CN108707749A - Special precipitating reagent of ionic minerals separation factory and preparation method thereof - Google Patents
Special precipitating reagent of ionic minerals separation factory and preparation method thereof Download PDFInfo
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- CN108707749A CN108707749A CN201810703535.3A CN201810703535A CN108707749A CN 108707749 A CN108707749 A CN 108707749A CN 201810703535 A CN201810703535 A CN 201810703535A CN 108707749 A CN108707749 A CN 108707749A
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Abstract
The invention discloses special precipitating reagents of a kind of ionic minerals separation factory and preparation method thereof, are made of main component using potassium sodium mine, sodium bicarbonate, sandworm culture rare-earth precipitation liquid and fruit shell or cellulose series biomass, preparation method includes：Potassium sodium mine, fruit shell or cellulose series biomass roasting, mix with sodium bicarbonate, powder precipitation agent are made, then be mixed to prepare with sandworm culture rare-earth precipitation liquid.Precipitating reagent produced by the present invention be particularly suitable in ionic mineral in, heavy rare earth precipitation, and with many advantages such as rate of deposition height, the good, natural environmental-protective of concentration effect.
Description
Technical field
The present invention relates to technical field of rare-earth separation, the especially a kind of special precipitating reagent of ionic minerals separation factory and its system
Preparation Method.
Background technology
China is the maximum rare earth resources big country in the whole world, and in explored resource, China rare earth reserves account for about the whole world
The 31% of total amount.The addition of rare earth can improve the quality and performance of other products, be widely used in each of modern society
The various high-technology fields such as field, including hybrid vehicle, mobile phone, superconductor and military affairs, thus have " 21 century Huang
The good reputation of gold ".Especially prominent, rare earth can greatly improve the combat performance of related modern military new and high technology weapon, be
A kind of very important strategic resource.
The big series of rare earth main component in China accounts for China's rare earth first, with the light rare earth resource that light rare earth is main partition
The 88% of industrial gross reserves is mainly distributed on one band of Inner Mongol Bayan Obo and Mianning, sichuan Province, mainly has lanthanum, cerium, praseodymium, neodymium and lacks
Measure samarium and europium etc.；Wherein typical mineral is packet header Bastnaesite-Monazite mixed rare earth concentrate, and such mineral deposits account for generation
The 25% of boundary's reserves is the first in the world.Second is that in, heavy rare earth be main partition in, heavy ion type rare earth resources, with rare
The ionic condition preservation seen in clay class mineral, integrated distribution on Jiangxi, Guangdong, Hunan, Fujian and other places, rich in samarium, europium,
Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium etc., value are very high.
Ion type rareearth ore is the exclusive extremely important mineral resources again in China, europium that ion type rareearth mineral deposit is rich in,
Terbium, dysprosium are to be difficult to obtain, added value high middle heavy rare earth element again from other Rare Earth Mines.Southern ion type rareearth ore exploit to
The present has more than 40 years history, since ion type rareearth mineral rare earth element mainly mutually exists with ion, using traditional object
Reason beneficiating method cannot be such that rare-earth original ore is enriched with, and be unable to get corresponding rare earth ore concentrate, can only use the beneficiating method of Chemical Leaching, carry
The technological process taken includes Situ Leaching, leachate removal of impurities, extracts mixed rare earth compound from leachate, manufactured various mixed
Rare earth compound such as mixed rare earth chlorides are closed, product, or the further raw material for being separated into single rare earth can be used as.
Wherein, by obtained mixed rare earth compound after Rare Earth Concentrate Decomposition, separating and extracting single pure rare earth element, in chemistry
It is more complicated and difficult in technique.Use at present it is more be solvent extraction, be using organic solvent from its
Different rare earth elements is extracted respectively in not miscible aqueous solution, single earth solution is obtained, then distinguishes again
Carry out precipitation separation.Obtained single earth solution, it is usually anti-with earth solution using ammonium bicarbonate soln as precipitating reagent
It answers, after the completion of reaction, slurries can obtain the positive carbonate of rare earth after being filtered, washed, and this technique can introduce NH using ammonium hydrogen carbonate4 +
Ion causes ammonia nitrogen in waste water exceeded, and harmful effect is generated to the environment of surrounding.
The patent of invention that Authorization Notice No. is CN105803199 discloses a kind of hydroxide precipitation method and prepares low-sulfur rare earth
The method of oxide is added containing the dissolved organic matters such as malic acid, acetylacetone,2,4-pentanedione, mixed configuration in rare earth sulfate solution
At precipitation stoste；Alkaline precipitating agent is added into precipitation stoste again and carries out precipitation reaction, the dosage of the precipitating reagent is precipitation institute
The 105%~120% of the theoretical amount of the rare earth in rare earth sulfate solution is stated, wherein alkaline precipitating agent includes ammonium hydroxide, hydroxide
One or more of sodium, calcium hydroxide, magnesium hydroxide, calcium oxide and magnesia.This method can obtain low-sulfur rare-earth oxidation
Object, but it has been still incorporated into a large amount of NH according to ammonium hydroxide4 +Ion can not fundamentally solve the problems, such as that ammonia nitrogen is exceeded, if adopting
With other hydroxide or oxide, still it is used as precipitating reagent by artificial synthesized chemical reagent with simple, precipitates
It is of high cost.
To solve the problems, such as ecological disruption, the special precipitating reagent of separation factory for reducing ammonia and nitrogen pollution is extremely important by a kind of exploitation
's.
Invention content
The invention discloses special precipitating reagents of a kind of ionic minerals separation factory and preparation method thereof, are particularly suitable for ion
In in type mineral, heavy rare earth precipitation, and with many advantages such as rate of deposition height, the good, natural environmental-protective of concentration effect.
To achieve the above object, the technical scheme is that：
A kind of special precipitating reagent of ionic minerals separation factory, includes the component of following parts by weight：10~25 parts of potassium sodium mine, bicarbonate
20~35 parts of sodium, 0.2~6 part of sandworm culture rare-earth precipitation liquid roast 1~10 part of auxiliary agent, and the roasting auxiliary agent is after burning
Grey pH>9.5 fruit shell or cellulose series biomass；The sandworm culture rare-earth precipitation liquid be by sandworm be seeded to
The shell-lime of kelp and sea shells class biology is that culture obtains on the culture medium of raw material.Preferably, including following parts by weight
Component：15 parts of potassium sodium mine, 25 parts of sodium bicarbonate, 1 part of sandworm culture rare-earth precipitation liquid, the grey pH> after burning;9.5 fruit
4 parts of shell or cellulose series biomass.
