For the rare earth extraction process integrating device of ion type rareearth ore re dip solution
Technical field
The utility model relates to the extraction of ion type rareearth ore, particularly relates to a kind of rare earth extraction process integrating device for ion type rareearth ore re dip solution.
Background technology
Ion adsorption type rare earth ore is mainly distributed in south China area, as Jiangxi, Hunan, Fujian, Guangdong, Guangxi, wherein maximum with Jiangxi intensive quantity.The type ore has the features such as distribution area is wide, reserves are large, radioactivity is low, exploitation is easy, extraction process is simple, production cost is low, good product quality.Be adsorbed on the clay minerals such as kaolin, halloysite and hydromica in ionic condition in Rare Earth Elements 80% ~ 90%, be adsorbed on the water insoluble or ethanol of rare-earth cation on clay mineral, but at strong electrolyte (as NaCl, (NH
4)
2sO
4, NH
4cl, NH
4ac etc.) can ion-exchange be there is in solution and enter solution and there is reversible reaction.
The exploitation of ionic adsorption rare-earth mineral and extraction live through four developmental stage, are respectively sodium-chlor pond leaching+oxalate precipitation method, ammonium sulfate pond leaching+oxalate precipitation method, ammonium sulfate dump leaching+oxalic acid or ammonium bicarbonate precipitation method, ammonium sulfate Situ Leaching+oxalic acid or ammonium bicarbonate precipitation method.Because Situ Leaching technique has the advantages such as vegetation deterioration area is little, cost is lower relative to pond leaching, heap leaching method, be widely used now.
At present, the extraction flow process of ion adsorption type rare earth ore can be sketched and be: by digging a well in the mining area containing ion type rareearth ore or ore deposit section, add ammonium sulfate leaching ore deposit agent by earth's surface fluid injection well, after infiltration or ion-exchange, adopt negative pressure drawing liquid and water seal leak stopping method to collect re dip solution.Re dip solution adopts ammoniacal liquor or bicarbonate of ammonia to regulate pH to 5.2 ~ 5.4 except the impurity such as de-iron, aluminium again, after removal of impurities, clear liquid adds appropriate oxalic acid or bicarbonate of ammonia carries out Precipitation crystal again, finally can obtain crystal formation oxalic acid mishmetal or carbonic acid mishmetal product.But the extraction of re dip solution still exists following shortcoming: the quantity of removal of impurities pond, settling tank is many, floor space is large, and after Mine closure, big area pond is idle, and massif vegetation causes irrecoverability to destroy; Rare earth rate of loss is high, and reagent consumption amount is large; Rare earth mining cut-off grade is high, causes the wasting of resources of lean ore; Remain in a large amount of ammonium sulfate in mine and low concentration of rare earth runs off in vain, not only cause the wasting of resources, and under natural force effect, cause the ammonia nitrogen in periphery runoff water and heavy metals exceeding standard.
Utility model content
The purpose of this utility model, exactly in order to overcome above-mentioned prior art Problems existing, provides a kind of rare earth extraction process integrating device for ion type rareearth ore re dip solution.
The purpose of this utility model is achieved through the following technical solutions: a kind of rare earth extraction process integrating device for ion type rareearth ore re dip solution, comprises the pretreatment unit, rare-earth enrichment unit, iron aluminium impurity removing unit and the rare-earth precipitation unit that are connected successively by pipeline;
Described pretreatment unit comprise be connected successively by pipeline feed surge tank, fresh feed pump and sand filtration or ultrafiltration/micro-filtration; Feed surge tank inlet ductwork connects re dip solution supplied materials pipeline, feed surge tank export pipeline connects fresh feed pump import, fresh feed pump outlet connects sand filtration or ultrafiltration/micro-filtration, the concentrated solution outlet of sand filtration counter-flushing liquid or ultrafiltration/micro-filtration connects stoste centralized pool or coagulant precipitation pond, and filtrate outlet connects rare-earth enrichment unit;
Described rare-earth enrichment unit comprises the first filtrate tank, pressure pump, cartridge filter, topping-up pump, nanofiltration membrane or the reverse osmosis membrane stack and the second filtrate tank that are connected successively by pipeline; The inlet ductwork of the first filtrate tank connects the filtrate outlet pipeline of described sand filtration or super/microfiltration membrane device, the filtrate outlet of nanofiltration membrane or reverse osmosis membrane stack connects the second filtrate tank inlet ductwork, and the concentrated solution outlet of nanofiltration membrane or reverse osmosis membrane stack connects iron aluminium impurity removing unit.
