CN103449568B - Method for treating wastewater with extremely low rare earth concentration by using coarse-grained clay in ionic rare-earth tailings - Google Patents
Method for treating wastewater with extremely low rare earth concentration by using coarse-grained clay in ionic rare-earth tailings Download PDFInfo
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Abstract
The invention discloses a method for treating wastewater with an extremely low rare earth concentration by using coarse-grained clay in ionic rare-earth tailings, which is implemented through that 20-200-mesh coarse-grained clay is screened out from ionic rare-earth tailings, after the coarse-grained clay is modified by using a 5-10% sodium chloride solution and then cleaned, the obtained coarse-grained clay is taken as an adsorbent; mine wastewater with an extremely low rare earth concentration is fed into an adsorption column or adsorption pool to carry out adsorption, so that most of rare earths and a small amount of ammonia nitrogen are adsorbed to the coarse-grained clay, and then the wastewater is purified. The coarse-grained clay saturated by adsorbing is analyzed respectively by using a low-concentration acid solution and 5-10% sodium chloride so as to obtain rare earth concentrated liquid, then rare earths are settled from the concentrated liquid by using alkali or carbonates, and then filtered and cleaned so as to obtain rare earth products. The wastewater subjected to adsorption treatment is integrally collected in a fresh water pond, and after a situation that the wastewater reaches discharge standards is detected, the wastewater can be directly discharged, or used for preparing solutions. According to the invention, the comprehensive recycling problem of mine wastewater with an extremely low rare earth concentration is solved, and the method disclosed by the invention is large in water treatment quantity, low in equipment requirements, and simple and feasible.
Description
Technical field
The present invention relates to a kind of method of utilizing the extremely low rare earth concentration waste water of coarse grained clay processing in ion type rareearth mine tailing, belong to rare-earth wet method metallurgy and Industrial Wastewater Treatment field.
Technical background
Rare earth is widely used in each fields such as industry, military affairs, agricultural, the Rare Earth Functional Materials that develop rapidly nearly decades has been brought into play especially irreplaceable effect in the technology such as new high-tech industry and military aerospace, and rare earth day by day becomes the generally acknowledged strategic resource in the whole world.Rare earth is a kind of non-renewable natural resources, along with the reinforcement of its exploitation dynamics, and the continuous growth of rare earth demand, higher-grade rare-earth mineral reduces, and rare earth reserves day by day reduce.Therefore, for the rare earth recovery technology in the high efficiency rare-earth extractive technique of low-grade rare-earth mineral and the extremely low rare earth concentration waste water that produces in Rare Earth Production process, obtained paying close attention to widely and studying.Especially in the angle of environment and conservation of resources, study the recovery and utilization technology of extremely low rare earth concentration waste water.
In the ion adsorption type rare earth ore mine wastewater of south, often remain a small amount of rare earth and the ammonia nitrogen of lower concentration.For example, the river of rare-earth mining area, Jiangxi analytical results in may part is: rare earth concentration is 2-3mg/L (REO meter), and ammonia nitrogen concentration is 6-7mg/L (N meter).If this part rare earth is not reclaimed, can cause rare earth and electrolyte content in the ambient water in mining area and even living quarters, downstream to increase, to accelerate rare earth and run off, influence ecological environment, threatens Water resources security.And research shows that rare earth ion is not biodegradable, can hide for a long time in environment along with food chain enters human body, in human body, accumulate for a long time causing various diseases and physiological function disorderly, be detrimental to health.
The enriching and recovering method of low concentration of rare earth ion has a lot, at present mainly with the precipitator method, extraction process, reverse osmosis method and ion-exchange-resin process etc.Wherein, the simplest with the precipitator method, normally adopt lime neutralization to make solution be alkalescence, rare earth is separated out with precipitation of hydroxide and separated with a large amount of water, but because the water yield is large, need to be adjusted to neutral could discharge with acid.Resin adsorption method is also fairly simple, but resin-carried amount is little, and cost is high, and rare earth is resolved comparatively difficulty.The problems such as extraction process is comparatively complicated, although this kind of method enrichment times is large, efficiency is high, and existence is compared too little, and extraction agent solution loss is large, and cost height and secondary pollution are large.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of method of utilizing the extremely low rare earth concentration waste water of coarse grained clay processing in ion type rareearth mine tailing is provided.