The custom that the sandworm mentioned in the technical program is Guangxi and one band of Guangdong to one kind biology for causing " sandworm foot "
Claim, at spring, summer and autumn, when temperature increases, people go rice terrace, livestock shack, ditch, small pond etc. to have dirty water
Place, foot touch water, will cause to infect, and patient, which often feels, very to itch unbearably, is to have suffered from " sandworm foot ".This kind of life
The scientific name of object is wriggler, is generally called wiggler.The present invention is this kind of biology of acquisition wriggler, is applied to rare earth after culture
In precipitation.
Further, further include the roasting auxiliary agent of following parts by weight：35~60 parts of tea bran, 2~10 parts of pine tree dried fruit fruit.
Preferably, the grey pH> after burning;9.5 fruit shell be wrinkle fruit paulownia seeds of a tung oil tree shell, tea seed episperm, cotton seed hull, wheat husk and
One or more of rice husk, the grey pH> after burning;9.5 cellulose series biomass is stalk, straw, hay and corn
It is one or more in core.
Preferably, it is described above using the shell-lime of kelp and sea shells class biology as the culture medium of raw material in mainly by with
The raw material of lower parts by weight is made：300~600 parts of kelp, 50~150 parts of the shell-lime of sea shells class biology, water 40000~
60000 parts；And per 1kg using the shell-lime of kelp and sea shells class biology in the culture medium of raw material, to contain sodium bicarbonate 150
~300g.
The above using the shell-lime of kelp and sea shells class biology as the preparation method of the culture medium of raw material include with
Lower step：A1. following raw material is weighed by weight：300~600 parts of kelp, sea shells class biology shell-lime 50~150
Part, 40000~60000 parts of water, mixing boil 1~5h, obtain mixture A；A2. object A to be mixed is cooled to 25~50 DEG C, according to every
1kg using the shell-lime of kelp and sea shells class biology as the culture medium of raw material in containing sodium bicarbonate 150~300g carbon is added
Sour hydrogen sodium, stirs evenly, cooling after sodium bicarbonate is completely dissolved, and filtering is able to the shell of kelp and sea shells class biology
Ash is the culture medium of raw material；A3. sandworm is inoculated in using the shell-lime of kelp and sea shells class biology as the culture medium of raw material
In, cultivate 40~72h, you can obtain sandworm culture rare-earth precipitation liquid.
It is furthermore preferred that the shell-lime using kelp and sea shells class biology further includes as the raw material of the culture medium of raw material
The component of following parts by weight：10~100 parts of red ginseng, 50~200 parts of Radix Codonopsis, 100~300 parts of mushroom, 10~90 parts of livestock blood,
10~100 parts of white sugar, 50~200 parts of ganoderma lucidum.
The above using the shell-lime of kelp and sea shells class biology as the preparation method of the culture medium of raw material include with
Lower step：B1. following raw material is weighed by weight：300~600 parts of kelp, the shell-lime 50~150 of sea shells class biology
Part, 40000~60000 parts of water, 10~100 parts of red ginseng, 50~200 parts of Radix Codonopsis, 100~300 parts of mushroom, livestock blood 10~90
Then above-mentioned raw materials are mixed and boil 1~5h, obtain mixture B by part, 10~100 parts of white sugar, 50~200 parts of ganoderma lucidum；
B2. object B to be mixed is cooled to 25~50 DEG C, according to every 1kg using the shell-lime of kelp and sea shells class biology as raw material
Culture medium in containing sodium bicarbonate 150~300g sodium bicarbonate is added, stir evenly, it is cold after sodium bicarbonate is completely dissolved
But, it filters, the shell-lime for being able to kelp and sea shells class biology is the culture medium of raw material；
B3. sandworm is inoculated in using the shell-lime of kelp and sea shells class biology as in the culture medium of raw material, culture 40~
72h, you can obtain sandworm culture rare-earth precipitation liquid.
The present invention still further provides the preferred preparation method of the special precipitating reagent of ionic minerals separation factory, including following
Step：
S1. potassium sodium mine is crushed, the potassium sodium mine after crushing is uniformly mixed with roasting auxiliary agent then, is roasted, until potassium sodium mine Cheng Peng
Loose powder shape, obtains mixture C；
S2. the mixture C is cooled to 30~70 DEG C, sodium bicarbonate is added and is uniformly mixed, after complete cooling, obtains mixture
D；
S3. the mixture D crushes, and sieving obtains powder precipitation agent；
S4. powder precipitation agent and water are according to weight ratio 1~8:15~40 mixing, add sandworm culture rare-earth precipitation liquid, mix
It closes uniformly, obtains mixed solution；
S5. the mixed solution is filtered, stands, obtains the special precipitating reagent of ionic minerals separation factory.
Preferably, in the step S1, potassium sodium miberal powder is broken to 100~300 mesh, and the temperature of roasting is 1200~1350 DEG C.
The raw material of the special precipitating reagent of above-described ionic minerals separation factory, making is mainly taken from the potassium sodium of nature
Mine, natural biology sandworm, discarded fruit shell/cellulose series biomass, raw material sources are abundant and of low cost, and sandworm passes through
The sandworm culture that culture obtains can interrupt the connection relation of rare earth ion and anions, in conjunction with potassium sodium mine and bicarbonate
Na in sodium+, mixed with Rare Earth Separation factory single rare earth solution, the rare earth ion of ion phase cemented out and to form carbonic acid dilute
Earth compounds precipitate, and obtain single rare-earth precipitation object.The experiment proved that ionic minerals separation using the present invention factory
After special precipitating reagent centering, heavy rare-earth solution are precipitated, the rate of deposition of rare earth it is high can reach 99.98%, it is seen then that this hair
The bright earth solution to ion type rareearth ore precipitates, and has the advantages that rate of deposition is high, concentration effect is good, can effectively improve money
Source utilization rate.Importantly, not introducing NH in entire precipitation process4 +Ion, supernatant ammonia nitrogen, total nitrogen after precipitation, COD are equal
Far below discharge index threshold value, in addition to total lead content, heavy metal and other indexs also substantially all discharge index reference value with
It is interior, the brought mother liquor ammonia nitrogen of the ammonium hydrogen carbonate raw material used in traditional handicraft, the excessively high problem of environmental pollution of total nitrogen are avoided, from
The problem of environmental pollution that precipitating rare earth element may be brought is avoided on source, is truly realized green extraction ion type rareearth, is
The environmental protection exploitation of Rare Earth Mine provides effective solution scheme.
