CN100457928C

CN100457928C - Carbonate deposition method of crystal type heavy rare earth

Info

Publication number: CN100457928C
Application number: CNB2007100272398A
Authority: CN
Inventors: 杨金华; 韩旗英; 凌诚; 李世清; 韩德义
Original assignee: GUANGDONG FUYUAN RARE EARTH NEW MATERIAL CO Ltd
Current assignee: GUANGDONG FUYUAN RARE EARTH NEW MATERIAL CO Ltd
Priority date: 2007-03-22
Filing date: 2007-03-22
Publication date: 2009-02-04
Anticipated expiration: 2027-03-22
Also published as: CN101037723A

Abstract

The invention relates to a method for precipitating crystal heavy-rare-earth carbonate, wherein pH of heavy-rare-earth chlorid solution is adjusted to 5.0 to 5.2 by the 8-10% carbon-ammonia water, adding polyacrylamide saturated-water solution in which the volume is 1-3 per thousand of that of heavy-rare-earth chlorid solution, filtering, and the filtrate is diluted to 0.4 to 0.5 M by water, adding eavy-rare-earth carbonate, as seed crystal, agitating to uniformly mix, then precipitating by 8-10% carbon-ammonia water, ending precipitating when pH is 6.2, adding water to 80-90% of volume of the precipitating container, stopping the press water for 12- 24 hours, washing the precipitate for 2 -3 times, filtrating, and crystal heavy-rare-earth carbonate is obtained. The invention has simple operation, low cost, high yield of heavy-rare-earth and good-quality product which contains low-water and low calcium carbonate, chloride ion or the like, is easy to filtrate, having convenient packaging, stacking and trasportation, and small contamination.

Description

The method of crystal type heavy rare earth carbonate deposition

Technical field

The invention belongs to non-ferrous metal hydrometallurgy field, relate to a kind of method of crystal type heavy rare earth carbonate deposition.

Background technology

Heavy rare-earth solution after the mishmetal grouping as finished product, need carry out precipitation process and transfer solid phase to.Intermediate processing mainly contains two kinds at present: a kind of is oxalic acid precipitation, its sedimentation effect is better, particle is bigger, precipitate impure few, but oxalic acid price height, toxicity is big, pollute the environment, its resolution of precipitate degree is bigger, influences rare earth yield, the precipitation cost is high and increased secondary separation intractability and cost, so the heavy rare earths big to output, that the output value is low does not have realistic meaning.Another kind is a carbon ammonium precipitation, its precipitation cost is low, heavy rare earths carbonate solubility product is less, the rare earth yield height, and subsequent disposal is convenient, but normal characteristic because of heavy rare earth element itself, the improper precipitate particles that will cause of deposition condition is tiny, filtration difficulty, product water ratio height, impurity such as chlorine root and calcium, iron are higher, make troubles for packing, transportation and use.

Summary of the invention

The present invention solves the deficiency that present mishmetal grouping back heavy rare earths chloride soln intermediate processing exists, and a kind of intermediate processing that precipitates the crystal type heavy rare earth carbonate that cost is low, rare earth yield is high is provided.

The technical solution adopted in the present invention and process are: 1. removal of impurities: the heavy rare earths chloride soln adds concentration 8～10% carbon ammonium water, transfer pH value 5.0～5.2, add 1～3 ‰ polyacrylamide saturated aqueous solution of heavy rare earths chloride soln volume, mix thoroughly, leave standstill clarification 2～5 hours.2. the heavy rare earths chloride soln dilutes and adds crystal seed: filter, filtrate is to precipitation vessel, it is 0.4～0.5M that thin up makes heavy rare earths chloride soln concentration, add heavy rare earths carbonate crystal seed, as precipitating for the first time, use oxalic acid precipitation heavy rare earths chloride soln and make crystal seed, the add-on of crystal seed is that it is converted into heavy rare-earth oxide and accounts for 25～35% of the contained rare earth content of precipitation heavy rare earths chloride soln, and fully mixes.3. precipitate: under agitation condition, add concentration 8～10% carbon ammonium water, when pH value 5.6～5.8, slow down carbon ammonium water and add speed, when pH value 6.2, stop to add carbon ammonium water immediately, continue to stir 10～20 minutes, and get about 100ml supernatant liquor filter paper filtering, filtrate adds the detection of saturated oxalic acid water should not have the white opacity phenomenon, or get 1～5ml filtrate with the disodium ethylene diamine tetraacetate of 0.05～0.2 volumetric molar concentration be the titration of the EDTA aqueous solution go out the filtrate rare earth concentration should be less than 0.005 mole, otherwise it is complete to precipitation to add carbon ammonium water, inaccurate to prevent pH value observation, causes rare-earth precipitation not exclusively to make the rare earth loss.4. setting-out: it is full to add water to precipitation vessel 80～90%, and setting-out left standstill 12～24 hours.5. wash water: after setting-out leaves standstill, supernatant liquid filtering is drained, it is full to add water to precipitation vessel 80-90% again, after fully mixing, leaves standstill clarification, and supernatant liquid filtering is drained, and repeats wash water 2～5 times, filters the supernatant liquor of draining, and obtains crystal type heavy rare earth carbonate.

