WO2015021727A1 - 一种含稀土溶液的处理方法 - Google Patents

一种含稀土溶液的处理方法 Download PDF

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Publication number
WO2015021727A1
WO2015021727A1 PCT/CN2013/090371 CN2013090371W WO2015021727A1 WO 2015021727 A1 WO2015021727 A1 WO 2015021727A1 CN 2013090371 W CN2013090371 W CN 2013090371W WO 2015021727 A1 WO2015021727 A1 WO 2015021727A1
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Prior art keywords
fine
grained clay
rare earth
adsorption
clay
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PCT/CN2013/090371
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English (en)
French (fr)
Inventor
李永绣
谢爱玲
王悦
宋丽莎
李昳林
周新木
周雪珍
刘艳珠
李静
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南昌大学
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Priority claimed from CN201310355981.7A external-priority patent/CN103466738B/zh
Priority claimed from CN201310400389.4A external-priority patent/CN103449568B/zh
Application filed by 南昌大学 filed Critical 南昌大学
Priority to US14/431,753 priority Critical patent/US10253394B2/en
Priority to CA2885496A priority patent/CA2885496C/en
Publication of WO2015021727A1 publication Critical patent/WO2015021727A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method for treating a rare earth-containing solution. Background technique
  • Rare earths are widely used in various fields such as industry, military, agriculture, etc.
  • the rare earth functional materials that have been rapidly developed in recent decades have played an irreplaceable role in high-tech industries and military aerospace technologies, making rare earths increasingly recognized globally. Strategic resources.
  • Rare earth is a non-renewable natural resource.
  • the demand for rare earths continues to grow.
  • high-grade rare earth ore and rare earth reserves are declining. Therefore, the rare earth high-efficiency extraction technology for low-grade rare earth ore and the technology for recovering rare earth from low-concentration rare earth-containing wastewater generated from rare earth production process have received extensive attention and research. With the improvement of resources and environmental protection requirements, it is more urgent to research and develop low-concentration rare earth-containing solutions for recycling and wastewater discharge standards.
  • rare earth elements are enriched in wastewater with a certain concentration of ammonia nitrogen.
  • a certain amount of rare earth is also contained in the weathered mud associated with the fluorocarbonate rare earth ore.
  • Contact with an aqueous solution containing acid and ammonium during the beneficiation process also causes some rare earth to enter the solution. The random discharge of these solutions will not only lead to the waste of rare earth resources, but also to the environment significantly affected.
  • Rare earth enrichment and recovery methods have been widely studied and applied.
  • precipitation methods there are mainly precipitation methods, extraction methods, reverse osmosis methods, and ion exchange resin methods.
  • the precipitation method is the simplest, and the solution is made alkaline by the neutralization of lime, and the rare earth is precipitated by hydroxide precipitation and separated from a large amount of water.
  • the resin adsorption method is also relatively simple, but the resin loading is small, the cost is high, and the desorption of the rare earth is difficult.
  • the extraction method is complicated. Although the method has a large enrichment ratio and high efficiency, it has problems such as too small a solution, large dissolution loss, high cost, and large secondary pollution.
  • the treatment methods of ammonia nitrogen in wastewater mainly include the following methods: stripping method, biological method, chemical precipitation method, and chlorination method.
  • the denitrification efficiency of the stripping method is high, but the ammonia nitrogen is not fundamentally removed.
  • Biological treatment has a good effect, but the treatment time is long, which is difficult to control in practical applications.
  • the chemical precipitation method is flexible in operation and good in treatment, but the cost is high.
  • the fluorination method is a very effective method, and the reaction process is as follows: NH 4 + + 1.5H0C1 ⁇ 0.5N 2 + 1.5H 2 O + 2.5H + + 1.5Cr.
  • the treatment process of the chlorination method is stable, is not affected by water temperature, has low equipment investment, complete reaction and complete disinfection. However, its pH value is very high, and pH control is a difficult point of the chlorination method. Summary of the invention
  • the invention provides a treatment method for a rare earth-containing solution, wherein the method comprises:
  • the conditions of adsorption of the coarse-grained clay are such that the rare earth concentration in the coarse-grained clay adsorption solution is not higher than 0.5 based on the rare earth oxide.
  • the particle size of more than 90% of the particles in the fine-grained clay is smaller than the particle size of the particles in the coarse-grained clay, and the particle size of the fine-grained clay is 1-250 ⁇ m, and the particle size of the coarse-grained clay is 150- 1000 ⁇ ;
  • the inventors of the present invention have found through intensive studies that the rare earth-containing solution is sequentially adsorbed by the fine-grained clay and the coarse-grained clay, and the rare earth can be efficiently recovered from the low-concentration rare earth-containing solution.
  • the fine-grained clay when the fine-grained clay is a Na + -type fine-grained clay and/or a fine-grained clay of the Na + -H + type, and/or, when the coarse-grained clay is a Na + -type coarse-grained clay and/or a Na + -H + -type coarse-grained clay, can be used in the rare earth solution
  • the rare earth concentration is reduced to a lower level and the rare earths therein are more efficiently recovered.
  • the fine-grained clay when the fine-grained clay is adsorbed as sedimentation adsorption, and the coarse-grained clay is adsorbed as a bed adsorbent, not only can the rare earth can be more efficiently recovered from the low-concentration rare earth-containing solution. Moreover, it is also beneficial to the solid-liquid separation operation in the industrial process, saving the amount of clay. It is speculated that the reason may be due to: The fine-grained clay has a small particle size, and if the column bed adsorption mode is adopted, the flow resistance is large; and the sedimentation adsorption mode using the fine-grained clay mineral as the adsorbent and the filter aid is adopted.
  • the fine-grained clay can not only exert its adsorption effect, but also completely adsorb and precipitate the rare earth, and can collect the precipitated fine particles on the surface of the clay particles to generate coprecipitation, thereby strengthening the sedimentation performance of the particles, thereby not only being able to be less
  • the rare earth is effectively recovered under the use of fine-grained clay, and the solid-liquid separation is also facilitated, which can greatly reduce the workload of the filtration operation.
  • the fine-grained clay has a large adsorption capacity, and the rare earth-containing solution is first adsorbed by the fine-grained clay, so that most of the rare earth in the rare earth-containing solution is attached to the fine-grained clay.
  • the adsorption capacity of the coarse-grained clay is small, the formed bed has good permeability, so when the coarse-grained clay is adsorbed as a bed adsorption, it is suitable for treating a wastewater solution having a large amount of water and a low rare earth concentration, thereby The residual rare earth in the fine clay adsorption solution can be substantially removed by adsorption by the coarse clay.
  • the rare earth-containing solution further contains ammonia nitrogen at a concentration of 20-500 mg/L
  • the treatment method of the rare earth-containing solution further includes before the adsorption of the fine-grained clay Or during the adsorption of the fine-grained clay
  • sodium hydroxide, sodium carbonate or sodium hypochlorite when sodium hydroxide, sodium carbonate or sodium hypochlorite is added to the rare earth-containing solution and reacted, the sodium hydroxide, sodium carbonate or sodium hypochlorite may adjust the rare earth-containing solution.
  • the pH of the ammonia nitrogen is removed and the concentration of ammonia nitrogen in the rare earth-containing solution can be significantly reduced on the basis of recovery of the rare earth.
  • the rare earth-containing solution contains a relatively high concentration of ammonia nitrogen (200-500 mg/L)
  • the pH adjustment of the fine-grained clay by simply using sodium hydroxide or sodium carbonate does not lower the ammonia nitrogen to the requirements.
  • the obtained fine-grained clay adsorption solution further contains a certain amount of ammonia nitrogen (30-100 mg/L), and may also contain certain chloride ions and sodium ions; or, the fine-grained clay is simply adsorbed with sodium hypochlorite.
  • the pH is adjusted and the ammonia nitrogen is lowered to the desired range, and the resulting fine-grained clay adsorption solution may also contain chloride ions having a concentration of 100-3000 mg/L and/or sodium ions having a concentration of 100-3000 mg/L.
  • the fine-grained clay adsorption solution contains ammonia nitrogen having a concentration of 30-100 mg/L in terms of nitrogen, and/or chloride ion having a concentration of 100-3000 mg/L.
  • the treatment method of the rare earth-containing solution further comprising, after adsorbing the fine-grained clay and before adsorbing the coarse-grained clay, the fine-grained clay Suck
  • the solution was subjected to bipolar membrane hydrolysis treatment.
  • This enables the concentration of chloride and sodium ions and ammonia nitrogen in the fresh water obtained after hydrolysis of the bipolar membrane to be significantly reduced to meet higher emission standards; and the acid produced in the acid chamber of the bipolar membrane hydrolysis device It can be used for the preparation of the acidic sodium salt solution, and the alkali produced in the alkali chamber can be used for recovering rare earth from the analytical solution by precipitation and extraction, which is very promising for industrial application.
  • Figure 1 is a graph showing the effect of different ammonia nitrogen concentrations on the removal efficiency of rare earths
  • Figure 2 is a graph showing the results of changes in ammonia nitrogen concentration with alkaline treatment conditions
  • Figure 3 is a graph showing the results of the pH of the system as a function of the reaction. detailed description
  • the method for treating a rare earth-containing solution provided by the present invention comprises:
  • the conditions of adsorption of the coarse-grained clay are such that the rare earth concentration in the coarse-grained clay adsorption solution is not higher than 0.5 based on the rare earth oxide.
  • the particle size of more than 90% of the particles in the fine-grained clay is smaller than the particle size of the particles in the coarse-grained clay, and the particle size of the fine-grained clay is 1-250 ⁇ m, and the particle size of the coarse-grained clay is 150- 1000 ⁇ ;
  • the fine-grained clay and coarse-grained clay generally comprise a negatively charged skeleton and a positively charged binding ion, wherein the positively charged binding ions generally include both H + , Na + , Mg 2+ , K + , Ca 2+ and so on.
  • the fine-grained clay and the coarse-grained clay have an adsorption ability to the rare earth in the rare earth-containing solution when the positively-charged binding ions are the above-mentioned several binding ions, in order to increase the adsorption efficiency, the rare earth for more effective recovery of the rare earth solution, the fine clay fine particle clays particularly preferably Na + type and / or Na + -H + type clay fines, and / or,
  • the coarse-grained clay is particularly preferably a Na + -type coarse-grained clay and/or a Na + -H + -type coarse-grained clay.
  • Na + type refers to the conversion of positively charged binding ions in the clay to Na +
  • the "Na + -H + type” refers to the conversion of positively charged binding ions in the clay. For Na + and H + .
  • the Na + -type fine-grained clay and the Na + -type coarse-grained clay may be prepared according to various methods known to those skilled in the art, for example, fine-grained clay and coarse-grained clay may be respectively used for sodium chloride and / or sodium sulfate solution immersion or column exchange, from the viewpoint of ease of operation, it is preferably obtained by soaking with sodium chloride and / or sodium sulfate solution. Specifically, the concentrations of the sodium chloride solution and the sodium sulfate solution may each independently be 0.3 to 3 mol/L.