The present invention takes natural potassium sodium mine, natural biology sandworm, discarded fruit shell/cellulose series biomass as former
Material, and the culture medium of sandworm is based on the shell-lime of common kelp and sea shells class biology, is all naturally without chemical industry dirt
The raw material of dye, and NH will not be introduced during precipitating rare earth4 +Ion, the supernatant indices after precipitation meet discharge and refer to
Mark requires, and can substantially reduce and additionally inject capital into terms of handling ammonia nitrogen, in addition, these raw materials are in nature generally existing, very
It is simple and easy to get to being agriculture and forestry organic waste material, cost of material can be substantially reduced, further, the present invention also added tea bran and pine
Dried fruit fruit is set, tea bran is the residue after tea seed oil expression, is the recycling of waste, pine tree dried fruit fruit raw material also derives from a wealth of sources, more has
Conducive to reducing cost of material and achieving the purpose that environmental protection and energy saving, to sum up, the cost of precipitating rare earth can be greatlyd save using the present invention
Input.
Apply the present invention in precipitating rare earth, ammonia nitrogen, total values of nitrogen might can be substantially reduced, solve precipitating rare earth to soil,
The serious pollution problem that water body environment is brought there is great reality to anticipate the maintenance of the Green Development, ecological environment of Rare Earth Mine
Justice.
Specific implementation mode
Below with reference to specific embodiment, the invention will be further described, but protection scope of the present invention be not limited to it is following
Embodiment.
The acquisition of sandworm：The present embodiment acquires sandworm from the water environment that can cause " sandworm foot ", for the present embodiment
Experiment.
Embodiment 1
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 100g, bicarbonate
Sodium 200g, sandworm culture rare-earth precipitation liquid 5g, hay (raw material for making plant ash) 10g.
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 60h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.With kelp and ocean
The shell-lime of shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：Kelp 60g, sea shells
The shell-lime 15g of class biology, water 6000g.
The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：A1. by kelp, sea shells class biology
Shell-lime and water mixing boil 5h, obtain mixture A；A2. object A to be mixed is cooled to 40 DEG C, and sodium bicarbonate, sodium bicarbonate is added
Weight ratio with liquid in mixture A is 5:2, it stirs evenly, cooling after sodium bicarbonate is completely dissolved, filtering is able to kelp
Shell-lime with sea shells class biology is that the culture medium of raw material (is with the shell-lime of kelp and sea shells class biology per 1kg
The culture medium of raw material is containing about sodium bicarbonate 285.7g)；A3. sandworm is inoculated in the shell-lime of kelp and sea shells class biology
In the culture medium of raw material, to keep 30 DEG C of culture 60h, you can obtain sandworm culture rare-earth precipitation liquid.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 100~150 mesh, then by after crushing potassium sodium mine and hay be uniformly mixed, keep 1200 DEG C of roastings, roasting time is
106h, until potassium sodium mine at Fluffy powdery, obtains mixture C；S2. the mixture C is cooled to 35 DEG C, it is mixed that sodium bicarbonate is added
It closes uniformly, after complete cooling, obtains mixture D；S3. mixture D crushes, and sieving obtains powder precipitation agent；S4. powder precipitation agent
With water according to weight ratio 1:5 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, obtain mixed solution；S5. it will mix
Solution filtering is closed, is stood, the special precipitating reagent of ion type mineral separation factory is obtained.
Embodiment 2
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 150g, bicarbonate
Sodium 250g, sandworm culture rare-earth precipitation liquid 10g, wrinkle fruit paulownia seeds of a tung oil tree shell 10g.
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 48h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.With kelp and ocean
The shell-lime of shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：Kelp 50g, sea shells
The shell-lime 10g of class biology, water 5000g.
The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：A1. by kelp, sea shells class biology
Shell-lime and water mixing boil 3h, obtain mixture A；A2. object A to be mixed is cooled to 30 DEG C, and sodium bicarbonate, sodium bicarbonate is added
Weight ratio with liquid in mixture A is 3:10, it stirs evenly, cooling after sodium bicarbonate is completely dissolved, filtering is able to sea
The shell-lime of band and sea shells class biology is the culture medium of raw material (per 1kg with the shell-lime of kelp and sea shells class biology
For raw material culture medium containing about sodium bicarbonate 230.8g)；A3. sandworm is inoculated in the shell of kelp and sea shells class biology
Ash is to keep 25 DEG C of culture 48h, you can obtain sandworm culture rare-earth precipitation liquid in the culture medium of raw material.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 150~200 mesh, then by after crushing potassium sodium mine and wrinkle fruit paulownia seeds of a tung oil tree shell be uniformly mixed, 1250 DEG C of roastings are kept, when roasting
Between be 96h, until potassium sodium mine is at Fluffy powdery, obtain mixture C；S2. mixture C is cooled to 30 DEG C, it is mixed that sodium bicarbonate is added
It closes uniformly, after complete cooling, obtains mixture D；S3. mixture D crushes, and sieving obtains powder precipitation agent；S4. powder precipitation agent
With water according to weight ratio 1:4 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, obtain mixed solution；S5. it will mix
Solution filtering is closed, is stood, the special precipitating reagent of ion type mineral separation factory is obtained.
Embodiment 3
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 250g, bicarbonate
Sodium 350g, sandworm culture rare-earth precipitation liquid 60g, tea seed episperm 100g.
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 65h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.With kelp and ocean
The shell-lime of shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：Kelp 30g, sea shells
The shell-lime 5g of class biology, water 4000g.
The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：A1. by kelp, sea shells class biology
Shell-lime and water mixing boil 2h, obtain mixture A；A2. object A to be mixed is cooled to 35 DEG C, and sodium bicarbonate, sodium bicarbonate is added
Weight ratio with liquid in mixture A is 1:3.5, it stirs evenly, cooling after sodium bicarbonate is completely dissolved, filtering is able to sea
The shell-lime of band and sea shells class biology is the culture medium of raw material (per 1kg with the shell-lime of kelp and sea shells class biology
For raw material culture medium containing about sodium bicarbonate 166.7g)；A3. sandworm is inoculated in the shell of kelp and sea shells class biology
Ash is to keep 20 DEG C of culture 65h, you can obtain sandworm culture rare-earth precipitation liquid in the culture medium of raw material.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 200~250 mesh, then by after crushing potassium sodium mine and tea seed episperm be uniformly mixed, keep 1300 DEG C of roastings, roasting time is
90h, until potassium sodium mine at Fluffy powdery, obtains mixture C；S2. mixture C is cooled to 30 DEG C, it is equal that sodium bicarbonate mixing is added
It is even, after complete cooling, obtain mixture D；S3. mixture D crushes, and sieving obtains powder precipitation agent；S4. powder precipitation agent and water
According to weight ratio 1:5 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, obtain mixed solution；S5. it will mix molten
Liquid filters, and stands, and obtains the special precipitating reagent of ion type mineral separation factory.