The present invention is easy to operate, operation is simple, the precipitation cost is low, rare earth yield is high, good product quality, the heavy rare earths carbonate that obtains is crystalline precipitation, filter easily, the product water ratio is low, lime carbonate in the product, chlorine root equal size have been reduced, packing, stacking, transportation and follow-up easy to use, and environmental pollution is little.

Embodiment

Embodiment one

Mishmetal extraction grouping back heavy rare earths chloride soln 1200L, rare earth concentration 1.47M, acidity 0.78N, major impurity Fe ₂O ₃183mg/L, CaO 30.5mg/L, PbO 0.8mg/L, ree distribution pattern Dy ₂O ₃0.11%, Ho ₂O ₃2.075%, Er ₂O ₃7.99%, Tm ₂O ₃0.99%, Yb ₂O ₃5.7%, Lu ₂O ₃0.77%, Y ₂O ₃81.8%, molecular-weight average is 122.13 as calculated, and the heavy rare earths chloride soln contains heavy rare-earth oxide 215.44Kg.The heavy rare earths chloride soln adds earlier in the settling bath, and under agitation the heavy rare earths chloride soln is adjusted pH value 5.2 with 10% carbon ammonium water, adds 3.6L polyacrylamide saturated aqueous solution and also fully mixes, and leaves standstill clarification 5 hours; Above-mentioned solution is filtered, the filter pump pump is to settling bath, thin up is to 0.5M, the 251.33Kg heavy rare earths carbonate that adds original precipitation reservation is made crystal seed, it is 75.4Kg that the add-on of crystal seed is converted into heavy rare-earth oxide, account for 35% of the contained rare earth content of precipitation heavy rare earths chloride soln, after fully mixing; Begin to add 10% carbon ammonium water precipitation, precipitation process often detects pH value and changes, when pH value 5.8, slow down carbon ammonium water and add speed, when pH value 6.2, stop to add carbon ammonium water immediately, continue to stir 20 minutes, and get about 100ml supernatant liquor filter paper filtering, filtrate adds saturated oxalic acid water and detects no white precipitate, illustrate that rare-earth precipitation is complete, it is full that water adds to settling bath 90%, leaves standstill setting-out, and throw out is through setting-out after 24 hours, supernatant liquid filtering is drained, settling bath adds water to 90% again expires, and fully mixes and carries out wash water, leaves standstill clarification then, supernatant liquid filtering is drained, repeat wash water 5 times, filter the supernatant liquor of draining at last, throw out is put into whizzer dry, obtain 943.83Kg crystal type heavy rare earth carbonate, make the heavy rare earths carbonate of crystal seed comprising 251.33Kg.

Crystal type heavy rare earth carbonate detects by analysis: total amount of rare earth 96.6%, burn till rate 31.6%, Fe ₂O ₃0.1%, CaO 0.05%, PbO 0.02%, Cl ^-0.02%, ree distribution pattern Dy ₂O ₃0.108%, Ho ₂O ₃2.092%, Er ₂O ₃8.011%, Tm ₂O ₃0.986%, Yb ₂O ₃5.706%, Lu ₂O ₃0.783%, Y ₂O ₃81.66%, can obtain heavy rare-earth oxide 212.71Kg as calculated, promptly rare earth yield is 98.73%.