  • the total amount of the sodium chloride solution and the sodium sulfate solution may be from 1 to 5 mL with respect to the fine-grained clay or coarse-grained clay of lg.
  • the soaking temperature may be from 1 to 50 ° C, preferably from 20 to 40 ° C; the soaking time may be from 10 to 60 min, preferably from 20 to 40 min.
  • the Na + -H + -type fine-grained clay and the Na + -H + -type coarse-grained clay may also be prepared according to various methods known to those skilled in the art, for example, fine-grained clay and coarse-grained, respectively.
  • the granulated clay is obtained by soaking with an acidic sodium chloride and/or sodium sulfate solution or column exchange, and is preferably obtained by soaking with an acidic sodium chloride and/or sodium sulfate solution from the viewpoint of ease of handling.
  • the acidic sodium chloride and/or sodium sulfate solution is a solution obtained by adjusting the pH of the sodium chloride and/or sodium sulfate solution to be acidic.
  • the pH of the acidic sodium chloride and/or sodium sulfate solution may be greater than 0 and less than or equal to 6, and the concentration may be 0.3 to 3 mol/L.
  • the total amount of the acidic sodium chloride solution and the sodium sulfate solution may be from 1 to 20 mL with respect to the fine-grained clay or coarse-grained clay of lg.
  • the soaking temperature may be 1 to 50 ° C, preferably 20 to 40 ° C; the soaking time may be 10 to 60 min, preferably 20 to 40 min.
  • the fine-grained clay and the coarse-grained clay may be various existing clays capable of adsorbing rare earths, for example, may be dried or wet by removing large-sized minerals of 20 mesh (804 ⁇ m) or more from a mixed mineral in nature. The method is obtained by screening.
  • the main components of the fine-grained clay and the coarse-grained clay may be the same or different, and each of them is independently one or more of kaolin, halloysite, montmorillonite, zeolite, mica, feldspar, etc., The amount varies depending on the place of origin.
  • the feldspar comprises one or more of potassium feldspar, albite, anorthite, and the like according to a positively charged binding ion.
  • the treatment method of the rare earth-containing solution can treat the various rare earth-containing solutions existing and recover the rare earth therein, in view of the large amount of waste water having a low rare earth concentration and the difficulty in handling
  • the rare earth concentration in the rare earth-containing solution based on the rare earth oxide is preferably from 5 to 300 mg/L, preferably from 20 to 100 mg/L, particularly preferably from 40 to 60 mg/L.
  • the adsorption of the fine-grained clay is suitable for sinking
  • the adsorption is reduced to recover the rare earth in the rare earth solution.
  • the "sedimentation adsorption" means that the rare earth-containing solution is first stirred and mixed with the fine-grained clay, and then left to settle. The mixing and mixing time may be 10-30 minutes, and the static settling time may be 2-5 hours. After the sedimentation adsorption, solid-liquid separation can be carried out by means of clarification and filtration, and the obtained fine-grained clay adsorption solution is used for the next treatment, and the obtained fine-grained clay adsorbed by the fine-grained clay is desorbed.
  • the conditions of the sedimentation adsorption include: the fine clay may be used in an amount of 0.01-15 g, preferably 5-10 g, relative to 1 L of the rare earth-containing solution ; and the adsorption temperature may be 1-50 V, It is 15-40 ° C; the pH may be 6-12, preferably 8-11; the adsorption time may be 0.5-24 hours, preferably 2-5 hours.
  • the coarse particle adsorption is suitable for adsorption by a column bed.
  • the adsorption conditions of the column bed include: the adsorption temperature may be 1-50 ° C, preferably 15-40 ° C; and the pH may be 5-9, preferably 7-8.
  • the scale of the column bed and the filler of the coarse-grained clay can be reasonably selected according to actual conditions, and will not be described herein.
  • the rare earth concentration of the rare earth oxide in the adsorbed water of the column bed exceeds 0.5 mg/L, the coarse-grained clay in the column bed should be replaced in time.
  • the rare earth-containing solution may further contain ammonia nitrogen at a concentration of 20 to 500 mg/L, preferably 50 to 120 mg/L.
  • the treatment method of the rare earth-containing solution further preferably includes adding sodium hydroxide and sodium carbonate to the rare earth-containing solution before the adsorption of the fine-grained clay and/or during the adsorption of the fine-grained clay.
  • the amount of the sodium hydroxide or sodium carbonate and the reaction conditions are such that the concentration of ammonia nitrogen in the obtained solution is from 15 to 100 mg/L
  • the amount of the sodium hypochlorite and the reaction conditions are such that The concentration of ammonia nitrogen in the solution is not higher than 15 mg/L, so that not only the rare earth can be recovered, but also the ammonia nitrogen in the rare earth-containing solution can be effectively removed.
  • the amount of the sodium hypochlorite is such that the molar ratio of the ammonia nitrogen to the generated Cl 2 in the rare earth-containing solution is preferably 1:6-10, more preferably 1:7-9.
  • the conditions of the reaction generally include: the reaction temperature may be 1-50 ° C, preferably 15-40 ° C; the initial pH may be 6-12, preferably 8-11; 0.5-24 hours, preferably 2-5 hours.
  • the sodium hypochlorite achieves the purpose of reducing ammonia nitrogen by reacting with ammonia nitrogen to release nitrogen.
  • the pH of the reaction system generally decreases. After the reaction reaches equilibrium, the pH of the solution can usually be 6- 12, preferably 6-9.
  • the rare earth-containing solution contains a relatively high concentration of ammonia nitrogen (200-500 mg/L)
  • the pH adjustment of the fine-grained clay by simply using sodium hydroxide or sodium carbonate does not lower the ammonia nitrogen to the requirements.
  • Range The obtained fine-grained clay adsorption solution further contains a certain amount of ammonia nitrogen (30-100 mg/L), and may also contain certain chloride ions and sodium ions; or, the fine-grained clay is simply adsorbed by sodium hypochlorite.
  • the pH and the ammonia nitrogen are lowered to the required range, and the resulting fine-grained clay adsorption solution may also contain a chloride ion having a concentration of 100-3000 mg/L and/or a sodium ion having a concentration of 100-3000 mg/L.
  • the method for treating the rare earth-containing solution further comprises adsorbing the fine-grained clay after the adsorption of the fine-grained clay and before the adsorption of the coarse-grained clay
  • the solution is subjected to bipolar membrane hydrolysis, and the bipolar membrane is hydrolyzed to a condition such that the ammonia nitrogen concentration in the obtained solution is not higher than 30 mg/L, and the concentrations of chloride ions and sodium ions are both less than 30 mg/L.
  • the bipolar membrane hydrolysis can be carried out in various existing bipolar membrane electrodialyzers.
  • the bipolar membrane electrodialysis apparatus generally comprises an acid chamber, an alkali chamber, a fresh water chamber and an polar water chamber, and the specific structure is well known to those skilled in the art, and no further description is given here.
  • the conditions for the hydrolysis of the bipolar membrane generally include: the voltage between the two electrodes may be 10-30 volts, preferably 25-30 volts; the residence time of the fine clay adsorption solution may be 10-60 minutes, preferably 20 -40 minutes. Wherein, the residence time refers to the time during which the fine-grained clay adsorption solution passes through the fresh water chamber.
  • the desorption method can be carried out in accordance with various existing methods as long as the rare earth adsorbed on the fine-grained clay and the coarse-grained clay can be desorbed.
  • the fine-grained clay after adsorption and precipitation by the fine-grained clay may be brought into contact with the coarse-grained clay and the sodium salt solution after being adsorbed by the coarse-grained clay to obtain a desorbed liquid.
  • the rare earth in the desorption liquid can be usually recovered by a precipitation method or an extraction method, and the fine-grained clay and the coarse-grained clay can be recycled.
  • the method of desorbing rare earth from the fine-grained clay after adsorption by the fine-grained clay comprises soaking the fine-grained clay after adsorption by the fine-grained clay with an acidic sodium salt solution.
  • said soaking conditions typically include: with respect to the fine particles of clay after the clay fines through said adsorption lg, the amount of the acidic salt solution may be l-20mL, preferably 5-10 mL; sodium salt of the acid
  • the pH of the solution may be greater than 0 and less than or equal to 6, preferably 1-3; the soaking temperature may be 1-50 ° C, preferably 15-40 ° C; the soaking time may be 10-90 min, preferably 20-60 min. .
  • the method of desorbing rare earth from the coarse-grained clay after adsorption by the coarse-grained clay is to carry out desorption of the bed by using a sodium salt solution as a desorption liquid.
  • a sodium salt solution sodium salt solution
  • the conditions for desorption of the column bed generally include: the pH of the sodium salt solution may be 4-7, preferably 5-6; the desorption temperature is 1-50 ° C, preferably 15-40 ° C; sodium salt solution
  • the time passed through the bed can be from 30 to 300 min, preferably from 60 to 120 min.
  • the amount of the sodium salt solution is used when the column is desorbed
  • the weight ratio to the amount of coarse clay may range from 0.3 to 1:1, preferably from 0.5 to 0.8:1.
  • the rare earth-containing solution contains rare earth, ammonia nitrogen, and chlorine ions and sodium ions
  • the treatment method of the rare earth-containing solution includes:
  • the clay adsorption conditions are such that the rare earth concentration of the rare earth oxide in the obtained fine clay adsorption solution is not higher than 1 mg/L, and the concentration of ammonia nitrogen in the fine particle clay adsorption solution obtained by using nitrogen can be obtained when sodium hypochlorite is used. Not higher than 15 mg/L; when sodium hydroxide or sodium carbonate is used, the concentration of ammonia nitrogen in terms of nitrogen in the obtained fine-grain clay adsorption solution can be made between 15 and 100 mg/L.
  • the bipolar membrane is hydrolyzed to a condition such that the ammonia nitrogen concentration in the solution is not higher than 30 mg/L, and the chloride ion and the sodium The concentration of ions is less than 30mg / L;
  • the bipolar membrane water splitting water + -H + coarse grit clay is clay-type adsorption Na + form coarse clay or Na, the condition that the coarse grit clay adsorbed obtained
  • the rare earth concentration in the clay adsorption solution based on the rare earth oxide is not higher than 0.5 mg / L;
  • the concentration of the rare earth, the concentration of the ammonia nitrogen, and the concentration of the chloride are respectively determined by arsenazo III spectrophotometry, spectrophotometry, and mercury thiocyanate spectrophotometry, specifically, respectively.
  • the absorbance of the sample was measured according to arsenazo III spectrophotometry, Nessler's reagent spectrophotometry and mercury thiocyanate spectrophotometry, and the corresponding rare earth concentration, ammonia nitrogen concentration and chloride root concentration were calculated according to the calibration curve.
  • the calibration curve is obtained as follows:
  • Calibration curve for arsenazo III spectrophotometry In 8 50 mL colorimetric tubes, add 0.00, 2.00, 3.00, 4.00, 5.00, 6.00, 8.00 and 100.0 mL, respectively, at a concentration of 2 mg/L (based on rare earth oxides)
  • the rare earth standard working solution, the corresponding rare earth content is 0.0, 4.0, 6.0, 8.0, 10.0, 12.0, 16.0 and 20.0 ug, respectively, and then added 10.OmL acetic acid-sodium acetate buffer solution having a pH of 3.30.