Embodiment 4
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 100g, bicarbonate
Sodium 200g, sandworm culture rare-earth precipitation liquid 8g, cotton seed hull 20g, tea bran 350g, pine tree dried fruit fruit 20g.
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 60h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.With kelp and ocean
The shell-lime of shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：Kelp 30g, sea shells
The shell-lime 20g of class biology, red ginseng 1g, Radix Codonopsis 5g, mushroom 10g, pig blood 1g, white sugar 1g, ganoderma lucidum 5g, water 4000g.
The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：B1. by kelp, sea shells class biology
Shell-lime, red ginseng, Radix Codonopsis, mushroom, chicken blood, white sugar, ganoderma lucidum and water mixing boil 3h, obtain mixture B；B2. object B to be mixed is cold
But to 30 DEG C, it is added sodium bicarbonate, the weight ratio of liquid is 1 in sodium bicarbonate and mixture A:4, it stirs evenly, waits for bicarbonate
It is cooling after sodium is completely dissolved, filtering, the shell-lime for being able to kelp and sea shells class biology be the culture medium of raw material (often 1kg with
The shell-lime of kelp and sea shells class biology is the culture medium of raw material containing about sodium bicarbonate 200g)；B3. by sandworm be inoculated in
The shell-lime of kelp and sea shells class biology is to keep 20 DEG C of culture 70h, you can obtain sandworm culture in the culture medium of raw material
Object rare-earth precipitation liquid.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 100~150 mesh, then potassium sodium mine, cotton seed hull, tea bran and the pine tree dried fruit fruit after crushing are uniformly mixed, kept for 1200 DEG C
Roasting, roasting time 105h, until potassium sodium mine at Fluffy powdery, obtains mixture C；S2. the mixture C is cooled to 35
DEG C, sodium bicarbonate is added and is uniformly mixed, after complete cooling, obtains mixture D；S3. mixture D crushes, and sieving obtains powder precipitation
Agent；S4. powder precipitation agent and water are according to weight ratio 1:5 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, obtain
Mixed solution；S5. mixed solution is filtered, is stood, obtain the special precipitating reagent of ion type mineral separation factory.
Embodiment 5
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 150g, bicarbonate
Sodium 250g, sandworm culture rare-earth precipitation liquid 10g, wrinkle fruit paulownia seeds of a tung oil tree shell 40g, tea bran 500g, pine tree dried fruit fruit 50g.
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 48h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.With kelp and ocean
The shell-lime of shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：Kelp 50g, sea shells
The shell-lime 10g of class biology, red ginseng 5g, Radix Codonopsis 10g, mushroom 20g, chicken blood 5g, white sugar 5g, ganoderma lucidum 10g, water 5000g.
The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：B1. by kelp, sea shells class biology
Shell-lime, red ginseng, Radix Codonopsis, mushroom, chicken blood, white sugar, ganoderma lucidum and water mixing boil 2.5h, obtain mixture B；B2. object B to be mixed
It is cooled to 30 DEG C, is added sodium bicarbonate, the weight ratio of sodium bicarbonate and liquid in mixture A is 10:3, it stirs evenly, waits for carbonic acid
Cooling after hydrogen sodium is completely dissolved, filtering is able to the shell-lime of kelp and sea shells class biology as culture medium (every 1kg of raw material
Shell-lime using kelp and sea shells class biology is the culture medium of raw material containing about sodium bicarbonate 230.8g)；B3. sandworm is inoculated with
In using the shell-lime of kelp and sea shells class biology in the culture medium of raw material, to keep 25 DEG C of culture 48h, you can obtain sandworm
Culture rare-earth precipitation liquid.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 200~250 mesh, the potassium sodium mine after crushing is uniformly mixed with wrinkle fruit paulownia seeds of a tung oil tree shell, tea bran, pine tree dried fruit fruit then, is kept
1250 DEG C of roastings, roasting time 95h, until potassium sodium mine at Fluffy powdery, obtains mixture C；S2. mixture C is cooled to 30 DEG C,
Sodium bicarbonate is added to be uniformly mixed, after complete cooling, obtains mixture D；S3. mixture D crushes, and sieving obtains powder precipitation agent；
S4. powder precipitation agent and water are according to weight ratio 1:4 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, must mix
Solution；S5. mixed solution is filtered, is stood, obtain the special precipitating reagent of ion type mineral separation factory.
Embodiment 6
A kind of special precipitating reagent of ion type mineral separation factory, includes the component of following parts by weight：Potassium sodium mine 250g, bicarbonate
Sodium 350g, sandworm culture rare-earth precipitation liquid 60g, hay (raw material for making plant ash) 100g, tea bran 600g, pine tree dried fruit fruit
100g。
The preparation method of sandworm culture rare-earth precipitation liquid is：Sandworm is seeded to kelp and sea shells classes biology
Shell-lime cultivates 46h to be cultivated on the culture medium of raw material, you can obtains sandworm culture rare-earth precipitation liquid.
Mainly by the raw material of following parts by weight in using the shell-lime of kelp and sea shells class biology as the culture medium of raw material
It is made：Kelp 60g, the shell-lime 15g of sea shells class biology, red ginseng 10g, Radix Codonopsis 20g, mushroom 30g, ox blood 9g, white sugar
10g, ganoderma lucidum 20g, water 6000g.The preparation method of sandworm culture rare-earth precipitation liquid, includes the following steps：B1. by kelp, sea
5h is boiled in shell-lime, red ginseng, Radix Codonopsis, mushroom, ox blood, white sugar, ganoderma lucidum and the water mixing of foreign shell biology, obtains mixture B；
B2. object B to be mixed is cooled to 40 DEG C, is added sodium bicarbonate, and the weight ratio of sodium bicarbonate and liquid in mixture A is 1:5, stirring
Uniformly, cooling after sodium bicarbonate is completely dissolved, filtering, the shell-lime for being able to kelp and sea shells class biology is raw material
Culture medium (per 1kg using the shell-lime of kelp and sea shells class biology be the culture medium of raw material containing about sodium bicarbonate 166.7g)；
B3. sandworm is inoculated in using the shell-lime of kelp and sea shells class biology in the culture medium of raw material, to keep 30 DEG C of cultures
46h, you can obtain sandworm culture rare-earth precipitation liquid.