The present invention adopts coarse grained clay in the ion type rareearth mine tailing after sodium-chlor modification as sorbent material, to be combined into the elementary cell that can adsorb recovering rare earth from extremely low rare earth concentration mine wastewater and remove ammonia nitrogen in conjunction with chromatography column device.Adsorption and enrichment rare earth from extremely low rare earth concentration waste water, and carry out recovering rare earth by methods such as sodium-chlor desorb and post precipitation, thus reach the object of rare-earth enrichment recovery.Treated solution middle-weight rare earths, ammonia nitrogen and other heavy metal content all can reach emission request, reach recovering rare earth and the dual purpose of processing waste water.
The method of the extremely low rare earth concentration waste water of coarse grained clay processing in ion type rareearth mine tailing of utilizing of the present invention comprises the following steps:
[1] adopt the method for screening from ion type rareearth mine tailing, to choose 20-200 object clay mineral, with the sodium chloride solution of 5-10%, it is carried out to modification, method of modifying comprises on infusion method and post two kinds of drip washing exchange processes, the weight ratio of sodium chloride solution and clay mineral is that 0.6:1 is between 6:1, leach clay mineral, washing makes free sodium enter solution, obtains sodium base coarse grained clay sorbent material, and filtrate cycle is used for preparing modification liquid or strippant solution;
[2] resulting sodium base coarse grained clay is loaded in exchange column or exchange pond, its post is than being that the ratio of post bed height and diameter is between 0.5-10;
[3] pending waste water is introduced in exchange column or exchange pond, pending waste water is fully contacted with the sodium base coarse grained clay on exchange column or in exchange pond, rare earth ion and part ammonia nitrogen are adsorbed by sodium base coarse grained clay, in the solution flowing out, do not contain rare earth ion, ammonia-nitrogen content is also few, can meet water emission request;
[4] wastewater streams comprises and flows from top to bottom and flow two kinds from the bottom up through the mode of exchange column;
[5] rare earth adsorbing on sodium base coarse grained clay in exchange column and the rare earth in solution just no longer adsorb rare earth after reaching balance, rare earth concentration in effluent liquid can increase, therefore, when effluent liquid middle-weight rare earths concentration is greater than 0.5ppm, effluent liquid can not directly discharge, but second exchange column of access or exchange pond, continue to make waste water to flow into from the first exchange column, flow into the second exchange column again, be now equivalent to post ratio and increased one times, flow velocity can reduce;
[6] when the rare earth concentration from the first exchange column effluent liquid approaches the rare earth concentration in waste water, waste water import is directly received on the second exchange column, proceed adsorption operations, and the first exchange column enters desorption phase, to resolve agent solution and introduce the first exchange column, strippant flow of solution direction is contrary with the flow direction of when absorption waste water, strippant solution is acid chlorization sodium solution between pH value 1-3 and the neutral sodium chloride solution between pH value 6-7, above-mentioned strippant Chlorine in Solution na concn is between 5-10%, on strippant solution and exchange column, the weight ratio of sodium base coarse grained clay sorbent material is 0.5-0.8:1, first use acid chlorization sodium solution, use again neutral sodium chloride solution, the ratio of acid chlorization sodium solution and neutral sodium chloride solution is 1:1, after adding strippant solution, continue the strippant solution that water ejects sodium chloride-containing,
[7] the strippant solution of collecting enters settling tank, adopts alkali or carbonate deposition rare earth, filters to obtain solid and obtain rare-earth products through washing, contains sodium-chlor and precipitation agent in filtrate, after being cycled to used in preparation precipitant solution or adjusting acidity for strippant solution;
[8] exchange column after the strippant solution that solution sucks rare earth and ejects sodium chloride-containing through water, for next round adsorption and desorption process, recycles.