  • test sample After standing for 20 minutes, the above 8 kinds of test samples were respectively added to a 10 mm cuvette at a wavelength of 655 nm, and the absorbance was measured with a blank reagent as the ordinate, and the corresponding rare earth content (ug) was used as the ordinate. On the abscissa, draw a calibration curve.
  • Calibration curve for mercury thiocyanate spectrophotometry In 8 50 mL colorimetric tubes, add 0.00, 2.00, 3.00, 4.00, 5.00, 6.00, 8.00 and lO.OOmL at a concentration of 1 mg/L (in terms of chlorine).
  • the standard working solution of sodium chloride the corresponding chloride content is 0.0, 2.0, 3.0, 4.0, 5.0, 6.0, 8.0 and B lO.Oug, respectively, and then added 8.0mL of nitric acid solution (wherein, nitric acid and water Volume ratio is 1:3), shake well, then add 2.5mL of thiocyanate at a concentration of 0.35% by weight, shake well, then add 2.5mL of ferric nitrate solution with a concentration of 150g / L, shake, and then separately Add water to the marking line.
  • nitric acid solution wherein, nitric acid and water Volume ratio is 1:3
  • test samples were respectively added to a 10 mm cuvette at a wavelength of 460 nm, and the absorbance was measured with a blank reagent as the ordinate, and the corresponding chloride content (ug) was used.
  • abscissa draw a calibration curve.
  • This preparation example is for explaining the preparation method of the fine-grained clay provided by the present invention.
  • lOOOOg was taken from the tailings of the Anyuan heap in Jiangxi (mainly composed of mica, kaolinite and potassium feldspar, the same below) through 100 mesh (150 micron, the same below) sieve, sieved under the grain Fine-grained clay with a diameter of 19-150 microns.
  • 100 g of the above fine-grained clay was taken and immersed in 500 mL of a 1.2 mol/L neutral sodium chloride aqueous solution for 30 minutes, and then filtered and the obtained solid phase product was washed with pure water, followed by 50 ° C. Drying gives a Na + -type fine-grained clay XN-1.
  • Preparation Example 2 This preparation example is for explaining the preparation method of the fine-grained clay provided by the present invention.
  • This preparation example is for explaining the preparation method of the fine-grained clay provided by the present invention.
  • This preparation example is for explaining the preparation method of the coarse-grained clay provided by the present invention.
  • the sieved material obtained after the 100-mesh sieve of the tailings from the Anyuan heap in Jiangxi Republic prepared in Preparation Example 1 was passed through a 20 mesh (804 ⁇ m, the same below) sieve at 25 ° C.
  • the material is a coarse-grained clay having a particle size of 150-804 microns.
  • 100 g of the above coarse-grained clay was taken and immersed in 500 mL of a neutral sodium chloride aqueous solution having a concentration of 1.3 mol/L for 30 minutes, and then filtered and the obtained solid phase product was washed with pure water, followed by baking at 50 ° C. Dry to obtain a Na + -type coarse-grained clay CN-1.
  • This preparation example is for explaining the preparation method of the coarse-grained clay provided by the present invention.
  • the sieved material obtained after the 100-mesh sieve of the tailings from the Anyuan heap in Jiangxi Republic prepared in Preparation Example 1 was passed through a 20 mesh (804 ⁇ m, the same below) sieve at 25 ° C.
  • the material is a coarse-grained clay having a particle size of 150-804 microns.
  • 100 g of the above coarse-grained clay was taken and immersed in 500 mL of an acidic sodium chloride aqueous solution having a concentration of 1.2 mol/L and a pH of 2 for 30 minutes, and then filtered and the obtained solid phase product was washed with pure water, followed by Drying at 50 ° C gave a coarse-grained clay CN-2 of the Na + -H + type.
  • This test example is used to test the performance of different fine-grained clays on the adsorption capacity of rare earths.
  • the fine-grained clays XN-1, XN-2, XN-3 and XN-4 were used as adsorbents, and the differential method was used to determine the O.lg fine-grained clay in 30 mL with the balance method.
  • the rare earth contents of the oxides were equilibrium concentrations and equilibrium adsorption amounts in the rare earth-containing solutions of 0, 0.25 mg, 0.30 mg, 0.35 mg, 0.40 mg, 0.50 mg, 0.60 mg, 0.70 mg, 0.80 mg, and 0.90 mg, respectively.
  • the Langmuir adsorption isotherm equation is applied, and the equilibrium concentration is taken as the abscissa, and the ratio of the corresponding equilibrium concentration and the equilibrium adsorption amount is plotted on the ordinate, and then the fitting parameter according to the adsorption isotherm curve is obtained.
  • the saturated adsorption capacity Qm (mg/g) and the correlation coefficient RL 2 were determined , and the results are shown in Table 1. It can be seen from the results in Table 1 that the adsorption of rare earth by fine-grained clay can well conform to the Langmuir adsorption model, which belongs to monolayer adsorption, but the fine-grained clay with different modification treatment has different characteristics for rare earth.
  • Adsorption effect fine-grained clay treated with neutral sodium chloride (Na + -type fine-grained clay) and fine-grained clay treated with acidic sodium chloride (Na + -H + -type fine-grained clay) It has a strong adsorption capacity and, therefore, is a preferred adsorbent.
  • This test example is used to illustrate the effect of the presence of ammonia nitrogen on the adsorption of rare earths.
  • each 30 mL of ammonia nitrogen concentration was 0, 9.6, 24.1, 48.7, 89.0, 241.4 (mg / L), and the rare earth concentration of the rare earth oxide was 13.3 (mg / L)
  • the mixed solution was vortexed with O.lOOg fine-grained clay XN-1 for one hour, and the adsorption removal effect of the rare earth is shown in Fig. 1. It can be seen from Fig.
  • This test example is used to illustrate the effect of sodium-containing basic compounds and initial pH on ammonia nitrogen removal and pH.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • the mixture was allowed to stand for 2 hours, and vacuum-filtered to separate the solid and liquid to obtain a fine-grained clay adsorption solution and a fine-grained clay after adsorption, wherein the pH of the fine-grained clay adsorption solution was 7.96, wherein the rare earth oxide was used.
  • the rare earth concentration was 0.68 mg/L, and the ammonia nitrogen concentration in terms of nitrogen was 13.71 mg/L.
  • the coarse sand clay which has been adsorbed and saturated by repeated accumulation is desorbed, wherein the saturated adsorption amount of the rare earth is 0.786 mg/g, the saturated adsorption amount of ammonia nitrogen is 0.101 mg/g, and 100 mL is obtained.
  • a neutral sodium chloride aqueous solution having a concentration of 1.2 mol/L is introduced into a sand core glass column filled with 70 g of the coarse-grained clay CN-1, and the residence time is controlled to be 60 min, and the effluent is collected to obtain a desorption liquid, wherein
  • the rare earth concentration based on the rare earth oxide was 540.96 mg/L, and the ammonia nitrogen concentration was 70.36 mg/L.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • the rare earth concentration of rare earth oxide is 56.10 mg/L
  • the ammonia nitrogen concentration by nitrogen is 51.29 mg/L
  • the chloride concentration of chlorine is 451.82 mg/L
  • the pH of the solution was adjusted to 11 with sodium hydroxide, and after stirring for 20 min, 100.0 g of Na + -type fine-grained clay XN-1 was continuously added, stirred for 20 min, and allowed to stand for 2 hours, and suction-filtered.
  • Solid-liquid separation obtaining a fine-grain clay adsorption solution and a fine-grained clay after adsorption, wherein the pH of the fine-grain clay adsorption solution is 8.84, wherein the rare earth concentration based on the rare earth oxide is 0.74 mg/L, based on nitrogen
  • the ammonia nitrogen concentration was 40.82 mg/L, and the chloride concentration in terms of chlorine was 452.50 mg/L.
  • the solution after adsorption and sedimentation by fine-grained clay was added to the fresh water chamber of the bipolar membrane electrodialysis apparatus at 25 °C to control the circulating flow rate to be 80 L/h, the regulating voltage was 25 V, and the acid chamber and the alkali chamber were added to 0.025.
  • a molar aqueous solution of hydrochloric acid and a 3 % by weight aqueous solution of sodium sulfate was added to the polar water chamber.
  • the pH of the solution in the fresh water chamber was 7.01, and the rare earth concentration in terms of rare earth oxide was 0.50 mg/L.
  • the ammonia nitrogen concentration was 28.02 mg/L, and the chloride concentration in terms of chlorine was 0.05 mg/L.
  • the bottle continuously receives the effluent, and the results show that the average concentration of rare earth rare earth oxide in the effluent is 0.08 mg/L, the average concentration of ammonia nitrogen in nitrogen is 21.50 mg/L, and the chloride concentration in terms of chlorine is 0.05 mg. /L.
  • the coarse sand clay which has been adsorbed and saturated by repeated accumulation is desorbed, wherein the saturated adsorption amount of the rare earth is 0.806 mg/g, the saturated adsorption amount of ammonia nitrogen is 0.097 mg/g, and 100 mL is obtained.
  • a neutral sodium chloride aqueous solution having a concentration of 1.2 mol/L is introduced into a sand core glass column filled with 70 g of the coarse-grained clay CN-1, and the residence time is controlled to be 60 min, and the effluent is collected to obtain a desorption liquid, wherein The rare earth concentration based on the rare earth oxide was 552.96 mg/L, and the ammonia nitrogen concentration was 62.64 mg/L.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • the clay adsorption solution has a pH of 7.87, wherein the rare earth concentration in terms of rare earth oxide is 0.81 mg/L, the ammonia nitrogen concentration in terms of nitrogen is 14.11 mg/L, and the chloride concentration in terms of chlorine is 1553.71 mg/L.
  • the solution after adsorption and sedimentation by fine-grained clay was added to the fresh water chamber of the bipolar membrane electrodialysis apparatus at 25 °C to control the circulating flow rate to be 80 L/h, the regulating voltage was 25 V, and the acid chamber and the alkali chamber were added to 0.025.
  • a hydrochloric acid solution of mol/L, a 3 wt% aqueous solution of sodium sulfate was added to the polar water chamber, and after 30 minutes of hydrolysis, the pH of the fresh water chamber solution was 7.14, and the rare earth concentration based on the rare earth oxide was 0.49 mg/L.
  • the ammonia nitrogen concentration was 12.10 mg/L, and the chlorine concentration in terms of chlorine was 1.25 mg/L.
  • the rare earth concentration in terms of rare earth oxide is 1029.91 mg/L
  • the ammonia nitrogen concentration in terms of nitrogen is 0.32 mg/L.
  • the coarse sand clay which has been adsorbed and saturated by repeated accumulation is desorbed, wherein the saturated adsorption amount of the rare earth is 0.836 mg/g, and the saturated adsorption amount of ammonia nitrogen is 0.095 mg/g, which will be 100 mL.