Ion type mineral detach the preparation method of the special precipitating reagent of factory, include the following steps：S1. potassium sodium miberal powder is broken
To 250~300 mesh, then by after crushing potassium sodium mine and hay, tea bran, pine tree dried fruit fruit be uniformly mixed, keep 1350 DEG C roasting
It burns, roasting time 85h, until potassium sodium mine at Fluffy powdery, obtains mixture C；S2. mixture C is cooled to 60 DEG C, carbonic acid is added
Hydrogen sodium is uniformly mixed, and after complete cooling, obtains mixture D；S3. mixture D crushes, and sieving obtains powder precipitation agent；S4. powder
Precipitating reagent and water are according to weight ratio 1:3 mixing, add sandworm culture rare-earth precipitation liquid, are uniformly mixed, obtain mixed solution；
S5. mixed solution is filtered, is stood, obtain the special precipitating reagent of ion type mineral separation factory.
The special precipitating reagent of ion type mineral separation factory made from Examples 1 to 6 is used for single rare earth (middle weight below
Rare earth) feed liquid precipitation separation, to verify the sedimentation effect of precipitated liquid of the present invention to various single light rare earth feed liquids, and precipitate
The environmental protection index of supernatant situation up to standard afterwards.
One, test raw material and equipment
1, the special precipitating reagent of ion type mineral separation factory made from Examples 1 to 6.
2, the gadolinium (Gd), terbium (Tb), dysprosium (Dy), samarium (Sm), europium (Eu), yttrium (Y), holmium (Ho), erbium (Er) of Rare Earth Separation factory,
Thulium (Tm), ytterbium (Yb), lutetium (Lu) feed liquid.
3, testing equipment：5L measuring cups, 1000mL graduated cylinders, use for laboratory pony mixer, pH meter etc..
Two, content of the test
1, basic data measures
Rare Earth Separation factory Gd, Y feed liquid is sent to Guangxi metallurgy institute respectively and measures rare earth concentration, testing result such as the following table 1 (compile by report
Number：H1706136)：
1 Gd, Y feed liquid rare earth concentration of table
| Y feed concentrations | 215.32g/L | Gd feed concentrations | 223.72g/L |
The rare earth concentration in Rare Earth Separation factory Tb, Dy, Sm, Eu, Ho, Er, Tm, Yb, Lu feed liquid, testing result are voluntarily detected respectively
Such as the following table 2：
2 Tb, Dy, Sm, Eu, Ho, Er, Tm, Yb, Lu feed liquid rare earth concentration of table
| Tb feed liquid rare earth concentrations | 187.02g/L | Dy feed liquid rare earth concentrations | 191.33g/L |
| Sm feed liquid rare earth concentrations | 196.73g/L | Eu feed liquid rare earth concentrations | 167.15g/L |
| Ho feed liquid rare earth concentrations | 173.67g/L | Er feed liquid rare earth concentrations | 202.51g/L |
| Tm feed liquid rare earth concentrations | 152.39g/L | Yb feed liquid rare earth concentrations | 162.37g/L |
| Lu feed liquid rare earth concentrations | 179.15g/L |
2, the ion type mineral separation special precipitating reagent of factory is heavy for Gd, Tb, Dy, Sm, Eu, Y, Ho, Er, Tm, Yb, Lu feed liquid
It forms sediment and detaches exploratory experiment method；
(1) one is tested：
1. taking certain Rare Earth Separation factory Gd feed liquid v1=308mL, rare earth concentration 223.72g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Gd feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1760mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 2 minutes, stands
It filters, the supernatant of filtering gained is installed, rare earth concentration and environmental protection index to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Gd compounds,
Product quality to be detected.
(2) two are tested：
1. taking the Y feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 215.32g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Y feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=2210mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 2 minutes, stands
It filters, the supernatant of filtering gained is installed, rare earth concentration and environmental protection index to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Y compounds, wait for
Detect product quality.
(3) three are tested：
1. taking the Tb feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 187.02g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Tb feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1590mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Tb compounds.
(4) four are tested：
1. taking the Dy feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 191.33g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Dy feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1610mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Dy compounds.
(5) five are tested：
1. taking the Sm feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 196.73g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Sm feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1680mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Sm compounds.
(6) six are tested：
1. taking the Eu feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 196.73g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Eu feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1450mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Eu compounds.
(7) seven are tested：
1. taking the Ho feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 173.67g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Ho feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1700mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Ho compounds.
(8) eight are tested：
1. taking the Er feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 202.51g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Er feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=2120mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Er compounds.
(9) nine are tested：
1. taking the Tm feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 152.39g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Tm feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1750mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Tm compounds.
(10) ten are tested：
1. taking the Yb feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 162.37g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Yb feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1840mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Yb compounds.
(11) 11 are tested：
1. taking the Lu feed liquids v of certain Rare Earth Separation factory1=300mL, rare earth concentration 152.39g/L are placed in the measuring cup of 5L；
2. being slowly added in dress Lu feed liquid measuring cups with the special precipitating reagent of ion type mineral separation factory under room temperature, precipitation is added in side
Agent side is stirred, and stops that precipitating reagent is added when pH value in reaction kettle is up to 6.25~6.5, and it is special to write down ion type mineral separation factory
With precipitating reagent dosage v2=1950mL is stirred 2 minutes, is stood and is added v after ten minutes3=1500mL pure water stirs 3 minutes, stands
It filters, the supernatant of filtering gained is installed to be detected after 1 to 2 hour.
3. filtering gained sediment is placed in measuring cup and pure water washing is added 3 times, filtering, drying obtain Lu compounds.
3, process and result are tested
(1) computational methods
Ion type mineral detach the special precipitating reagent rare-earth precipitation rate calculating formula of factory：
In formula：η rare-earth precipitation rates；M is mass M=ρ of feed liquid middle rare earth1*V1, ρ1For feed liquid rare earth concentration, V1For feed liquid body
Product；M is the quality m=ρ of supernatant middle rare earth2*(V1+V2+v3), ρ2For supernatant rare earth concentration, V2For the body of precipitating reagent is added
Product, v3For the amount of pure water is added.
