concentration of 6% is sprayed to obtain pyrolysis oil, pyrolysis gas and NaBr; eddy current is used to separate pyrolysis slag, and the phosphor powder is obtained by separation. Add 6 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% into each kilogram of phosphor powder for acid leaching treatment. The reaction temperature is set to 40 C. and the reaction time is 60 min. Filtrate 1 and filter residue 1 are obtained by filtration, the leaching efficiency of Y.sup.3+ is 99.96%; add Na.sub.2O.sub.2 alkali melting agent with a slag-alkali mass ratio of 1:6 in filter residue 1 for high-temperature alkali melting, set the calcination temperature at 750 C., calcination time 65 min, add 4 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% in every kilogram of filter residue 1 to carry out acid leaching treatment, set the reaction temperature to 75 C. and the reaction time to 25 min, and filter to obtain filtrate 2. The leaching efficiency of Eu.sup.3+, Tb.sup.3+ and Ce.sup.3+ is 99.58%; mix filtrate 1 and filtrate 2, add 2% mass of PEG 20000 dispersant of the mixed solution, stir and mix, add 25% mass of 30 g/L oxalic acid solution of the mixed solution, adjust the pH of the solution to 2.0 with ammonia, and settle for 4 hours at 25 C., after filtration, washing and drying, rare earth oxalate is obtained, and the total recovery rate of rare earth is 99.75%.

Embodiment 3

(5) The waste light-emitting electronic components are sent to the steel strip continuous pyrolysis furnace for pyrolysis for 95 min, and N.sub.2 is introduced into the furnace as a protective gas, the initial pyrolysis temperature was set at 340 C. and the final pyrolysis temperature was set at 520 C. The temperature of zone 1 is 340 C., the temperature of zone 2 is 470 C., and the temperature of zone 3 is 520 C. to obtain oil and gas mixture and residue; under the protection of N.sub.2 atmosphere, the residue with residual heat is sent to the gas generator, and water vapor at 800 C. is introduced, the reaction was carried out under 3.0 MPa for 4 min to obtain pyrolysis residue and water gas; the oil and gas mixture is sent to the spray condensation tower, and the NaOH alkali solution with a mass percentage concentration of 6% is sprayed to obtain pyrolysis oil, pyrolysis gas and NaBr; eddy current is used to separate pyrolysis slag, and the phosphor powder is obtained by separation. Add 6 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% into each kilogram of phosphor powder for acid leaching treatment. The reaction temperature is set to 40 C. and the reaction time is 60 min. Filtrate 1 and filter residue 1 are obtained by filtration, the leaching efficiency of Y.sup.3+ is 99.95%; add Na.sub.2O.sub.2 alkali melting agent with a slag-alkali mass ratio of 1:4 in filter residue 1 for high-temperature alkali melting, set the calcination temperature at 800 C., calcination time 65 min, add 4 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% in every kilogram of filter residue 1 to carry out acid leaching treatment, set the reaction temperature to 75 C. and the reaction time to 25 min, and filter to obtain filtrate 2. The leaching efficiency of Eu.sup.3+, Tb.sup.3+ and Ce.sup.3+ is 99.53%; mix filtrate 1 and filtrate 2, add 2% mass of PEG 20000 dispersant of the mixed solution, stir and mix, add 25% mass of 30 g/L oxalic acid solution of the mixed solution, adjust the pH of the solution to 2.0 with ammonia, and settle for 4 hours at 25 C., after filtration, washing and drying, rare earth oxalate is obtained, and the total recovery rate of rare earth is 99.59%.

Embodiment 4

(6) The waste light-emitting electronic components are sent to the steel strip continuous pyrolysis furnace for pyrolysis for 100 min, and N.sub.2 is introduced into the furnace as a protective gas, the initial pyrolysis temperature was set at 320 C. and the final pyrolysis temperature was set at 540 C. The temperature of zone 1 is 320 C., the temperature of zone 2 is 480 C., and the temperature of zone 3 is 540 C. to obtain oil and gas mixture and residue; under the protection of N.sub.2 atmosphere, the residue with residual heat is sent to the gas generator, and water vapor at 800 C. is introduced, the reaction was carried out under 3.0 MPa for 4 min to obtain pyrolysis residue and water gas; the oil and gas mixture is sent to the spray condensation tower, and the NaOH alkali solution with a mass percentage concentration of 6% is sprayed to obtain pyrolysis oil, pyrolysis gas and NaBr; eddy current is used to separate pyrolysis slag, and the phosphor powder is obtained by separation. Add 6 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% into each kilogram of phosphor powder for acid leaching treatment. The reaction temperature is set to 40 C. and the reaction time is 60 min. Filtrate 1 and filter residue 1 are obtained by filtration, the leaching efficiency of Y.sup.3+ is 99.96%; add Na.sub.2O.sub.2 alkali melting agent with a slag-alkali mass ratio of 1:4 in filter residue 1 for high-temperature alkali melting, set the calcination temperature at 700 C., calcination time 60 min, add 4 L of hydrochloric acid with a mass fraction of 38% and 2 L of hydrogen peroxide with a mass fraction of 30% in every kilogram of filter residue 1 to carry out acid leaching treatment, set the reaction temperature to 85 C. and the reaction time to 20 min, and filter to obtain filtrate 2. The leaching efficiency of Eu.sup.3+, Tb.sup.3+ and Ce.sup.3+ is 99.56%; mix filtrate 1 and filtrate 2, add 2% mass of PEG 20000 dispersant of the mixed solution, stir and mix, add 25% mass of 30 g/L oxalic acid solution of the mixed solution, adjust the pH of the solution to 2.0 with ammonia, and settle for 4 hours at 25 C., after filtration, washing and drying, rare earth oxalate is obtained, and the total recovery rate of rare earth is 99.64%.