  • a neutral sodium chloride aqueous solution having a concentration of 1.2 mol/L is introduced into a sand core glass column filled with 70 g of the coarse-grained clay CN-1, and the residence time is controlled to be 60 min, and the effluent is collected to obtain a desorption liquid, wherein
  • the rare earth concentration based on the rare earth oxide was 576.64 mg/L, and the ammonia nitrogen concentration was 66.19 mg/L.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • Example 5 At 25 ° C, 1000 mL of simulated wastewater (the rare earth concentration of rare earth oxide was 49.32 mg / L, and the ammonia nitrogen concentration by nitrogen was 54.81 mg / L) was treated according to the method of Example 1, different The Na + -type fine-grained clay XN-1 is replaced with the same parts by weight of Na + -H + -type fine-grained clay XN-2, and the Na + -type coarse-grained clay CN-1 is of the same weight The Na + -H + type coarse-grained clay CN-2 is substituted to obtain a rare earth concentration of 0.87 mg/L in terms of rare earth oxide in the fine-grained clay adsorption solution, and an ammonia nitrogen concentration of 12.89 mg/L in terms of nitrogen. The average concentration of rare earths based on rare earth oxides in the effluent after adsorption of coarse-grained clay is 0.10 mg/L, and the average concentration of ammonia nitrogen in terms of nitrogen is 8.49 mg/L.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • This embodiment is for explaining the treatment method of the rare earth-containing wastewater provided by the present invention.
  • the rare earth-containing wastewater was treated according to the method of Example 1, except that when the fine-grained clay was desorbed, an aqueous solution of sodium chloride having a pH of 1.03 was replaced with an aqueous solution of sodium chloride having a pH of 5.63.
  • the rare earth concentration in the rare earth rich solution is 54.19 mg/L in terms of rare earth oxide, and the ammonia nitrogen concentration in nitrogen is 0.98 mg/L. Comparative example 1
  • This comparative example is used to illustrate the treatment of the reference rare earth-containing wastewater.
  • the rare earth-containing wastewater is treated according to the method of Example 1, except that the Na + -type fine-grained clay is used.
  • XN-1 was replaced by the same weight part of Na + type coarse-grained clay CN-1, and the rare earth concentration of the rare earth oxide in the effluent of the obtained sand core glass column was 4.02 mg/L, and the ammonia nitrogen concentration by nitrogen. It is 11.57 g/L.

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Abstract

摘要本发明提供了一种含铵稀土溶液的处理方法，其中，该方法包括：（1）将所述含稀土溶液用细粒粘土进行细粒粘土吸附，所述细粒粘土吸附的条件使得到的细粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于1mg/L；（2）将所述细粒粘土吸附溶液用粗粒粘土进行粗粒粘土吸附，所述粗粒粘土吸附的条件使得到的粗粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于0.5mg/L；所述细粒粘土中90%以上颗粒的粒径小于所述粗粒粘土中颗粒的粒径，且所述细粒粘土的粒径为1-250μm，所述粗粒粘土的粒径为 50-1000μm；（3）从经过所述细粒粘土吸附之后的细粒粘土与经过所述粗粒粘土吸附之后的粗粒粘土中解吸出稀土。采用该方法能够有效地回收稀土。

Description

一种含稀土溶液的处理方法
技术领域
本发明涉及一种含稀土溶液的处理方法。 背景技术
稀土被广泛应用于工业、 军事、 农业等各领域， 近几十年迅速发展的稀土功能材 料在高新技术产业和军事航天等技术中更是发挥了不可替代的作用，使稀土日渐成为了 全球公认的战略资源。 稀土是一种不可再生的自然资源， 随着其开发力度的加强， 稀土 需求量不断增长。 然而， 高品位稀土矿和稀土储量正在日渐减少。 因此， 针对低品位稀 土矿的稀土高效提取技术以及从稀土生产过程中产生的低浓度含稀土废水中回收稀土 的技术得到了广泛的关注和研究。 随着资源和环境保护要求的提高， 研究和发展低浓度 含稀土溶液的回收利用技术和废水达标排放技术显得更为紧迫。
离子吸附型稀土矿开采过程及其后续雨水淋浸产生的矿山废水中往往残留有少量 的稀土和一定浓度的氨氮， 废水量大， 难以处理。 例如， 江西某稀土矿区的河水在五月 份的分析结果为： 以稀土氧化物 （REO)计的稀土浓度为 30mg/L， 以氮 （N)计的氨氮 浓度为 51mg/L。 若对此部分稀土不进行回收， 势必会加快稀土的流失， 导致矿区乃至 下游生活区的环境水中的稀土及电解质含量增加， 影响生态环境， 威胁水资源安全。 由 于风化壳的广泛存在， 在全球范围内还有很多类似于中国南方的离子型稀土， 只是含量 低一些， 例如 10-300mg/kg。 这些极低稀土含量的风化壳尽管目前还没有作为稀土资源 来进行开采， 但一旦其他资源量减小， 开采成本增加， 它们也将成为一类潜在的稀土资 源。 况且在其他工业和农林业生产过程中电解质的使用会导致这些离子型稀土的浸出， 具有回收利用价值， 若不加以处理也会导致环境污染。 此外， 由于稀土离子的不可生物 降解的特性， 其可长期潜伏在环境中随着食物链进入人体， 在人体内长期蓄积将导致各 种疾病和生理功能紊乱， 危害人体健康。
再者， 在稀土分离企业以及一些矿物加工和冶炼过程中也有许多这种含低浓度稀 土离子的废水需要处理并回收稀土。 例如， 在铝土矿、 磷矿、 锆英砂、 钛铁矿等矿物处 理过程中， 稀土元素会在废水中富集， 并伴有一定浓度的氨氮。 在氟碳酸盐稀土矿伴生 的风化泥中也含有一定量的稀土，在其选矿过程中与含酸和铵的水溶液接触也会导致一 些稀土进入溶液。 这些溶液的随意排放不仅会导致稀土资源的浪费， 而且还会对环境产 生严重影响。
稀土富集回收方法已经得到广泛的研究和应用。 目前主要有沉淀法、 萃取法、 反 渗透法以及离子交换树脂法等。 其中， 以沉淀法最为简单， 通常是采用石灰中和使溶液 呈碱性， 使稀土以氢氧化物沉淀析出而与大量的水分离。 但由于水量大， 需要用酸调节 至中性才能排放， 且形成的沉淀为胶态， 颗粒细小， 回收困难， 而且钙的存在也会给后 续纯化处理带来压力。 树脂吸附法也比较简单， 但树脂负载量小， 成本高， 稀土解吸较 为困难。 萃取法较为复杂， 尽管该种方法富集倍数大、 效率高， 但是存在相比太小， 萃 取剂溶解损失大、 成本高和二次污染大等问题。
目前， 废水中氨氮的处理方法主要有以下几种： 吹脱法、 生物法、 化学沉淀法、 折点氯化法等。吹脱法脱氮效率高，但氨氮并没有从根本上去除。生物法处理效果较好， 但是处理时间较长， 在实际应用中难于控制。 化学沉淀法操作灵活， 处理效果好， 但是 费用较高。 折点氯化法是一种非常有效的方法， 其反应过程如下： NH4 ++1.5H0C1→ 0.5N2+1.5H2O+2.5H++1.5Cr。 所述折点氯化法处理效果稳定、 不受水温影响、 设备投资 少、 反应迅速完全并有消毒作用， 然而， 其对 pH值要求很高， pH值控制是折点氯化法 的难点。 发明内容