Described iron aluminium impurity removing unit comprises the first agitation vat and the first whizzer that are connected successively by pipeline, the inlet ductwork of the first agitation vat connects the concentrated solution outlet pipeline of described nanofiltration membrane or reverse osmosis membrane stack, and the centrifugate outlet of the first whizzer connects rare-earth precipitation unit; In the first agitation vat, be provided with the first stirrer, top is connected with the first pH regulator device.Aerating apparatus is connected with in the bottom of the first agitation vat.
Described rare-earth precipitation unit comprises the second agitation vat, crystallizer, the second whizzer and the centrifuge mother liquor holding tank that are connected successively by pipeline, the inlet ductwork of the second agitation vat connects the filtrate outlet pipeline of described first whizzer, and the centrifugate outlet of the second whizzer connects centrifuge mother liquor holding tank inlet ductwork; In the second agitation vat, be provided with the second stirrer, top is connected with the second pH regulator device.
Described aerating apparatus comprises gas compression pump and automatic electromagnetic valve, and the import of gas compression pump connects the source pipeline of air, and gas compression pump outlet connects automatic electromagnetic valve, and the outlet of automatic electromagnetic valve connects the first agitation vat.
The top of described first agitation vat is connected with the first pH regulator device, described first pH regulator device comprises bicarbonate of ammonia or ammoniacal liquor Automatic Dosing valve and pH sensor, the import of bicarbonate of ammonia or ammoniacal liquor Automatic Dosing valve connects the source pipeline of bicarbonate of ammonia or ammoniacal liquor, outlet connection first agitation vat, pH sensor is arranged on and dosing mouth far-end, is usually arranged on the bottom of the first agitation vat.
The first stirrer is provided with in described first agitation vat.
Described second pH regulator device comprises oxalic acid/bicarbonate of ammonia Automatic Dosing valve and pH sensor, the import of oxalic acid/bicarbonate of ammonia Automatic Dosing valve connects the source pipeline of oxalic acid/bicarbonate of ammonia, outlet connection second agitation vat, pH sensor is arranged on the bottom of the second agitation vat.
Membrane filtration aperture in described ultrafiltration/micro-filtration is 10 ~ 1000nm.
In described nanofiltration membrane stack, the rejection of nanofiltration membrane to magnesium sulfate is more than or equal to 97%.
Described first agitation vat and the second agitation vat can be respectively the bucket of two or more series connection or parallel connection.
Adopt the utility model device process ion type rareearth ore re dip solution, there is following advantage and disadvantage:
1, floor space is little, is only 10% ~ 20% of traditional technology occupation of land, without vegetation destruction;
2, whole set process device is packaged type, automated operation, not only in succession can apply to multiple exploitation point, reduces the one-time investment of equipment;
3, integrated equipment continuous seepage, productive capacity is stablized;
4, whole set process total rare earth recovery rate can up to 97% ~ 98%;
5, the consumption of bicarbonate of ammonia is only 50 ~ 60% of traditional technology, and the consumption of sulfuric acid is only 10 ~ 20% of traditional technology dosing;
6, the cut-off grade of rare earth mining can reduce greatly, significantly can extend the exploitation time limit in mine on the original basis, drastically increase rare earth resources utilization ratio.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the rare earth extraction process integrating device of the utility model ion type rareearth ore re dip solution.
Embodiment
Below in conjunction with the drawings and specific embodiments, the utility model is described in detail.
See Fig. 1, Techniques For Extraction of Rare Earths integrating device of the present utility model, comprises the pretreatment unit, rare-earth enrichment unit, iron aluminium impurity removing unit and the rare-earth precipitation unit that are connected successively by pipeline;
Above-mentioned pretreatment unit comprise be connected successively by pipeline feed surge tank 1, fresh feed pump 21 and sand filtration or ultrafiltration/micro-filtration 2; Feed surge tank 1 import connects re dip solution supplied materials pipeline, feed surge tank 1 exports and connects fresh feed pump 21 import by pipeline, fresh feed pump 21 exports and connects sand filtration or ultrafiltration/micro-filtration, the concentrated solution outlet of sand filtration counter-flushing liquid or ultrafiltration/micro-filtration connects stoste centralized pool or coagulant precipitation pond by recycling pipeline 23, filtrate outlet connects the first filtrate tank 24 import by pipeline, and the first filtrate tank 24 exports and connects rare-earth enrichment unit.Membrane filtration aperture in above-mentioned ultrafiltration/micro-filtration is 10 ~ 1000nm.Sand filtration or ultrafiltration/micro-filtration 2 are provided with counter-flushing pipeline 22.