Embodiment two

Mishmetal extraction grouping back heavy rare earths chloride soln 1500L, rare earth concentration 1.55M, acidity 0.66N, major impurity Fe ₂O ₃205mg/L, CaO 32.2mg/L, PbO 0.68mg/L, ree distribution pattern Dy ₂O ₃0.08%, Ho ₂O ₃2.18%, Er ₂O ₃8.03%, Tm ₂O ₃0.94%, Yb ₂O ₃5.57%, Lu ₂O ₃0.69%, Y ₂O ₃82.06%, molecular-weight average 121.8 as calculated, and it is 283.19Kg that the heavy rare earths chloride soln contains heavy rare-earth oxide.The heavy rare earths chloride soln adds in the settling tank, the heavy rare earths chloride soln is adjusted pH value 5.0 with 8% carbon ammonium water under agitation condition, adding 1.5L polyacrylamide saturated aqueous solution also fully mixes, leave standstill clarification 2 hours, above-mentioned solution is filtered, the filter pump pump is to settling tank, thin up is to 0.4M, the 242.24Kg heavy rare earths carbonate that adds original precipitation reservation is made crystal seed, the add-on of crystal seed is converted into heavy rare-earth oxide 71Kg, account for 25% of the contained rare earth content of precipitation heavy rare earths chloride soln, after fully mixing, begin to add 8% carbon ammonium water precipitation, precipitation process often detects pH value and changes, when pH value 5.6, slow down carbon ammonium water and add speed, when pH value 6.2, stop to add carbon ammonium water immediately, continue to stir 10 minutes, and get about 100ml supernatant liquor filter paper filtering, filtrate get 5ml with the disodium ethylene diamine tetraacetate of 0.0826M be the titration of the EDTA aqueous solution to go out the filtrate rare earth concentration be 0.0035M, illustrate that rare earth precipitates fully substantially, it is full that water adds to settling tank 80%, leave standstill setting-out, throw out, after 12 hours is drained supernatant liquid filtering through setting-out, and settling tank adds water to 80% again expires, fully mix and carry out wash water, leave standstill clarification then, supernatant liquid filtering is drained, repeat wash water 2 times, filter the supernatant liquor of draining at last, throw out is put into whizzer dry, obtain 1183.84Kg crystal type heavy rare earth carbonate, make the heavy rare earths carbonate of crystal seed comprising 242.24Kg.

Crystal type heavy rare earth carbonate detects by analysis: total amount of rare earth 96.72%, burn till rate 30.64%, Fe ₂O ₃0.11%, CaO 0.06%, PbO 0.023%, Cl ^-0.054%, ree distribution pattern Dy ₂O ₃0.08%, Ho ₂O ₃2.19%, Er ₂O ₃8.05%, Tm ₂O ₃0.96%, Yb ₂O ₃5.55%, Lu ₂O ₃0.67%, Y ₂O ₃82.11%, can obtain heavy rare-earth oxide 279.83 as calculated, promptly rare earth yield is 98.81%.

Show from analysis result: the present invention has that rare earth yield height, product moisture content are low, the product The characteristics that non-rare earth impurity content is low.

Claims

1, a kind of method of crystal type heavy rare earth carbonate deposition is characterized in that:

(1) the heavy rare earths chloride soln is added concentration 8～10% carbon ammonium water, make pH value 5.0～5.2, then, add 1～3 ‰ polyacrylamide saturated aqueous solution of heavy rare earths chloride soln volume, mix thoroughly, left standstill 2～5 hours;

(2) filter, the filtrate thin up makes heavy rare earths feed concentration 0.4～0.5M, adds heavy rare earths carbonate crystal seed, and the add-on of crystal seed accounts for 25～35% of the contained rare earth content of heavy rare earths chloride soln for it is converted into heavy rare-earth oxide, mixes thoroughly;

(3) under agitation add concentration 8～10% carbon ammonium water, when pH value 6.2, promptly stop to add carbon ammonium water, restir 10～20 minutes;

(4) adding water to precipitation vessel 80～90% expires, and leaves standstill setting-out 12～24 hours;

(5) supernatant liquid filtering, it is full to add water to precipitation vessel 80-90% again, stirs, and leaves standstill, and supernatant liquid filtering repeats wash water 2～5 times, filters, obtains crystal type heavy rare earth carbonate.

2, the method for crystal type heavy rare earth carbonate deposition according to claim 1 is characterized in that described supernatant liquor is to detect or the disodium ethylene diamine tetraacetate titration with oxalic acid water.