本发明的目的是为了提供一种含稀土溶液的处理方法。
本发明提供了一种含稀土溶液的处理方法， 其中， 该方法包括：
( 1 )将所述含稀土溶液用细粒粘土进行细粒粘土吸附， 所述细粒粘土吸附的条件 使得到的细粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 lmg/L;
(2)将所述细粒粘土吸附溶液用粗粒粘土进行粗粒粘土吸附， 所述粗粒粘土吸附 的条件使得到的粗粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 0.5mg/L;
所述细粒粘土中 90%以上颗粒的粒径小于所述粗粒粘土中颗粒的粒径， 且所述细 粒粘土的粒径为 1-250μηι， 所述粗粒粘土的粒径为 150-1000μηι;
(3 )从经过所述细粒粘土吸附之后的细粒粘土与经过所述粗粒粘土吸附之后的粗 粒粘土中解吸出稀土。
本发明的发明人经过深入研究发现， 将所述含稀土溶液依次用所述细粒粘土和粗 粒粘土进行吸附， 能够有效地从低浓度的含稀土溶液中回收稀土。
根据本发明的一种优选实施方式， 当所述细粒粘土为 Na+型的细粒粘土和 /或 Na+-H+型的细粒粘土， 和 /或， 所述粗粒粘土为 Na+型的粗粒粘土和 /或 Na+-H+型的粗粒 粘土时， 能够将所述稀土溶液中的稀土浓度降至更低的水平， 并对其中的稀土进行更有 效地回收。
根据本发明的另一种优选实施方式， 当所述细粒粘土吸附为沉降吸附， 且所述粗 粒粘土吸附为柱床吸附时， 不仅能够从低浓度的含稀土溶液中更有效地回收稀土， 而且 还有利于工业处理过程中的固液分离操作， 节约粘土用量。 推测其原因， 可能是由于： 所述细粒粘土的颗粒较小， 如果采用柱床吸附方式， 其流动阻力很大； 而采用以细粒粘 土矿物为吸附剂和助滤剂的沉降吸附方式， 所述细粒粘土既能发挥其吸附作用， 使稀土 完全被吸附和沉淀， 又能将沉淀细颗粒聚集在粘土颗粒表面， 产生共沉淀， 强化了颗粒 的沉降性能， 从而不仅能够在较少的细粒粘土用量下对稀土进行有效回收， 而且还便于 固液分离，可以大大减少过滤操作的工作量。此外，所述细粒粘土具有较大的吸附容量， 将所述含稀土溶液先用所述细粒粘土吸附， 能够使得所述含稀土溶液中的大部分稀土附 着于所述细粒粘土上。 而虽然所述粗粒粘土的吸附容量较小， 但形成的柱床渗透性好， 因此当所述粗粒粘土吸附为柱床吸附时， 适合于处理水量大且稀土浓度低的废水溶液， 从而能够使得所述细粒粘土吸附溶液中残余的稀土基本都被所述粗粒粘土吸附去除。
根据本发明的另一种优选实施方式， 当所述含稀土溶液中还含有浓度为 20-500mg/L 的氨氮， 且所述含稀土溶液的处理方法还包括在所述细粒粘土吸附之前和 / 或在所述细粒粘土吸附的过程中， 在所述含稀土溶液中加入氢氧化钠、 碳酸钠或次氯酸 钠并反应时， 所述氢氧化钠、 碳酸钠或者次氯酸钠可以调节所述含稀土溶液的 pH并去 除其中的氨氮， 从而在对稀土进行回收的基础上， 还能够显著降低所述含稀土溶液中氨 氮的浓度。
通常来说， 当所述含稀土溶液中含有较高浓度的氨氮 （200-500mg/L) 时， 所述细 粒粘土吸附时单纯采用氢氧化钠或者碳酸钠调节 pH并不能将氨氮降到要求的范围内， 得到的细粒粘土吸附溶液中还含有一定量的氨氮 （30-100mg/L)， 并且还可能含有一定 的氯离子和钠离子； 或者， 所述细粒粘土吸附时单纯采用次氯酸钠调节 pH并将氨氮降 到要求范围， 得到的细粒粘土吸附溶液中也可能使溶液中含有浓度为 100-3000mg/L的 氯离子和 /或浓度为 100-3000mg/L的钠离子。为此，根据本发明的另一种优选实施方式， 当所述细粒粘土吸附溶液中含有以氮计浓度为 30-100mg/L 的氨氮， 和 /或浓度为 100-3000mg/L的氯离子， 和 /或浓度为 100-3000mg/L的钠离子时， 所述含稀土溶液的处 理方法还包括在所述细粒粘土吸附之后并在所述粗粒粘土吸附之前，将所述细粒粘土吸 附溶液进行双极膜水解离处理。这样能够使得所述双极膜水解之后得到的淡水中氯离子 和钠离子以及氨氮的浓度显著降低， 满足更高要求的排放标准； 而且在双极膜水解离装 置的酸室中产出的酸可以用于所述酸性钠盐溶液的配制，在碱室中产出的碱可以用于从 解析液中用沉淀和萃取法回收稀土， 极具工业应用前景。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。 附图说明
附图是用来提供对本发明的进一步理解， 并且构成说明书的一部分， 与下面的具 体实施方式一起用于解释本发明， 但并不构成对本发明的限制。 在附图中：
图 1为不同氨氮浓度对稀土去除效果的影响结果图；
图 2为氨氮浓度随着碱性处理条件变化的结果图；
图 3为体系的 pH值随着反应进行变化的结果图。 具体实施方式
以下对本发明的具体实施方式进行详细说明。 应当理解的是， 此处所描述的具体 实施方式仅用于说明和解释本发明， 并不用于限制本发明。
本发明提供的含稀土溶液的处理方法包括：
( 1 )将所述含稀土溶液用细粒粘土进行细粒粘土吸附， 所述细粒粘土吸附的条件 使得到的细粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 lmg/L;
(2)将所述细粒粘土吸附溶液用粗粒粘土进行粗粒粘土吸附， 所述粗粒粘土吸附 的条件使得到的粗粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 0.5mg/L;
所述细粒粘土中 90%以上颗粒的粒径小于所述粗粒粘土中颗粒的粒径， 且所述细 粒粘土的粒径为 1-250μηι， 所述粗粒粘土的粒径为 150-1000μηι;
(3 )从经过所述细粒粘土吸附之后的细粒粘土与经过所述粗粒粘土吸附之后的粗 粒粘土中解吸出稀土。
所述细粒粘土和粗粒粘土通常包括带负电的骨架以及带正电的结合离子， 其中， 所述带正电的结合离子通常同时包括 H+、 Na+、 Mg2+、 K+、 Ca2+等。 尽管当带正电的结 合离子为上述几种结合离子时，所述细粒粘土和粗粒粘土对所述含稀土溶液中的稀土均 具有吸附能力， 但是为了提高吸附效率， 从而对所述含稀土溶液中的稀土进行更为有效 地回收， 所述细粒粘土特别优选为 Na+型的细粒粘土和 /或 Na+-H+型的细粒粘土， 和 /或， 所述粗粒粘土特别优选为 Na+型的粗粒粘土和 /或 Na+-H+型的粗粒粘土。其中，所述 "Na+ 型"是指将粘土中的带正电的结合离子转化为 Na+， 而所述 "Na+-H+型"是指将粘土中 的带正电的结合离子转化为 Na+和 H+。
所述 Na+型的细粒粘土和所述 Na+型的粗粒粘土可以按照本领域技术人员公知的各 种方法制备得到，例如，可以分别将细粒粘土和粗粒粘土用氯化钠和 /或硫酸钠溶液浸泡 或者柱交换得到， 从操作简便性的角度考虑， 优选用氯化钠和 /或硫酸钠溶液浸泡得到。 具体地， 所述氯化钠溶液和硫酸钠溶液的浓度可以各自独立地为 0.3-3mol/L。 在浸泡过 程中， 相对于 lg的所述细粒粘土或粗粒粘土， 所述氯化钠溶液和硫酸钠溶液的总用量 可以为 1 -5mL。此外，浸泡温度可以为 1 -50 °C，优选为 20-40 °C；浸泡时间可以为 10-60min, 优选为 20-40min。
此外， 所述 Na+-H+型的细粒粘土和 Na+-H+型的粗粒粘土也可以按照本领域技术人 员公知的各种方法制备得到， 例如， 可以分别将细粒粘土和粗粒粘土用酸性的氯化钠和 /或硫酸钠溶液浸泡或者柱交换得到，从操作简便性的角度考虑，优选用酸性的氯化钠和 /或硫酸钠溶液浸泡得到。 其中， 所述酸性的氯化钠和 /或硫酸钠溶液为将所述氯化钠和 / 或硫酸钠溶液的 pH值调节至酸性而得到的溶液。 具体地， 所述酸性的氯化钠和 /或硫酸 钠溶液的 pH值可以为大于 0且小于等于 6、浓度可以为 0.3-3mol/L。在浸泡过程中， 相 对于 lg的所述细粒粘土或粗粒粘土， 所述酸性的氯化钠溶液和硫酸钠溶液的总用量可 以为 l-20mL。此外，浸泡温度可以为 1-50°C，优选为 20-40°C；浸泡时间可以为 10-60min， 优选为 20-40min。
所述细粒粘土和粗粒粘土可以为现有的各种能够吸附稀土的粘土， 例如， 可以为 从自然界的混合矿物中通过去除 20 目 （804μηι) 以上的大颗粒矿物后经过干法或湿法 筛分而得到的。 所述细粒粘土和粗粒粘土的主要成分可以相同， 也可以不同， 并各自独 立地为高岭土、 埃洛石、 蒙脱土、 沸石、 云母、 长石等中的一种或多种， 其含量随产地 而异。 其中， 根据带正电的结合离子的不同， 所述长石包括钾长石、 钠长石、 钙长石等 中的一种或多种。
根据本发明， 尽管所述含稀土溶液的处理方法可以对现有的各种含稀土的溶液进 行处理并对其中的稀土进行回收，但是鉴于低稀土浓度的废水量大且不易进行处理的缺 陷， 所述含稀土溶液中以稀土氧化物计的稀土浓度优选为 5-300mg/L， 优选为 20-100mg/L, 特别优选为 40-60mg/L。
由于所述细粒粘土的饱和吸附量较大且阻力较大， 所述细粒粘土吸附适合采用沉 降吸附以回收所述稀土溶液中的稀土。 所述 "沉降吸附"是指先将所述含稀土溶液与细 粒粘土搅拌混合， 然后再静置沉降。 其中， 所述搅拌混合的时间可以为 10-30分钟， 所 述静置沉降的时间可以为 2-5小时。 经所述沉降吸附之后， 可以采用澄清和过滤方式进 行固液分离， 将得到的细粒粘土吸附溶液用于下一步处理， 并将得到的经过所述细粒粘 土吸附的细粒粘土进行解吸。 具体地， 所述沉降吸附的条件包括： 相对于 1L的所述含 稀土溶液， 所述细粒粘土的用量可以为 0.01-15g， 优选为 5-10g; 吸附温度可以为 1-50 V , 选为 15-40°C ; pH值可以为 6-12， 优选为 8-11 ; 吸附时间可以为 0.5-24小时， 优选 为 2-5小时。
由于所述粗粒粘土的饱和吸附量较小但形成的柱床渗透性好， 所述粗粒吸附适合 于采用柱床吸附。 具体地， 所述柱床吸附的条件包括： 所述吸附温度可以为 1-50°C， 优 选为 15-40°C ; pH值可以为 5-9， 优选为 7-8。 当所述粗粒粘土采用柱床吸附时， 柱床的 规模以及粗粒粘土的填充料可以根据实际情况进行合理选择， 在此不作赘述。 此外， 当 所述柱床吸附出水中以稀土氧化物计的稀土浓度超过 0.5mg/L时， 应该及时更换柱床中 的粗粒粘土。