Waste water Rare Earth Ion concentration after absorption can be reduced to below 0.5mg/L, and ammonia nitrogen concentration also can be reduced to claimed range.The applicable waste water Rare Earth Ion concentration of present method is from 1mg/L-10mg/L, and ammonia nitrogen concentration is from 5mg/L to 20mg/L.The rare-earth enrichment liquid concentration of resolving can reach 400-500mg/L, available general precipitator method recovering rare earth.
Beneficial effect of the present invention: the present invention mainly solves the waste water that contains a small amount of rare earth and ammonia nitrogen, the recycling problem of especially southern ion adsorption type rare earth ore mountain waste water, can guarantee the removal of efficiently concentrating and the part ammonia nitrogen of low concentration of rare earth, and equipment is simple, operate simple and easy, with low cost.Have sorbent material source wide, cheap, the simple and high advantage of rare earth yield of technique, can be widely used in Rare-earth Mine waste water, is with a wide range of applications.
The explanation of accompanying drawing book
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is T=25 ℃, the adsorption isothermal line of coarse sand sorbent material to mixed rare earth ions under t=1h condition;
Fig. 3 is T=25 ℃, the Langmuir adsorption isothermal line under t=1h concussion null readings;
Fig. 4 be T=25 ℃ of concussion adsorb during balance percentage ratio and every gram of coarse sand sorbent material to mixed rare earth ions Qe with mixed rare earth ions starting point concentration C
0variation relation figure, in figure ordinate zou for absorption percentage;
Fig. 5 is that total rare earth (TRE) adsorptive capacity m (REO meter) and effluent liquid rare earth concentration C (REO meter) are with the relationship change curve of effluent liquid cumulative volume V;
Fig. 6 be before rare earth leakage coarse sand to the accumulation adsorptive capacity of rare earth the fitting a straight line with effluent liquid cumulative volume;
Fig. 7 be after rare earth leakage coarse sand to the accumulation adsorptive capacity of rare earth the change curve with effluent liquid cumulative volume;
Fig. 8 be after rare earth leakage coarse sand to the accumulation adsorptive capacity of rare earth the fitting a straight line with effluent liquid cumulative volume.
Embodiment
Embodiment 1
Under one hour condition of constant temperature (T=25 ℃) constant volume (30mL) vibration, the adsorption isothermal line of 0.2g coarse sand sorbent material under 0.05mg, 0.07mg, 0.1mg, 0.15mg, 0.2mg, 0.25mg, 0.3mg, 0.35mg, 0.4mg mixed rare earth ions (REO meter).Adsorption isothermal line is drawn figure as shown in Figure 2.The concentration of mixed rare earth ions (in REO, as follows) in solution when wherein X-coordinate Ce is balance, the actual saturated extent of adsorption of mixed rare earth ions on 1g coarse sand sorbent material when ordinate zou Qe is balance.Fig. 3 is in embodiment 1, the Langmuir adsorption isothermal line of coarse sand sorbent material to mixed rare earth ions (0.05～0.35mg), the concentration C e of mixed rare earth ions in solution when wherein X-coordinate is balance, the ratio of the actual adsorptive capacity (Qe) of mixed rare earth ions, i.e. Ce/Qe on concentration mixed rare earth ions Ce when ordinate zou is balance in solution and 1g coarse sand sorbent material.Table 1 is according to the data results analysis after Langmuir adsorption isothermal line equation model.Fig. 4 be T=25 ℃ of concussion adsorb during balance percentage ratio and every gram of coarse sand sorbent material to mixed rare-earth oxide (REO meter) Qe with mixed rare earth ions (REO meter) starting point concentration C
0variation relation figure.Result shows: at 25 ℃, coarse sand sorbent material meets Langmuir Adsorption Model to the absorption of rare earth, and its theoretical saturated adsorption capacity Qm is 3.0933umolRE
2o
3/ g, is equivalent to 0.902mg RE
2o
3/ g.