(2) process and result of Gd compounds are precipitated：
The special precipitating reagent of factory is detached to Gd feed liquids according to the ion type mineral of the method testing example 1~6 of experiment one
Precipitate separating effect.Test result is shown in Table 3：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 3 Examples 1 to 6 of table to Gd feed liquids
Take the supernatant of the embodiment 5 of precipitation good separating effect that Guangxi metallurgy institute is sent to detect rare earth concentration, testing result is shown in Table 4
(report number：H1706136,H1801002)：
4 embodiment 5 of table precipitates the testing result of Gd feed liquids
Testing result and the result voluntarily detected are very close.
The supernatant of the embodiment 5 of precipitation good separating effect is taken to send the detection of Guangxi Lv Bao environmental monitorings Co., Ltd environmentally friendly number
According to testing result is shown in Table 5 (report numbers：Green guarantor's ring prison Zi [2017 Nian ]No. 05-34)：
Supernatant environment protection digital testing result after 5 embodiment of table, 5 precipitating rare earth Gd
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Gd feed liquids similarly can effectively control ammonia and nitrogen pollution, reduce COD contents.
Drying is obtained Gd compounds to send to national tungsten and rare-earth products Quality Supervision and Inspection Center detection product quality, inspection
It is (report number state examines XT words (2017) 07492) to survey result：Total amount (REO) is 96.84% after Gd rare earth compounds are burnt.
(3) process and result of Y compounds are precipitated：
It sinks to Y feed liquids according to the special precipitating reagent of ion type mineral separation factory of the method testing example 1~6 of experiment two
Shallow lake separating effect.Test result is shown in Table 6：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 6 embodiment 2 and 5 of table to Y feed liquids
Take the supernatant of the embodiment 5 of precipitation good separating effect that Guangxi metallurgy institute is sent to detect rare earth concentration, testing result is shown in Table 7
(report number：H1706136)：
7 embodiment 5 of table precipitates the testing result of Y feed liquids
Testing result is identical as the result voluntarily detected.
The supernatant of Example 5 send Guangxi Lv Bao environmental monitorings Co., Ltd to detect environment protection digital, and testing result is shown in Table 8
(report number：Green guarantor's ring prison Zi [2017 Nian ]No. 05-34)：
Supernatant environment protection digital testing result after 8 embodiment of table, 5 precipitating rare earth Y
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Y feed liquids similarly can effectively avoid ammonia and nitrogen pollution.
Drying is obtained Y compounds to send to Jiangxi Province's tungsten and rare-earth products Quality Supervision and Inspection Center detection product quality,
Testing result is (report number state examines XT words (2017) 04965)：Total amount (REO) is 99.18% after Y rare earth compounds are burnt, pure
Degree is 99.998%.
(4) process and result of Tb compounds are precipitated：
Since Tb is similar to Gd chemical property, the experiment of Tb feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral separation factory special precipitating reagent, test it according to the method for experiment three and effect detached to the precipitation of Tb feed liquids
Fruit.Test result is shown in Table 9：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 9 embodiment 2 and 5 of table to Tb feed liquids
The supernatant of Example 2 voluntarily detects environment protection digital, and testing result is shown in Table 10：
Supernatant environment protection digital testing result after 10 embodiment of table, 2 precipitating rare earth Tb
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Tb feed liquids similarly can effectively avoid ammonia and nitrogen pollution.
(5) process and result of Dy compounds are precipitated：
Since Dy is similar to Gd chemical property, the experiment of Dy feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral separation factory special precipitating reagent, test it according to the method for experiment four and effect detached to the precipitation of Dy feed liquids
Fruit.Test result is shown in Table 9：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 9 embodiment 2 and 5 of table to Dy feed liquids
The supernatant of Example 2 voluntarily detects environment protection digital, and testing result is shown in Table 10：
Supernatant environment protection digital testing result after 10 embodiment of table, 2 precipitating rare earth Dy
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Dy feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(6) process and result of Sm compounds are precipitated：
Since Sm is similar to Gd chemical property, the experiment of Sm feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral separation factory special precipitating reagent, test it according to the method for experiment five and effect detached to the precipitation of Sm feed liquids
Fruit.Test result is shown in Table 11：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 11 embodiment 2 and 5 of table to Sm feed liquids
The supernatant of Example 2 voluntarily detects environment protection digital, and testing result is shown in Table 12：
Supernatant environment protection digital testing result after 12 embodiment of table, 2 precipitating rare earth Sm
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Sm feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(7) process and result of Eu compounds are precipitated：
Since Eu is similar to Gd chemical property, the experiment of Eu feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral separation factory special precipitating reagent, test it according to the method for experiment six and effect detached to the precipitation of Eu feed liquids
Fruit.Test result is shown in Table 13：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 13 embodiment 2 and 5 of table to Eu feed liquids
The supernatant of Example 2 voluntarily detects environment protection digital, and testing result is shown in Table 14：
Supernatant environment protection digital testing result after 14 embodiment of table, 2 precipitating rare earth Eu
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Eu feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(8) process and result of Ho compounds are precipitated：
Since Ho is similar to Y chemical property, the experiments of Ho feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral detach the special precipitating reagent of factory, its precipitation separating effect to Ho feed liquids is tested according to the method for experiment seven.
Test result is shown in Table 15：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 15 embodiment 2 and 5 of table to Ho feed liquids
The supernatant of Example 2 voluntarily detects environment protection digital, and testing result is shown in Table 16：
Supernatant environment protection digital testing result after 16 embodiment of table, 2 precipitating rare earth Ho
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Ho feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(9) process and result of Er compounds are precipitated：
Since Er is similar to Y chemical property, the experiments of Er feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral detach the special precipitating reagent of factory, its precipitation separating effect to Er feed liquids is tested according to the method for experiment eight.
Test result is shown in Table 17：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 17 embodiment 2 and 5 of table to Er feed liquids
The supernatant of Example 5 voluntarily detects environment protection digital, and testing result is shown in Table 18：
Supernatant environment protection digital testing result after 18 embodiment of table, 5 precipitating rare earth Er
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Er feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(10) process and result of Tm compounds are precipitated：
Since Tm is similar to Y chemical property, the experiments of Tm feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral detach the special precipitating reagent of factory, its precipitation separating effect to Tm feed liquids is tested according to the method for experiment nine.