Above-mentioned rare-earth enrichment unit comprises the first filtrate tank 24, pressure pump 3, cartridge filter 4, topping-up pump 5, nanofiltration membrane stack or the reverse osmosis membrane stack 6 and the second filtrate tank 61 that are connected successively by pipeline; The import of pressure pump 3 connects the first filtrate tank 24 and exports, and the first filtrate tank 24 import connects the filtrate outlet of sand filtration or super/microfiltration membrane device, and the filtrate outlet of nanofiltration membrane stack or reverse osmosis membrane stack connects the second filtrate tank 61.The concentrated solution 62 of nanofiltration membrane stack or reverse osmosis membrane stack exports and connects iron aluminium impurity removing unit through pipeline.The rejection of nanofiltration membrane to magnesium sulfate in above-mentioned nanofiltration membrane stack is more than or equal to 97%.
Above-mentioned iron aluminium impurity removing unit comprises the first agitation vat 7 and the first whizzer 8 be connected successively by pipeline.The concentrated solution 62 that feed 72 import of the first agitation vat connects described nanofiltration membrane stack or reverse osmosis membrane stack exports, first agitation vat discharge port 73 connects the first whizzer feed 81 import through pipeline, the centrifugal deposition 82 of the first whizzer is iron, aluminium slag, and the centrifugate 83 of the first whizzer exports and connects rare-earth precipitation unit through pipeline; Be connected with aerating apparatus 9 in the bottom of the first agitation vat, according to the attainable mixing effect of aerating apparatus 9, can arrange the first stirrer 71 in agitation vat, to increase mixing effect, the top of the first agitation vat is connected with the first pH regulator device 10.Aerating apparatus 9 comprises gas compression pump 91 and automatic electromagnetic valve 92, and the import of gas compression pump connects the source pipeline 93 of air, and gas compression pump outlet connects automatic electromagnetic valve, and the outlet of automatic electromagnetic valve connects the first agitation vat.First pH regulator device 10 comprises bicarbonate of ammonia or ammoniacal liquor Automatic Dosing valve 101 and pH sensor 102, the import of bicarbonate of ammonia or ammoniacal liquor Automatic Dosing valve connects the source pipeline 103 of bicarbonate of ammonia or ammoniacal liquor, outlet connection first agitation vat, pH sensor is arranged on the first agitation vat bottom.
Above-mentioned rare-earth precipitation unit comprises the second agitation vat 11, crystallizer 12, second whizzer 13 and the whizzer mother liquor holding tank 131 that are connected successively by pipeline.The centrifugate 83 of described first whizzer of feed 112 import connection of the second agitation vat exports, and the sediment 133 of the second whizzer is crystal formation oxalic acid or carbonic acid mishmetal, and the centrifugate export pipeline of the second whizzer connects whizzer mother liquor holding tank 131; In the second agitation vat, be provided with the second stirrer 111, top is connected with the second pH regulator device 14.Second pH regulator device 14 comprises oxalic acid/bicarbonate of ammonia Automatic Dosing valve 141 and pH sensor 142, the import of oxalic acid/bicarbonate of ammonia Automatic Dosing valve connects the source pipeline 143 of oxalic acid/bicarbonate of ammonia, outlet connection second agitation vat, pH sensor is arranged on and the second agitation vat bottom.
Principle of work of the present utility model is, re dip solution pumps into sand filtration or ultrafiltration/micro-filtration, tiny suspended particle, microorganism etc. wherein can be retained, to prevent from causing dirty stifled or pollution to subsequent nano-filtration film or reverse osmosis membrane, greatly can reduce the film replacement cycle and improve membrane sepn efficiency.
Sand filtration or ultrafiltration/micro-filtration permeate are through nanofiltration membrane or reverse osmosis membrane system, its rare earth ion can nearly 100% be forced to retain, rare earth cycles of concentration can reach 10 ~ 50, when ensureing that total amount of rare earth is substantially constant, greatly reduces the process water yield of subsequent technique.
Nanofiltration membrane or reverse osmosis membrane concentrated solution by adding bicarbonate of ammonia or ammoniacal liquor, and constantly stir, and regulate material liquid pH value to 5.2 ~ 5.4, impel iron, aluminum ion etc. to generate hydroxide colloid and separate out.
The aerating apparatus that agitation vat before removal of impurities is equipped with is filled with air by automatic batch-type, makes the divalence ferrous ion in feed liquid be converted into ferric ion, can react generation ferric hydroxide colloid to realize iron ion when pH is about 4.0.The capacity of agitation vat is enough large, and the precipitin reaction of iron, aluminium can be made abundant, and colloidal solid is grown up, and improves follow-up solid-liquid separation efficiency.