Table 1 T=25 ℃, the Langmuir adsorption isothermal line equation model result under t=1h
Embodiment 2
The ammonia nitrogen simulated wastewater solution of the extremely low rare earth concentration of preparation, wherein ammonia nitrogen NH
4-N (N meter) concentration is 30.24mg/L, and rare earth concentration (REO) is 4.77mg/L; Taking 70g coarse sand sorbent material, to be encased in internal diameter be 24mm, be highly in the core glass chromatography column of 200mm, sorbent material packing height is about 160mm, with addition funnel, the simulated wastewater solution preparing is passed in the chromatography column that sorbent material is housed, regulate addition funnel piston, make liquid level in post remain on 35mm left and right, open chromatography column piston, with 50ml graduated cylinder, receive continuously effluent liquid, with ammonia-nitrogen content and content of rare earth in azo arsenic III spectrophotometry method analysis stream fluid.Connect liquid cumulative volume and be less than 200ml, ammonia nitrogen concentration in effluent liquid (N meter) is all lower than 0.7mg/L, when connecing liquid cumulative volume and being 250ml, ammonia nitrogen concentration in effluent liquid (N meter) is 2.36mg/L, connecing liquid cumulative volume is that 250ml starts, ammonia nitrogen concentration in effluent liquid (N meter) is 30.24mg/L, be consistent with adding solution ammonia nitrogen concentration, now, the total removal amount of ammonia nitrogen is 13.96mg, now, coarse sand sorbent material reaches capacity to the removal effect of ammonia nitrogen, and every gram of average removal amount of coarse sand is 0.1994mg/g.While connecing liquid cumulative volume to 5350ml, pick out liquid and not yet observe rare earth leakage phenomenon, having adsorbed total amount of rare earth (REO meter) is 25.53mg, connects liquid cumulative volume and start to occur rare earth leakage in 5375ml, and initial leakage concentration is 0.27mg/L.When fluid middle-weight rare earths concentration waiting reaches 1.70mg/L, adsorbed total amount of rare earth and reached 34.70mg, every gram of adsorbent rare earth content of coarse sand is 0.4957mg, 54.95% of reasonable opinion saturated adsorption value.Result shows: for extremely low concentration rare earth ammonia nitrogen waste water, coarse sand sorbent material has certain ammonia nitrogen removal ability, but because the treatment capacity of the sorbent material of unit mass is little, for its ammonia nitrogen removal ability of high density ammoniated wastewater, is difficult to reach target call; For the earth solution of extremely low concentration, the water yield is large, and perviousness requires to play a major role.Therefore, although the rare earth adsorptive capacity of the sorbent material of unit mass is lower, but because the water yield of processing is large, be suitable for industrial application.If improve rare earth loaded amount, can the pre-treatment for high concentration rare earth waste water in the later stage.
Embodiment 3
Preparation rare earth ion concentration (REO meter) is the mixed rare earth solution of 111.28mg/L; Taking 36.56g coarse sand sorbent material, to be encased in internal diameter be 24mm, be highly in the core glass chromatography column of 200mm, sorbent material packing height is about 100mm, with addition funnel, the mixed rare earth solution of the 111.28mg/L preparing is passed in the chromatography column that sorbent material is housed, regulate addition funnel piston, make liquid level in post remain on 75mm left and right, open chromatography column piston, with 10ml graduated cylinder, receive continuously effluent liquid, with azo arsenic III spectrophotometry method analysis stream fluid Rare-Earth Content.When connecing liquid and amass as 10ml with stopwatch record while connecing liquid, the time used is 1 minute and 29 seconds; With pure water, substitute sorbent material and earth solution, while keeping in post the about 175mm of liquid level to connect liquid amassing as 10ml, the time used is 4 minutes and 1 second, has proved that earth solution circulation in adsorption column is good, and the penetrating quality of coarse sand sorbent material is good.Connect and when fluid accumulation is added to 150ml, pick out liquid and not yet observe rare earth leakage phenomenon, having adsorbed total amount of rare earth (REO meter) is 16.69mg, connects when fluid accumulation is added to 160ml and starts to occur rare earth leakage, and initial leakage concentration is 1.00mg/L.When fluid middle-weight rare earths concentration waiting (REO meter) reaches 45.00mg/L, adsorb total amount of rare earth (REO meter) and reached 29.87mg, every gram of adsorbent rare earth content of coarse sand (REO meter) is 0.8170mg, 90.58% of reasonable opinion saturated adsorption value.Fig. 5 is that total rare earth (TRE) adsorptive capacity m (REO meter) and effluent liquid rare earth concentration C (REO meter) are with the relationship change curve of the increase of effluent liquid cumulative volume V.Result shows, the penetrating quality of coarse sand sorbent material and the aqueous solution trafficability performance between sorbent material is good; For the rare earth liquid waste disposal of higher concentration, coarse sand sorbent material can reach higher adsorptive capacity, but it is little to process the water yield.