Test result is shown in Table 19：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 19 embodiment 2 and 5 of table to Tm feed liquids
The supernatant of Example 5 voluntarily detects environment protection digital, and testing result is shown in Table 20：
Supernatant environment protection digital testing result after 20 embodiment of table, 5 precipitating rare earth Tm
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Tm feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(11) process and result of Yb compounds are precipitated：
Since Yb is similar to Y chemical property, the experiments of Yb feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral detach the special precipitating reagent of factory, its precipitation separating effect to Yb feed liquids is tested according to the method for experiment ten.
Test result is shown in Table 21：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 21 embodiment 2 and 5 of table to Yb feed liquids
The supernatant of Example 5 voluntarily detects environment protection digital, and testing result is shown in Table 22：
Supernatant environment protection digital testing result after 22 embodiment of table, 5 precipitating rare earth Yb
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Yb feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
(12) process and result of Lu compounds are precipitated：
Since Lu is similar to Y chemical property, the experiments of Lu feed liquids takes the preferable embodiment 2 of sedimentation effect and embodiment 5
Ion type mineral detach the special precipitating reagent of factory, and test it according to the method for experiment 11 detaches effect to the precipitation of Lu feed liquids
Fruit.Test result is shown in Table 23：
Precipitation separating effect of the ion type mineral separation special precipitating reagent of factory of 23 embodiment 2 and 5 of table to Lu feed liquids
The supernatant of Example 5 voluntarily detects environment protection digital, and testing result is shown in Table 24：
Supernatant environment protection digital testing result after 24 embodiment of table, 5 precipitating rare earth Lu
NH is not introduced by the special precipitating reagent of ion type mineral separation factory in this present embodiment4 +, raw material is prepared from source
Ammonia and nitrogen pollution is controlled, the special precipitating reagent of ion type mineral separation factory in other embodiment group and the scope of the invention is used for
Precipitation Lu feed liquids can similarly effectively prevent ammonia and nitrogen pollution.
Above is referred in the table of environment protection digital, ND expressions are not detected.Rare-earth industry pollutant emission standard is GB26451-
2011。
Three, test result analysis and discussion
By experiment one~11 show ion type mineral separation factory special precipitating reagent precipitating rare earth separation factory Gd, Tb, Dy,
Sm, Eu, Y, Ho, Er, Tm, Yb, Lu feed liquid rate of deposition are high, and concentration effect is good, can effectively improve resource recovery.
The ion type mineral separation factory special precipitating reagent of the present embodiment for precipitating rare earth separation factory Gd, Tb, Dy,
The technique of Sm, Eu, Y, Ho, Er, Tm, Yb, Lu feed liquid has compared with the depositing technologies such as ammonium bicarbonate used in traditional handicraft
The advantages such as process conditions are simple, easy to operate, low energy consumption.
The each environmental protection index data of supernatant shown from above-mentioned table, which can be seen that, is below rare-earth industry pollutant row
Standard (GB26451-2011) is put, the only total lead content of part supernatant is slightly higher, this is mostly derived from ionic mineral itself and contains
More lead causes rare earth feed liquid lead content itself also higher.Generally speaking, the present invention can efficiently solve rare earth for a long time
Detach factory's relief liquor total nitrogen, the excessively high serious problem of environmental pollution of ammonia nitrogen.
It is learnt by state's inspection XT words (2017) 04965,07492 survey report analysis result：Ion type mineral rare earth point
From obtained by special precipitating reagent precipitating rare earth separation factory of factory Gd feed liquids, Gd compounds are by TREO after calcination (after burning) 96.84%, slightly
Low, the impurity content that reason comes from Gd feed liquids is high, and especially Al ion concentrations reach 14.171g/L (report numbers：
H1706136)；Y compounds are by TREO after calcination (after burning) 99.18%, product hierarchy 4N, and product quality is excellent.
In summary：The special precipitating reagent of ion type mineral separation factory is that a kind of rate of deposition is high, concentration effect is good, technique
A kind of environmentally friendly rare-earth precipitation agent of many merits such as condition is simple, easy to operate, low energy consumption, natural environmental-protective.
Claims (10)
1. a kind of special precipitating reagent of ionic minerals separation factory, which is characterized in that include the component of following parts by weight：Potassium sodium mine 10
~ 25 parts, 20 ~ 35 parts of sodium bicarbonate, 0.2 ~ 6 part of sandworm culture rare-earth precipitation liquid roasts 1 ~ 10 part of auxiliary agent, the roasting auxiliary agent
For the grey pH> after burning;9.5 fruit shell or cellulose series biomass；
The sandworm culture rare-earth precipitation liquid is that sandworm is seeded to the shell-lime of kelp and sea shells class biology is former
Culture obtains on the culture medium of material.
2. the special precipitating reagent of ionic minerals separation according to claim 1 factory, which is characterized in that further include following weight
The roasting auxiliary agent of part：35 ~ 60 parts of tea bran, 2 ~ 10 parts of pine tree dried fruit fruit.
3. the special precipitating reagent of ionic minerals separation according to claim 1 factory, which is characterized in that including following parts by weight
Component：15 parts of potassium sodium mine, 25 parts of sodium bicarbonate, 1 part of sandworm culture rare-earth precipitation liquid, the grey pH> after burning;9.5 fruit
4 parts of shell or cellulose series biomass.
4. the special precipitating reagent of ionic minerals separation according to claim 1 factory, which is characterized in that the grey pH> after burning;
9.5 fruit shell is one or more of wrinkle fruit paulownia seeds of a tung oil tree shell, tea seed episperm, cotton seed hull, wheat husk and rice husk, after burning
Grey pH>9.5 cellulose series biomass is one or more in stalk, straw, hay and corncob.
5. the special precipitating reagent of ionic minerals separation according to claim 1 factory, which is characterized in that described with kelp and sea
The shell-lime of foreign shell biology in the culture medium of raw material of the raw material of following parts by weight by being mainly made：300 ~ 600 parts of kelp,
50 ~ 150 parts of the shell-lime of sea shells class biology, 40000 ~ 60000 parts of water；And per 1kg with kelp and sea shells class biology
Shell-lime be raw material culture medium in, contain 150 ~ 300g of sodium bicarbonate.
6. the special precipitating reagent of ionic minerals separation according to claim 5 factory, which is characterized in that described with kelp and sea
The shell-lime of foreign shell biology is that the raw material of the culture medium of raw material further includes the component of following parts by weight：10 ~ 100 parts of red ginseng,
50 ~ 200 parts of Radix Codonopsis, 100 ~ 300 parts of mushroom, 10 ~ 90 parts of livestock blood, 10 ~ 100 parts of white sugar, 50 ~ 200 parts of ganoderma lucidum.