所述含稀土溶液中还可以含有浓度为 20-500mg/L、优选为 50-120mg/L的氨氮。此 时，所述含稀土溶液的处理方法还优选包括在所述细粒粘土吸附之前和 /或在所述细粒粘 土吸附的过程中， 在所述含稀土溶液中加入氢氧化钠、 碳酸钠或次氯酸钠并反应， 所述 氢氧化钠或碳酸钠的用量以及反应的条件使得到的溶液中以氮计的氨氮的浓度为 15-100mg/L,所述次氯酸钠的用量以及反应的条件使得到的溶液中以氮计的氨氮的浓度 不高于 15mg/L， 这样不仅能够对稀土进行回收， 还能够将所述含稀土溶液中氨氮进行 有效脱除。
根据本发明， 在上述去除氨氮的步骤中， 特别优选加入次氯酸钠并反应。 此时， 所述次氯酸钠的用量使得所述含稀土溶液中氨氮与产生的 Cl2的摩尔比优选为 1 :6-10， 更优选为 1 :7-9。此夕卜，所述反应的条件通常包括：反应温度可以为 1-50°C，优选为 15-40 °C ; 起始 pH值可以为 6-12， 优选为 8-11 ; 反应时间可以为 0.5-24小时， 优选为 2-5小 时。 在此过程中， 所述次氯酸钠通过与氨氮反应放出氮气而实现降低氨氮的目的， 随着 反应过程的进行， 反应体系的 pH值通常会降低， 反应达到平衡后溶液的 pH值通常可 以为 6-12， 优选为 6-9。
根据本发明， 当所述含稀土溶液中含有较高浓度的氨氮 （200-500mg/L) 时， 所述 细粒粘土吸附时单纯采用氢氧化钠或者碳酸钠调节 pH 并不能将氨氮降到要求的范围 内， 得到的细粒粘土吸附溶液中还含有一定量的氨氮 （30-100mg/L)， 并且还可能含有 一定的氯离子和钠离子； 或着， 所述细粒粘土吸附时单纯采用次氯酸钠调节 pH并将氨 氮降到要求范围，得到的细粒粘土吸附溶液中也可能使溶液中含有浓度为 100-3000mg/L 的氯离子和 /或浓度为 100-3000mg/L的钠离子。此时，根据本发明的一种优选实施方式， 当所述细粒粘土吸附溶液中含有以氮计浓度为 30-100mg/L 的氨氮， 和 /或浓度为 100-3000mg/L的氯离子， 和 /或浓度为 100-3000mg/L的钠离子时， 所述含稀土溶液的处 理方法还包括在所述细粒粘土吸附之后并在所述粗粒粘土吸附之前，将所述细粒粘土吸 附溶液进行双极膜水解离，所述双极膜水解离的条件使得到的溶液中以氮计的氨氮浓度 不高于 30mg/L， 且氯离子和钠离子的浓度均小于 30mg/L。
所述双极膜水解离可以在现有的各种双极膜电渗析仪中进行。 其中， 所述双极膜 电渗析仪通常包括酸室、 碱室、 淡水室和极水室， 具体结构为本领域技术人员公知， 在 此不作赘述。 所述双极膜水解离的条件通常包括： 两极间的电压可以为 10-30伏， 优选 为 25-30伏； 所述细粒粘土吸附溶液的停留时间可以为 10-60分钟， 优选为 20-40分钟。 其中， 所述停留时间是指所述细粒粘土吸附溶液通过淡水室的时间。
根据本发明， 在步骤 （3 ) 中， 所述解吸的方法可以按照现有的各种方法进行， 只 要能够使得吸附在所述细粒粘土和所述粗粒粘土上的稀土解吸出来即可， 例如， 可以将 经过所述细粒粘土吸附沉淀之后的细粒粘土与经过所述粗粒粘土吸附之后的粗粒粘土 与钠盐溶液进行接触， 得到解吸液。 此外， 所述解吸液中的稀土通常可以采用沉淀法或 者萃取法进行回收， 而细粒粘土和粗粒粘土可以循环使用。
优选地， 从经过所述细粒粘土吸附之后的细粒粘土中解吸出稀土的方法包括将经 过所述细粒粘土吸附之后的细粒粘土用酸性钠盐溶液浸泡。 而所述浸泡条件通常包括： 相对于 lg的经过所述细粒粘土吸附之后的细粒粘土， 所述酸性钠盐溶液的用量可以为 l-20mL, 优选为 5-10mL; 所述酸性钠盐溶液的 pH值可以为大于 0且小于等于 6， 优选 为 1-3 ; 浸泡温度可以为 1-50°C， 优选为 15-40°C ; 浸泡时间可以为 10-90min， 优选为 20-60min。
优选地， 从经过所述粗粒粘土吸附之后的粗粒粘土中解吸出稀土的方法为以钠盐 溶液为解吸液进行柱床解吸。 在进行所述柱床解吸时， 解吸液 （钠盐溶液） 的流动方向 与吸附时吸附液的方向相反。 所述柱床解吸的条件通常包括： 所述钠盐溶液的 pH值可 以为 4-7， 优选为 5-6; 解吸温度为 1-50°C， 优选为 15-40°C ; 钠盐溶液通过柱床的时间 可以为 30-300min， 优选为 60-120min。此外， 在所述柱床解吸时， 所述钠盐溶液的用量 与粗粒粘土用量之间的重量比可以为 0.3-1 :1， 优选为 0.5-0.8:1。
根据本发明的一种具体实施方式， 所述含稀土溶液同时含有稀土、 氨氮以及氯离 子和钠离子， 所述含稀土溶液的处理方法包括：
( 1 )将细粒粘土和粗粒粘土分别用中性或酸性的氯化钠和 /或硫酸钠溶液浸泡， 得 到 Na+型的细粒粘土或 Na+-H+型的细粒粘土以及 Na+型的粗粒粘土或 Na+-H+型的粗粒粘 土； 所述细粒粘土中 90%以上颗粒的粒径小于所述粗粒粘土中颗粒的粒径， 且所述细粒 粘土的粒径为 l-250um， 所述粗粒粘土的粒径为 150-1000um;
(2) 将所述含稀土溶液与次氯酸钠接触， 并将接触后的溶液用 Na+型的细粒粘土 或 Na+-H+型的细粒粘土进行细粒粘土吸附，所述接触以及细粒粘土吸附的条件使得到的 细粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 lmg/L， 且当使用次氯酸钠时可 以使得到的细粒粘土吸附溶液中以氮计的氨氮的浓度不高于 15mg/L; 当使用氢氧化钠 或碳酸钠时可以使得到的细粒粘土吸附溶液中以氮计的氨氮的浓度在 15-100mg/L之间。
(3 )将所述细粒粘土吸附溶液进行双极膜水解离， 所述双极膜水解离的条件使得 到的溶液中以氮计的氨氮浓度不高于 30mg/L，且氯离子和钠离子的浓度均小于 30mg/L;
(4)将所述双极膜水解离出水用 Na+型的粗粒粘土或 Na+-H+型的粗粒粘土进行粗 砂粘土吸附，所述粗砂粘土吸附的条件使得到的粗粒粘土吸附溶液中以稀土氧化物计的 稀土浓度不高于 0.5mg/L;
(5 )从经过所述细粒粘土吸附沉淀之后的细粒粘土与经过所述粗砂吸附之后的粗 粒粘土中解吸出稀土， 并采用沉淀法或萃取法从得到的高稀土浓度解吸液中回收稀土， 其中， 解吸之后的细粒粘土和粗粒粘土循环使用。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中， 稀土的浓度、 氨氮的浓度及氯根的浓度分别采用偶氮胂 III分光光度法、 氏试剂分光光度法和硫氰酸汞分光光度法进行测定， 具体地， 分别根据 偶氮胂 III分光光度法、 纳氏试剂分光光度法和硫氰酸汞分光光度法测量样品的吸光度， 并根据校准曲线分别计算出相应的稀土浓度、 氨氮浓度和氯根浓度。 其中， 校准曲线分 别按如下步骤得到：
偶氮胂 III分光光度法的校准曲线： 在 8个 50mL比色管中， 分别加入 0.00、 2.00、 3.00、 4.00、 5.00、 6.00、 8.00和 lO.OOmL浓度为 2mg/L (以稀土氧化物计) 的稀土标准 工作溶液， 其所对应的稀土含量分别为 0.0、 4.0、 6.0、 8.0、 10.0、 12.0、 16.0禾卩 20.0ug， 再分别加入 lO.OmL pH值为 3.30的乙酸 -乙酸钠缓冲溶液， 然后分别加水至标线， 摇匀， 再分别加入 2mL浓度为 0.2重量％的偶氮胂 III显色剂， 摇匀， 得到测试样。 放置 20min 后， 在波长 655nm下， 将上述 8种测试样分别加入 10mm比色皿中， 以空白试剂作参 比， 测量吸光度， 并以其为纵坐标， 以其对应的稀土含量 （ug) 为横坐标， 绘制校准曲 线。
纳氏试剂分光光度法的校准曲线： 在 8个 50mL比色管中， 分别加入 0.00、 0.50、
1.00、 2.00、 4.00、 6.00、 8.00禾口 lO.OOmL浓度为 10mg/L (以氮计) 的氨氮标准工作溶 液， 其所对应的氨氮含量分别为 0.0、 5.0、 10.0、 20.0、 40.0、 60.0、 80.0和 lOO.Oug, 加 水至标线。 然后分别加入 l .OmL酒石酸钾钠溶液， 摇匀， 再分别加入 1.5mL纳式试剂， 摇匀，得到测试样。放置 lOmin后，在波长 420nm下，将上述 8种测试样分别加入 20mm 的比色皿中，以空白试剂作参比，测量吸光度并以其为纵坐标，以其对应的氨氮含量 (ug) 为横坐标， 绘制校准曲线。
硫氰酸汞分光光度法的校准曲线： 在 8个 50mL比色管中， 分别加入 0.00、 2.00、 3.00、 4.00、 5.00、 6.00、 8.00和 lO.OOmL浓度为 lmg/L (以氯计) 的氯化钠标准工作溶 液， 其所对应的氯根含量分别为 0.0、 2.0、 3.0、 4.0、 5.0、 6.0、 8.0禾 B lO.Oug, 再分别加 入 8.0mL的硝酸溶液 （其中， 硝酸与水的体积比为 1 :3 )， 摇匀， 再分别加入 2.5mL浓 度为 0.35重量％的硫氰酸汞， 摇匀， 再分别加入 2.5mL浓度为 150g/L的硝酸铁溶液， 摇匀， 然后分别加水至标线。 放置 20min后， 在波长 460nm下， 将上述 8种测试样分 别加入 10mm比色皿中， 以空白试剂作参比， 测量吸光度， 并以其为纵坐标， 以其对应 的氯根含量 （ug) 为横坐标， 绘制校准曲线。
以下实施例和对比例中， pH值的测定均采用 pH-S分析仪直接测定。 制备例 1
该制备例用于说明本发明提供的细粒粘土的制备方法。
在 25 °C下， 将 lOOOg取自江西安远堆浸后的尾矿 （主要成分为云母、 高岭石和钾 长石， 下同） 过 100目 （150微米， 下同） 筛， 筛下粒径为 19-150微米的细粒粘土。 取 100g的上述细粒粘土， 并将其用 500mL浓度为 1.2mol/L的中性氯化钠水溶液震荡浸泡 30min, 然后过滤并将得到的固相产物用纯水洗涤， 接着在 50°C下烘干得到 Na+型的细 粒粘土 XN-1。 制备例 2 该制备例用于说明本发明提供的细粒粘土的制备方法。
在 25°C下， 将 1000g取自江西安远堆浸后的尾矿过 100目筛， 筛下粒径为 19-150 微米的细粒粘土。 取 100g的上述细粒粘土， 并将其用 500mL浓度为 1.2mol/L、 pH值 为 2的酸性氯化钠水溶液震荡浸泡 30min， 然后过滤并将得到的固相产物用纯水洗涤， 接着在 50°C下烘干得到 Na+-H+型的细粒粘土 XN-2。 制备例 3