Embodiment 4
The simulated wastewater that preparation rare earth concentration is 111mg/L; Taking 61g coarse sand sorbent material, to be encased in internal diameter be 24mm, be highly in the core glass chromatography column of 200mm, sorbent material packing height is about 155mm, with addition funnel, the simulated wastewater solution preparing is passed in the chromatography column that sorbent material is housed, regulate addition funnel piston, make liquid level in post remain on 45mm left and right, open chromatography column piston, with the graduated cylinder of different size, receive continuously effluent liquid, with azo arsenic III spectrophotometer method analysis stream fluid Rare-Earth Content.Connect liquid cumulative volume and be less than 370ml, effluent liquid middle-weight rare earths concentration is 0mg/L, does not observe the leakage phenomenon of rare earth; When connecing liquid cumulative volume and being 370ml, effluent liquid middle-weight rare earths concentration is 1.85mg/L, and now, coarse sand sorbent material has adsorbed rare earth 41.25mg, and every gram of coarse sand is 0.6567mg/g to the adsorptive capacity of rare earth.When effluent liquid middle-weight rare earths leakage concentration reaches 43.98mg/L, receiving liquid cumulative volume is 491ml, total rare earth adsorptive capacity is 51.91mg, every gram of coarse sand is 0.8510mg/g to the adsorptive capacity of rare earth, 94.38% of reasonable opinion saturated adsorption value, higher than the ratio in embodiment 2, prove under the condition of identical pillar internal diameter, post is than higher, and coarse sand reaches capacity sooner to the sorptive power of rare earth.Fig. 6, Fig. 7 be respectively before the leakage of the present embodiment middle-weight rare earths and rare earth leakage after coarse sand to the accumulation adsorptive capacity of rare earth the result to the mapping of effluent liquid cumulative volume, Fig. 6 shows before rare earth leakage, coarse sand is that its fitting result is as shown in table 2 along with a straight line of crossing initial point increases to the accumulation adsorptive capacity of rare earth.Fig. 7 shows that, after rare earth leakage, the variation track of adsorptive capacity starts to depart from original straight line, becomes a convex curve slightly making progress, if the data after leakage are carried out to fitting of a straight line, fitting result is as shown in Fig. 8 and table 3.The result of embodiment 3 and embodiment 4 all shows: for higher concentration RE waste water, coarse sand sorbent material still has the ability of absorption rare earth ion, but wastewater treatment capacity is little, rare earth is easy to leakage, and the increase of effluent liquid middle-weight rare earths concentration is more slow, there is very long conditions of streaking, the absorption of coarse sand to low concentration of rare earth waste water relatively, coarse sand comparatively fast reaches the absorption saturation capacity of coarse sand to the sorptive power of high concentration rare earth waste water.Therefore, for the earth solution of higher concentration, the processing water yield of coarse sand is little, is suitable for follow-uply to the pre-treatment of high-concentration waste water and improve rare earth loaded amount, improves the rare earth concentration in stripping liquid.