7. the special precipitating reagent of ionic minerals separation according to claim 5 factory, which is characterized in that described with kelp and sea
The shell-lime of foreign shell biology is that the preparation method of the culture medium of raw material includes the following steps：A1. it weighs by weight following
Raw material：300 ~ 600 parts of kelp, sea shells class biology 40000 ~ 60000 parts of 50 ~ 150 parts of shell-lime, water, mixing boils 1 ~
5h obtains mixture A；
A2. object A to be mixed is cooled to 25 ~ 50 DEG C, according to every 1kg using the shell-lime of kelp and sea shells class biology as raw material
Sodium bicarbonate is added containing 150 ~ 300g of sodium bicarbonate in culture medium, stirs evenly, it is cooling after sodium bicarbonate is completely dissolved,
Filtering, the shell-lime for being able to kelp and sea shells class biology are the culture medium of raw material；
A3. sandworm is inoculated in using the shell-lime of kelp and sea shells class biology in the culture medium of raw material, to cultivate 40 ~ 72h,
It can be obtained sandworm culture rare-earth precipitation liquid.
8. the special precipitating reagent of ionic minerals separation according to claim 6 factory, which is characterized in that described with kelp and sea
The shell-lime of foreign shell biology is that the preparation method of the culture medium of raw material includes the following steps：B1. it weighs by weight following
Raw material：300 ~ 600 parts of kelp, 40000 ~ 60000 parts of 50 ~ 150 parts of shell-lime, water, the red ginseng 10 ~ 100 of sea shells class biology
Part, 50 ~ 200 parts of Radix Codonopsis, 100 ~ 300 parts of mushroom, 10 ~ 90 parts of livestock blood, 10 ~ 100 parts of white sugar, 50 ~ 200 parts of ganoderma lucidum, then
Above-mentioned raw materials are mixed and boil 1 ~ 5h, obtain mixture B；
B2. object B to be mixed is cooled to 25 ~ 50 DEG C, according to every 1kg using the shell-lime of kelp and sea shells class biology as raw material
Sodium bicarbonate is added containing 150 ~ 300g of sodium bicarbonate in culture medium, stirs evenly, it is cooling after sodium bicarbonate is completely dissolved,
Filtering, the shell-lime for being able to kelp and sea shells class biology are the culture medium of raw material；
B3. sandworm is inoculated in using the shell-lime of kelp and sea shells class biology in the culture medium of raw material, to cultivate 40 ~ 72h,
It can be obtained sandworm culture rare-earth precipitation liquid.
9. such as the preparation method of the special precipitating reagent of claim 1 ~ 8 any one of them ionic minerals separation factory, feature exists
In including the following steps：
S1. potassium sodium mine is crushed, the potassium sodium mine after crushing is uniformly mixed with roasting auxiliary agent then, is roasted, until potassium sodium mine Cheng Peng
Loose powder shape, obtains mixture C；
S2. the mixture C is cooled to 30 ~ 70 DEG C, sodium bicarbonate is added and is uniformly mixed, after complete cooling, obtains mixture
D；
S3. the mixture D crushes, and sieving obtains powder precipitation agent；
S4. powder precipitation agent and water are according to weight ratio 1 ~ 8:15 ~ 40 mixing, add sandworm culture rare-earth precipitation liquid, mix
Uniformly, mixed solution is obtained；
S5. the mixed solution is filtered, stands, obtains the special precipitating reagent of ionic minerals separation factory.
10. the special precipitating reagent of ionic minerals separation as claimed in claim 9 factory, which is characterized in that
In the step S1, potassium sodium miberal powder is broken to 100 ~ 300 mesh, and the temperature of roasting is 1200 ~ 1350 DEG C.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152693A (en) * | 2014-07-16 | 2014-11-19 | 江西理工大学 | Method for precipitating rare earth from ionic rare earth ore magnesium sulfate leaching solution |
| CN105861831A (en) * | 2015-01-23 | 2016-08-17 | 有研稀土新材料股份有限公司 | Method for precipitation recycling of rare earth from rare earth salt solution |
| CN106399689A (en) * | 2016-11-21 | 2017-02-15 | 包头稀土研究院 | Method for preparing mixed rare earth oxides by herbaceous plant precipitating agent |
| CN106636683A (en) * | 2016-10-14 | 2017-05-10 | 赣州弘茂稀土工程有限公司 | Rare earth in-situ leaching and enriching process for ionic rare earth ore |
| CN106967892A (en) * | 2017-05-12 | 2017-07-21 | 中国科学院合肥物质科学研究院 | A kind of precipitating reagent and its preparation and application for precipitating ion absorbent-type Rare Earth Mine leachate Rare Earth Ion |
| CN107217139A (en) * | 2017-05-31 | 2017-09-29 | 赣州稀土开采技术服务有限公司 | Southern ion type rareearth ore is without ammonia production practice |
| CN107686332A (en) * | 2017-09-18 | 2018-02-13 | 广东博华陶瓷有限公司 | A kind of production technology of environmental protection Ceramic Tiles modelled after an antique |
-
2018
- 2018-07-01 CN CN201810703535.3A patent/CN108707749A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104152693A (en) * | 2014-07-16 | 2014-11-19 | 江西理工大学 | Method for precipitating rare earth from ionic rare earth ore magnesium sulfate leaching solution |
| CN105861831A (en) * | 2015-01-23 | 2016-08-17 | 有研稀土新材料股份有限公司 | Method for precipitation recycling of rare earth from rare earth salt solution |
| CN106636683A (en) * | 2016-10-14 | 2017-05-10 | 赣州弘茂稀土工程有限公司 | Rare earth in-situ leaching and enriching process for ionic rare earth ore |
| CN106399689A (en) * | 2016-11-21 | 2017-02-15 | 包头稀土研究院 | Method for preparing mixed rare earth oxides by herbaceous plant precipitating agent |
| CN106967892A (en) * | 2017-05-12 | 2017-07-21 | 中国科学院合肥物质科学研究院 | A kind of precipitating reagent and its preparation and application for precipitating ion absorbent-type Rare Earth Mine leachate Rare Earth Ion |
| CN107217139A (en) * | 2017-05-31 | 2017-09-29 | 赣州稀土开采技术服务有限公司 | Southern ion type rareearth ore is without ammonia production practice |
| CN107686332A (en) * | 2017-09-18 | 2018-02-13 | 广东博华陶瓷有限公司 | A kind of production technology of environmental protection Ceramic Tiles modelled after an antique |
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