该制备例用于说明本发明提供的细粒粘土的制备方法。
在 25°C下， 将 1000g取自江西安远堆浸后的尾矿用 5000mL纯水震荡浸泡 30min， 并将浸泡产物过 100 目筛， 筛下粒径为 19-150微米的细粒粘土， 并将其用纯水洗涤， 接着在 50°C下烘干得到细粒粘土 XN-3。
取 10g上述细粒粘土 XN-3, 用 50mL、 pH值为 2.0的硫酸水溶液震荡浸泡 30min， 然后过滤并将得到的固相产物用纯水洗涤， 接着在 50°C下烘干得到 H+型的细粒粘土 XN-4 o 制备例 4
该制备例用于说明本发明提供的粗粒粘土的制备方法。
在 25°C下， 将制备例 1中所述的取自江西安远堆浸后的尾矿过 100目筛后得到的 筛上物再过 20目 （804微米， 下同） 筛， 筛下物即为粒径为 150-804微米的粗粒粘土。 取 100g上述粗粒粘土，并将其用 500mL浓度为 1.3mol/L的中性氯化钠水溶液震荡浸泡 30min, 然后过滤并将得到的固相产物用纯水洗涤， 接着在 50°C下烘干得到 Na+型的粗 粒粘土 CN-1。 制备例 5
该制备例用于说明本发明提供的粗粒粘土的制备方法。
在 25°C下， 将制备例 1中所述的取自江西安远堆浸后的尾矿过 100目筛后得到的 筛上物再过 20目 （804微米， 下同） 筛， 筛下物即为粒径为 150-804微米的粗粒粘土。 取 100g的上述粗粒粘土， 并将其用 500mL浓度为 1.2mol/L、 pH值为 2的酸性氯化钠 水溶液震荡浸泡 30min， 然后过滤并将得到的固相产物用纯水洗涤， 接着在 50°C下烘干 得到 Na+-H+型的粗粒粘土 CN-2。 测试例 1
该测试例用于说明不同细粒粘土对稀土吸附能力性能的测试。
在 25°C下， 分别以细粒粘土 XN-1、 XN-2、 XN-3和 XN-4为吸附剂， 采用差量法 并用震荡平衡的方式确定 O.lg细粒粘土在 30mL 以稀土氧化物计稀土含量分别为 0、 0.25mg、 0.30mg、 0.35mg、 0.40mg、 0.50mg、 0.60mg、 0.70mg、 0.80mg和 0.90mg的含 稀土溶液中的平衡浓度和平衡吸附量。然后套用朗格缪尔吸附等温线方程， 以上述平衡 浓度为横坐标， 以其对应的平衡浓度和平衡吸附量的比值为纵坐标作出拟合曲线， 再根 据所述吸附等温曲线的拟合参数确定饱和吸附容量 Qm (mg/g) 以及相关系数 RL2， 结 果如表 1所示。 从表 1的结果可以看出， 细粒粘土对稀土的吸附均能较好地符合朗格缪 尔吸附模型， 属单分子层吸附， 但经过不同改性处理的细粒粘土对稀土具有不同的吸附 效果， 经中性氯化钠处理后的细粒粘土 （Na+型的细粒粘土） 和经酸性氯化钠处理后的 细粒粘土 （Na+-H+型的细粒粘土） 对稀土的吸附能力较强， 因此， 为优选的吸附剂。
表 1
Figure imgf000013_0001
测试例 2
该测试例用于说明氨氮的存在对稀土吸附的影响。
在 25°C下， 各取 30mL以氮计的氨氮浓度分别为 0、 9.6、 24.1、 48.7、 89.0、 241.4 (mg/L), 且以稀土氧化物计的稀土浓度均为 13.3 (mg/L) 的混合溶液， 并将其分别与 O.lOOg细粒粘土 XN-1震荡接触一小时， 稀土的吸附去除效果如图 1所示。 从图 1可以 看出， 随着溶液中氨氮浓度的增加， 平衡时稀土吸附量和吸附率均减小； 且当以氮计的 氨氮浓度小于 89.0mg/L时， 稀土的平衡吸附量和吸附率随氨氮浓度的增加急剧下降， 当以氮计的氨氮浓度大于 89.0mg/L时， 下降减缓， 但吸附率低于 50%。 由此可见， 对 于含有较高浓度的氨氮的含稀土溶液，在进行细粒粘土吸附沉降之前和 /或过程中，应考 虑去除氨氮。 测试例 3
该测试例用于说明含钠的碱性化合物和起始 pH值对氨氮去除效果以及 pH值的影 响。
在 25 °C下， 取五份 500mL模拟废水 （以稀土氧化物计的稀土浓度为 52.40mg/L， 以氮计的氨氮浓度为 100.20mg/L)。取其中三份模拟废水在搅拌条件下， 均按 N:C12=1 :7 投加次氯酸钠， 再分别用硫酸将三份模拟废水的起始 pH值分别调节至 12、 11和 7， 三 份均投加 2.5g的 Na+型的细粒粘土 XN-1。搅拌下反应， 随着反应进行， 测定 pH值， 取 样测定氨氮浓度， 搅拌 3h后静置沉降 2小时， 真空抽滤使固液分离。 用氢氧化钠将其 它两份模拟废水的 pH值调节至 12和 11， 两份均投加 2.5g的 Na+型的细粒粘土 XN-1 , 搅拌下反应， 随着反应进行， 测定 pH值， 取样测定氨氮浓度， 搅拌 3h后静置沉降 2 小时， 真空抽滤使固液分离。 随着反应的进行， 氨氮浓度变化结果如图 2所示， pH值 变化结果如图 3所示。 从图 2的结果可以看出， 次氯酸钠的去除效果要明显优于氢氧化 钠的去除效果，且当使用次氯酸钠去除溶液中的氨氮时，起始 pH值为 7-11时效果更佳。 从图 3的结果可以看出， 当使用 pH值为 7-11的次氯酸钠去除溶液中的氨氮时， 随着反 应的进行， 反应体系的 pH值不断变化。 实施例 1
该实施例用于说明本发明提供的含稀土废水的处理方法。
( 1 ) 细粒粘土吸附沉淀：
在 25 °C下， 取 lOOOmL模拟废水（以稀土氧化物计的稀土浓度为 46.34mg/L， 以氮 计的氨氮浓度为 56.79mg/L)， 在搅拌条件下， 往该模拟废水中按 N:C12=1 :8投加次氯酸 钠溶液， 此时的溶液 pH值为 12.5， 用硫酸调节溶液 pH值到 11， 搅拌 20min后， 继续 加入 5.00g的 Na+型的细粒粘土 XN-1 , 搅拌 20min后静置沉降 2小时， 真空抽滤使固液 分离， 得到细粒粘土吸附溶液和经过吸附之后的细粒粘土， 其中， 细粒粘土吸附溶液的 pH 为 7.96， 其中以稀土氧化物计的稀土浓度为 0.68mg/L， 以氮计的氨氮浓度为 13.71mg/L。
(2) 粗砂粘土吸附：
在 25 °C下，将 70g的 Na+型的粗粒粘土 CN-1装入到内径为 24mm、高度为 200mm 的砂芯玻璃柱中， Na+型的粗粒粘土 CN-1的填充高度为 160mm， 用加液漏斗将所述细 粒粘土吸附溶液通入到该砂芯玻璃柱中， 调节加液漏斗活塞， 使砂芯玻璃柱内液面高度 保持在 35mm左右，打开砂芯玻璃柱的活塞，用 lOOOmL容量瓶接收流出液， 结果表明， 流出液中以稀土氧化物计的稀土浓度为 0.11mg/L、 以氮计的氨氮浓度为 7.85g/L。
( 3 ) 解吸：
在 25 °C下， 将 50mL浓度为 0.5mol/L的 pH值为 1.03的氯化钠水溶液加入经过所 述细粒粘土吸附沉淀之后的细粒粘土中震荡浸泡 1小时并固液分离，得到解吸液，其中， 以稀土氧化物计的稀土浓度为 831.01mg/L、 以氮计的氨氮浓度为 1.02mg/L。
此外， 在 25 °C下， 将经多次累积吸附达到吸附饱和的粗砂粘土进行解吸， 其中， 稀土的饱和吸附量为 0.786mg/g， 氨氮的饱和吸附量为 0.101mg/g， 将 lOOmL 浓度为 1.2mol/L的中性氯化钠水溶液引入装填有 70g所述的粗粒粘土 CN-1的砂芯玻璃柱中， 控制停留时间为 60min， 收集流出液， 即得到解吸液， 其中， 以稀土氧化物计的稀土浓 度为 540.96mg/L、 氨氮浓度为 70.36mg/L。 实施例 2
该实施例用于说明本发明提供的含稀土废水的处理方法。
( 1 ) 细粒粘土吸附沉淀：
在 25 °C下， 取 lOOOmL模拟废水（以稀土氧化物计的稀土浓度为 56.10mg/L， 以氮 计的氨氮浓度为 51.29mg/L， 以氯计的氯根浓度为 451.82mg/L)， 在搅拌条件下， 用氢 氧化钠调节溶液 pH值到 11，搅拌 20min后，继续加入 lO.OOg的 Na+型的细粒粘土 XN-1， 搅拌 20min后静置沉降 2小时， 抽滤使固液分离， 得到细粒粘土吸附溶液和经过吸附之 后的细粒粘土， 其中， 细粒粘土吸附溶液的 pH为 8.84， 其中以稀土氧化物计的稀土浓 度为 0.74mg/L， 以氮计的氨氮浓度为 40.82mg/L， 以氯计的氯根浓度为 452.50mg/L。
(2) 双极膜水解离：
在 25 °C下， 将经细粒粘土吸附沉淀后的溶液加入到双极膜电渗析仪的淡水室中， 控制循环流量为 80L/h，调节电压为 25V,酸室和碱室均加入 0.025mol/L的盐酸水溶液， 极水室加入 3重量％的硫酸钠水溶液， 经 30分钟水解离后， 淡水室中溶液 pH为 7.01， 以稀土氧化物计的稀土浓度为 0.50mg/L， 以氮计的氨氮浓度为 28.02mg/L， 以氯计的氯 根浓度为 0.05mg/L。
( 3 ) 粗粒粘土吸附：
在 25 °C下，将 70g的 Na+型的粗粒粘土 CN-1装入到内径为 24mm、高度为 200mm 的砂芯玻璃柱中， Na+型的粗粒粘土 CN-1的填充高度为 160mm， 用加液漏斗将所述的 经双极膜水解离后的溶液通入到该砂芯玻璃柱中， 调节加液漏斗活塞， 使砂芯玻璃柱内 液面高度保持在 35mm左右， 打开砂芯玻璃柱的活塞， 用 lOOOmL容量瓶连续接收流出 液， 结果表明， 流出液中以稀土氧化物计的稀土平均浓度为 0.08mg/L、 以氮计的氨氮平 均浓度为 21.50mg/L， 以氯计的氯根浓度为 0.05mg/L。
(4) 解吸：
在 25 °C下，将 lOOmL浓度为 0.5mol/L的 pH值为 1.07的氯化钠水溶液加入经过所 述细粒粘土吸附沉淀之后的细粒粘土中震荡浸泡 1小时并固液分离，得到解吸液，其中， 以稀土氧化物计的稀土浓度为 963.26mg/L、 以氮计的氨氮浓度为 1.60mg/L。
此外， 在 25 °C下， 将经多次累积吸附达到吸附饱和的粗砂粘土进行解吸， 其中， 稀土的饱和吸附量为 0.806mg/g， 氨氮的饱和吸附量为 0.097mg/g， 将 lOOmL 浓度为 1.2mol/L的中性氯化钠水溶液引入装填有 70g所述的粗粒粘土 CN-1的砂芯玻璃柱中， 控制停留时间为 60min， 收集流出液， 即得到解吸液， 其中， 以稀土氧化物计的稀土浓 度为 552.96mg/L、 氨氮浓度为 62.64mg/L。 实施例 3
该实施例用于说明本发明提供的含稀土废水的处理方法。
( 1 ) 细粒粘土吸附沉淀：