Before the leakage of table 2 rare earth, adsorptive capacity is with the fitting of a straight line result of effluent volume
| Intercept | Slope | R 2 |
| 3.55271E-14 | 0.11128 | 1 |
After table 3 leakage, rare earth content is with the fitting of a straight line result of effluent volume
| Intercept | Slope | R 2 |
| 10.10224 | 0.08564 | 0.99334 |
Embodiment 5
Preparation massfraction is the NaCl solution of 7% neutrality (pH=5.75) and acidity (pH=2.05) as strippant, strippant is joined respectively in the adsorption column that has adsorbed rare earth by addition funnel, with 50ml volumetric flask, receive effluent liquid, analysis stream fluid Rare-Earth Content, result is respectively as shown in table 4, table 5.The acidity that shows to improve stripping liquid is conducive to the desorb of rare earth.Therefore, actual desorption method is: first use the desorb of acid chlorization sodium solution, then to use neutral sodium-chlor desorb, object be to make the desorb of rare earth energy complete, be unlikely to again to make the hydrogen ion concentration on clay too high, avoid adsorbing the water outlet pH causing after rare earth and reduce problem.
The desorption result (rare earth loaded amount is 29.87 milligrams) of table 4pH=2.05NaCl strippant
The desorption result (rare earth loaded amount is 31.95 milligrams) of table 5pH=5.75NaCl strippant
Embodiment 6
Coarse sand after resolving in embodiment 5 continues on for the processing of simulated wastewater, and ammonia nitrogen concentration in simulated wastewater (N meter) is 30.24mg/L, and rare earth concentration (REO meter) is 4.77mg/L, and experiment condition is controlled identical with embodiment 5.Analytical results is: during balance, every gram of coarse sand is 0.1978mg/g to the removal amount of ammonia nitrogen, during rare earth leakage, every gram of coarse sand is 0.2272mg/g to the adsorptive capacity of rare earth, wastewater treatment capacity when result shows that coarse sand is used for the second time remains unchanged substantially, the removal amount of ammonia nitrogen is had to atomic little decline, adsorptive capacity to rare earth remains unchanged substantially, and result shows that coarse sand, as the sorbent material of rare earth and ammonia nitrogen, can reuse.
Embodiment 7
Preparation rare earth concentration (REO meter) 6.036mg/L, the simulated wastewater of ammonia nitrogen concentration (N meter) 34.07mg/L; The sodium base coarse sand that takes 2 parts of 200g is loaded in 2 500ml gas washing bottles that are cascaded; Simulated wastewater is passed into from bottom to top in the gas washing bottle that coarse sand is housed, in the outlet of second gas washing bottle, connect sample analysis, every 500/1000ml connects sample analysis.When effluent volume is accumulated to 1000ml, ammonia nitrogen starts leakage, and leakage concentration is 5.76mg/L; When volume is accumulated to 5500ml, in effluent liquid, ammonia nitrogen concentration is consistent with simulated wastewater, shows that coarse sand has adsorbed ammonia nitrogen saturated, no longer includes adsorption, and now every gram of coarse sand is 0.1830mg/g to the adsorptive capacity of ammonia nitrogen.When effluent volume is accumulated to 20L, rare earth does not also start leakage, when 20.5L, in effluent liquid, detecting rare earth concentration (REO meter) is 0.1490mg/L, now every gram of coarse sand is 0.1341mg/g to the adsorptive capacity of rare earth, the effluent liquid middle-weight rare earths concentration of now analyzing in first gas washing bottle is consistent with simulated wastewater middle-weight rare earths concentration, be that coarse sand in first gas washing bottle has adsorbed saturated to rare earth, now can unload first gas washing bottle resolves, and after second gas washing bottle, connect a wash bottle of being equipped with as the coarse sand of absorption and continue absorption, with this, realize continuous series connection absorption mode, reach that RE waste water processes high-efficiency and continuous processing intent.