在 25 °C下， 取 2000mL模拟废水（以稀土氧化物计的稀土浓度为 58.67mg/L， 以氮 计的氨氮浓度为 60.31mg/L， 以氯计的氯根浓度为 450.43mg/L)， 在搅拌条件下， 往该 模拟废水中按 N:C12=1 :9投加次氯酸钠溶液， 此时的溶液 pH值为 12.4， 用硫酸调节溶 液 pH值到 11， 搅拌 20min后， 继续加入 lO.OOg的 Na+型的细粒粘土 XN-1， 搅拌 20min 后静置沉降 3小时， 真空抽滤使固液分离， 得到细粒粘土吸附溶液和经过吸附之后的细 粒粘土， 其中， 细粒粘土吸附溶液 pH 值为 7.87， 其中以稀土氧化物计的稀土浓度为 0.81mg/L， 以氮计的氨氮浓度为 14.11mg/L， 以氯计的氯根浓度为 1553.71mg/L。
(2) 双极膜水解离：
在 25 °C下， 将经细粒粘土吸附沉淀后的溶液加入到双极膜电渗析仪的淡水室中， 控制循环流量为 80L/h， 调节电压为 25V， 酸室和碱室均加入 0.025mol/L的盐酸溶液， 极水室加入 3重量％的硫酸钠水溶液， 经 30分钟水解离后， 淡水室溶液 pH值为 7.14， 以稀土氧化物计的稀土浓度为 0.49mg/L， 以氮计的氨氮浓度为 12.10mg/L， 以氯计的氯 根浓度为 1.25mg/L。 ( 3 ) 粗粒粘土吸附：
在 25 °C下，将 70g的 Na+型的粗粒粘土 CN-1装入到内径为 24mm、高度为 200mm 的砂芯玻璃柱中， Na+型的粗粒粘土 CN-1的填充高度为 160mm， 用加液漏斗将所述的 经双极膜水解离后的溶液通入到该砂芯玻璃柱中， 调节加液漏斗活塞， 使砂芯玻璃柱内 液面高度保持在 35mm左右， 打开砂芯玻璃柱的活塞， 用 lOOOmL容量瓶连续接收流出 液， 结果表明， 流出液中以稀土氧化物计的稀土平均浓度为 0.13mg/L、 以氮计的氨氮平 均浓度为 9.41mg/L， 以氯计的氯根浓度为 1.20mg/L。
(4) 解吸：
在 25 °C下，将 lOOmL浓度为 0.5mol/L的 pH值为 1.10氯化钠水溶液加入经过所述 细粒粘土吸附沉淀之后的细粒粘土中震荡浸泡 1小时并固液分离， 得到解吸液， 其中， 以稀土氧化物计的稀土浓度为 1029.91mg/L、 以氮计的氨氮浓度为 0.32mg/L。
此外， 在 25 °C下， 将经多次累积吸附达到吸附饱和的粗砂粘土进行解吸， 其中， 稀土的饱和吸附量为 0.836mg/g， 氨氮的饱和吸附量为 0.095mg/g， 将 lOOmL 浓度为 1.2mol/L的中性氯化钠水溶液引入装填有 70g所述的粗粒粘土 CN-1的砂芯玻璃柱中， 控制停留时间为 60min， 收集流出液， 即得到解吸液， 其中， 以稀土氧化物计的稀土浓 度为 576.64mg/L、 氨氮浓度为 66.19mg/L。 实施例 4
该实施例用于说明本发明提供的含稀土废水的处理方法。
在 25 °C下， 取 lOOOmL模拟废水（以稀土氧化物计的稀土浓度为 49.32mg/L， 以氮 计的氨氮浓度为 54.81mg/L)， 按照实施例 1的方法对其进行处理， 不同的是， 所述 Na+ 型的细粒粘土 XN-1用相同重量份的 Na+-H+型细粒粘土 XN-2替代， 且所述 Na+型的粗 粒粘土 CN-1用相同重量份的 Na+-H+型的粗粒粘土 CN-2替代， 使得到细粒粘土吸附溶 液中以稀土氧化物计的稀土浓度为 0.87mg/L， 以氮计的氨氮浓度为 12.89mg/L; 粗粒粘 土吸附后的流出液中以稀土氧化物计的稀土平均浓度为 0.10mg/L、以氮计的氨氮平均浓 度为 8.49mg/L。 实施例 5
该实施例用于说明本发明提供的含稀土废水的处理方法。
在 25 °C下， 取两份 500mL模拟废水 （以稀土氧化物计的稀土浓度为 46.86mg/L， 以氮计的氨氮浓度为 100.20mg/L)， 按照实施例 1的方法对废水进行处理， 不同的是， 次氯酸钠溶液的投加量按 N:C12的比例分别替换为 1 :5禾 B 1 :10。其中， 以 N:C12=1 :5投加 量处理后得到的细粒粘土吸附溶液中以稀土氧化物计的稀土浓度为 0.62mg/L，氨氮浓度 为 48.82mg/L; 而以 N:C12=1 :10投加量处理后得到的细粒粘土吸附溶液中以稀土氧化物 计的稀土浓度为 0.58mg/L， 氨氮浓度为 0.12mg/L。 实施例 6
该实施例用于说明本发明提供的含稀土废水的处理方法。
按照实施例 1 的方法对所述含稀土的废水进行处理， 不同的是， 在解吸细粒粘土 时， 将 pH值为 1.03的氯化钠水溶液用 pH值为 5.63的氯化钠水溶液替代， 得到的稀土 富集液中以氧化稀土计的稀土浓度为 54.19mg/L、 以氮计的氨氮浓度为 0.98mg/L。 对比例 1
该对比例用于说明参比的含稀土废水的处理方法。
按照实施例 1的方法对含稀土废水进行处理， 不同的是， 将所述 Na+型的细粒粘土
XN-1用相同重量份的 Na+型的粗粒粘土 CN-1替代，最终得到的砂芯玻璃柱流出液中以 稀土氧化物计的稀土浓度为 4.02mg/L、 以氮计的氨氮浓度为 11.57g/L。 以上详细描述了本发明的优选实施方式， 但是， 本发明并不限于上述实施方式中 的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型， 这些简单变型均属于本发明的保护范围。
另外需要说明的是， 在上述具体实施方式中所描述的各个具体技术特征， 在不矛 盾的情况下， 可以通过任何合适的方式进行组合。 为了避免不必要的重复， 本发明对各 种可能的组合方式不再另行说明。
此外， 本发明的各种不同的实施方式之间也可以进行任意组合， 只要其不违背本 发明的思想， 其同样应当视为本发明所公开的内容。

Claims

权利要求
1、 一种含稀土溶液的处理方法， 其特征在于， 该方法包括：
( 1 ) 将所述含稀土溶液用细粒粘土进行细粒粘土吸附， 所述细粒粘土吸附的条件 使得到的细粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 lmg/L;
(2) 将所述细粒粘土吸附溶液用粗粒粘土进行粗粒粘土吸附， 所述粗粒粘土吸附 的条件使得到的粗粒粘土吸附溶液中以稀土氧化物计的稀土浓度不高于 0.5mg/L;
所述细粒粘土中 90%以上颗粒的粒径小于所述粗粒粘土中颗粒的粒径， 且所述细粒 粘土的粒径为 1-250μηι， 所述粗粒粘土的粒径为 150-1000μηι;
( 3 ) 从经过所述细粒粘土吸附之后的细粒粘土与经过所述粗粒粘土吸附之后的粗 粒粘土中解吸出稀土。
2、 根据权利要求 1所述的处理方法， 其中， 所述细粒粘土为 Na+型的细粒粘土和 / 或 Na+-H+型的细粒粘土， 和 /或， 所述粗粒粘土为 Na+型的粗粒粘土和 /或 Na+-H+型的粗 粒粘土。
3、 根据权利要求 2所述的处理方法， 其中， 所述 Na+型的细粒粘土和所述 Na+型的 粗粒粘土分别为将细粒粘土和粗粒粘土用氯化钠和 /或硫酸钠溶液浸泡或者柱交换得到； 所述 Na+-H+型的细粒粘土和所述 Na+-H+型的粗粒粘土分别为将细粒粘土和粗粒粘土用酸 性的氯化钠和 /或硫酸钠溶液浸泡或者柱交换得到。
4、根据权利要求 1-3中任意一项所述的处理方法， 其中， 所述细粒粘土和粗粒粘土 的主要成分相同或不同， 并各自独立地为高岭土、 埃洛石、 蒙脱土、 沸石、 云母和长石 中的一种或多种。
5、 根据权利要求 1 所述的处理方法， 其中， 所述含稀土溶液中以稀土氧化物计的 稀土浓度为 5-300mg/L。
6、根据权利要求 1-3和 5中任意一项所述的处理方法， 其中， 所述细粒粘土吸附为 沉降吸附， 且所述粗粒粘土吸附为柱床吸附。
7、 根据权利要求 6所述的处理方法， 其中， 所述沉降吸附的条件包括： 相对于 1L 的所述含稀土溶液，所述细粒粘土的用量为 0.01-15g，吸附温度为 1-50°C， pH值为 6-12， 吸附时间为 0.5-24小时。
8、 根据权利要求 6所述的处理方法， 所述柱床吸附的条件包括： 吸附温度为 1-50
°C， pH值为 5-9。
9、 根据权利要求 6所述的处理方法， 其中， 步骤 （3 ) 中， 从经过所述细粒粘土吸 附之后的细粒粘土中解吸出稀土的方法包括将经过所述细粒粘土吸附之后的细粒粘土用 酸性钠盐溶液浸泡； 优选地， 所述浸泡条件包括： 相对于 lg的经过所述细粒粘土吸附之 后的细粒粘土， 所述酸性钠盐溶液的用量为 l-20mL， 所述酸性钠盐溶液的 pH值为 1-3， 浸泡温度为 1-50°C， 浸泡时间为 10-90min。
10、 根据权利要求 6所述的处理方法， 其中， 步骤 （3 ) 中， 从经过所述粗粒粘土 吸附之后的粗粒粘土中解吸出稀土的方法为以钠盐溶液为解吸液进行柱床解吸；优选地， 所述柱床解吸的条件包括： 所述钠盐溶液的 pH值为 4-7， 解吸温度为 1-50°C， 钠盐溶液 通过柱床的时间为 30-300min。
11、 根据权利要求 5所述的处理方法， 其中， 所述含稀土溶液中还含有以氮计浓度 为 20-500mg/L 的氨氮； 该方法还包括在所述细粒粘土吸附之前和 /或在所述细粒粘土吸 附的过程中， 在所述含稀土溶液中加入氢氧化钠、 碳酸钠或次氯酸钠并反应， 所述氢氧 化钠或碳酸钠的用量以及反应的条件使得到的溶液中以氮计的氨氮的浓度为 15-100mg/L, 所述次氯酸钠的用量以及反应的条件使得到的溶液中以氮计的氨氮的浓度 不高于 15mg/L。
12、 根据权利要求 11 所述的处理方法， 其中， 所述次氯酸钠的用量使得所述含稀 土溶液中氨氮与产生的 Cl2的摩尔比为 1:6-10， 所述反应的条件包括： 反应温度为 1-50 °C， 起始 pH值为 6-12， 反应时间为 0.5-24小时。
13、 根据权利要求 1、 5或 11所述的处理方法， 其中， 所述细粒粘土吸附溶液中含 有以氮计浓度为 30-100mg/L的氨氮， 和 /或浓度为 100-3000mg/L的氯离子， 和 /或浓度为 100-3000mg/L的钠离子； 该方法还包括在所述细粒粘土吸附之后并在所述粗粒粘土吸附 之前， 将所述细粒粘土吸附溶液进行双极膜水解离， 所述双极膜水解离的条件使得到的 溶液中以氮计的氨氮浓度不高于 30mg/L， 且氯离子和钠离子的浓度均小于 30mg/L。
14、 根据权利要求 13所述的处理方法， 其中， 所述双极膜水解离的条件包括： 两 极间的电压为 10-30伏， 所述细粒粘土吸附溶液的停留时间为 10-60分钟。
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