Embodiment 8
50ml rare earth concentration (REO meter) is regulated to pH=9 left and right with sodium hydroxide solution for the desorb pregnant solution of 463mg/L (rare-earth enrichment percentage is 84.05%), make rare earth ion with the form precipitation of rare earth hydrate, obtaining residual Re concentration in product filtering separation post analysis supernatant liquor is 0.38mg/L, the rate of recovery of rare-earth precipitation is 99.92%, calculate rare earth from waste water be adsorbed onto precipitation obtain product, its rate of recovery is 83.98%.Result shows can in a large number, effectively reclaim the rare earth in waste water by coarse sand absorption method, realizes the object of resource recycling.
Claims (1)
1. a method of utilizing the extremely low rare earth concentration waste water of coarse grained clay processing in ion type rareearth mine tailing, is characterized in that: said method comprising the steps of:
[1] adopt the method for screening from ion type rareearth mine tailing, to choose 20-200 object clay mineral, with the sodium chloride solution of 5-10%, selected clay mineral is carried out to modification, method of modifying comprises on infusion method and post two kinds of drip washing exchange processes, the weight ratio of sodium chloride solution and clay mineral is that 0.6:1 is between 6:1, leach clay mineral, washing makes free sodium enter solution, obtains sodium base coarse grained clay sorbent material, and filtrate cycle is used for preparing modification liquid or strippant solution;
[2] resulting sodium base coarse grained clay is loaded in exchange column or exchange pond, controls post than being that the ratio of post bed height and diameter is between 0.5-10;
[3] pending waste water is introduced in exchange column or exchange pond, pending waste water is fully contacted with the sodium base coarse grained clay on exchange column or in exchange pond, rare earth ion and part ammonia nitrogen are adsorbed by sodium base coarse grained clay, in the solution flowing out, do not contain rare earth ion, ammonia-nitrogen content is also few, can meet water emission request; [4] wastewater streams comprises and flows from top to bottom and flow two kinds from the bottom up through the mode of exchange column;
[5] rare earth adsorbing on sodium base coarse grained clay in exchange column and the rare earth in solution just no longer adsorb rare earth after reaching balance, rare earth concentration in effluent liquid can increase, therefore, when effluent liquid middle-weight rare earths concentration is greater than 0.5ppm, effluent liquid can not directly discharge, but second exchange column of access or exchange pond, continue to make waste water to flow into from the first exchange column, flow into the second exchange column again, be now equivalent to post ratio and increased one times, flow velocity can reduce;
[6] when the rare earth concentration from the first exchange column effluent liquid approaches the rare earth concentration in waste water, waste water import is directly received on the second exchange column, proceed adsorption operations, and the first exchange column enters desorption phase, strippant solution is introduced to the first exchange column, strippant flow of solution direction is contrary with the flow direction of when absorption waste water, strippant solution is acidity between pH value 1-3 and the neutral sodium chloride solution between pH value 6-7, the concentration of above-mentioned strippant Chlorine in Solution sodium is between 5-10%, on strippant solution and exchange column, the weight ratio of sodium base coarse grained clay sorbent material is 0.5-0.8:1, first use acid chlorization sodium solution, use again neutral sodium chloride solution, the ratio of acid chlorization sodium solution and neutral sodium chloride solution is 1:1, after adding strippant solution, continue the strippant solution that water ejects sodium chloride-containing,
[7] the strippant solution of collecting enters settling tank, employing alkali or carbonate deposition rare earth, and filtration obtains solid and obtains rare-earth products through washing, contains sodium-chlor and precipitation agent in filtrate, after being cycled to used in preparation precipitant solution or adjusting acidity, is used as strippant solution;
[8] exchange column after the strippant solution that solution sucks rare earth and ejects sodium chloride-containing through water, for next round adsorption and desorption process, recycles.
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| PCT/CN2013/090371 WO2015021727A1 (en) | 2013-08-15 | 2013-12-24 | Method for treating solution containing rare earth |
| US14/431,753 US10253394B2 (en) | 2013-08-15 | 2013-12-24 | Method for treating solution containing rare earth |
| CA2885496A CA2885496C (en) | 2013-08-15 | 2013-12-24 | Method for treating solution containing rare earth |
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