CN105734296A - Comprehensive utilization method of neodymium iron boron waste acid leaching slag - Google Patents
Comprehensive utilization method of neodymium iron boron waste acid leaching slag Download PDFInfo
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- CN105734296A CN105734296A CN201610246932.3A CN201610246932A CN105734296A CN 105734296 A CN105734296 A CN 105734296A CN 201610246932 A CN201610246932 A CN 201610246932A CN 105734296 A CN105734296 A CN 105734296A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/22—Compounds of iron
- C09C1/24—Oxides of iron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a comprehensive utilization method of neodymium iron boron waste acid leaching slag. The neodymium iron boron waste acid leaching slag is mixed with neodymium iron boron waste acid leaching slag acid leaching liquid, prepared by acid leaching and separation procedures, in a neutralization reactor; neutralized slurry is filtered to recover neutralized liquid and neutralized residues; the neutralized liquid serves as a raw material for preparing iron oxide red; the neutralized residues and acid leaching residue eluating liquid, obtained in the acid leaching procedure, are mixed and added in sulfuric acid for acid leaching reaction and filtration to obtain acid leaching liquid and acid leaching residues; the acid leaching liquid is used for neutralizing ingredients; the acid leaching residues and latter eluating liquid, prepared in the oxide iron red preparation procedure, are mixed to prepare pulp; rare earth sulfate in the acid leaching residues is dissolved out by filtering and washing; and filter eluating liquid, prepared after preparation, is sent to a rare earth extracting procedure for preparing a rare earth product. The comprehensive utilization method realizes comprehensive utilization of iron, micro rare earth and cobalt resources in the neodymium iron boron waste acid leaching slag, and realizes effective separation and enrichment of the rare earth and the cobalt elements.
Description
Technical field
The invention belongs to industrial solid castoff technical field of comprehensive utilization, be specifically related to the method for comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue.
Background technology
Neodymium iron boron waste material acid leaching residue is that neodymium iron boron waste material carries and adopts acid-soaked waste residue produced by excellent molten method production breakdown neodymium iron boron waste material in neodymium process, and its Main Ingredients and Appearance is Fe2O3, REO, Co etc..Currently without suitable method of comprehensive utilization, some enterprises or it can be used as iron-smelting raw material to sell, or done and store up process, not only occupied ground, and contaminated environment.
Summary of the invention
In order to comprehensively utilize the valuable resource in neodymium iron boron waste material acid leaching residue, eliminating environmental pollution, the present invention proposes the method for comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue.Achieve the comprehensive utilization of ferrum, trace rare-earth and cobalt resource in neodymium iron boron waste material acid leaching residue, prepare the iron oxide red commercial pigments of satisfactory quality and achieved efficiently separating and being enriched with its middle rare earth and cobalt element, comprehensively utilize for rare earth and the further of cobalt element, prepare rare earth oxide and cobalt compound is laid a good foundation.
For achieving the above object, the technical solution used in the present invention is:
The method of comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue, it is characterised in that sequentially include the following steps: leaching and the separation of ferrum, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue:
Step one: neodymium iron boron waste material acid leaching residue is mixed with from the neodymium iron boron waste material acid leaching residue acid leaching liquor obtained by acidleach, separation circuit in neutralization reactor, controlling neutral temperature is 70 DEG C-100 DEG C, the neutralization response time is 180-360min, reaction end pH value is 0.5, making the free acid in acid leaching liquor be consumed, ferrum in neodymium iron boron waste material acid leaching residue, rare earth and cobalt element obtain preliminary dissolution；
Step 2: the slip in neutralization reactor is filtered under 70 DEG C of-100 DEG C of conditions and receives to obtain neutralizer and neutralization residue, the Main Ingredients and Appearance of neutralizer is the sulfate of ferrum and cobalt, it is used as the raw material of preparation iron oxide red, neutralizes the cobalt that residue Main Ingredients and Appearance is silicon dioxide, ferrum oxide, rare earth oxide, rare earth sulfate and trace；
Step 3: send acidleach operation by neutralization residue, with the later stage eluate of iron oxide red preparation section institute output by solid-to-liquid ratio 1:1.5-1:2.5 mixing in acid-leaching reaction device, then add concentrated sulphuric acid by 1.5-1.9 times of theoretical amount under 70 DEG C of-100 DEG C of conditions, carry out acid-leaching reaction, the control acid-leaching reaction time is 180-360min, making the further dissolution of ferrum therein, rare earth and cobalt, reaction terminates to receive to obtain the acid leaching liquor of the sulfate that Main Ingredients and Appearance is ferrum and cobalt and acidleach residue through filtering；
Step 4: step one, course of reaction described in three is strong acid hot environment, rare earth sulfuric acid salt solubility is relatively low with this understanding, major part is composed with the form of soluble-salt and is stored in residue, step 2 gained will mix under normal temperature condition with the later stage eluate of iron oxide red preparation section institute output and makes pulping through step 3 acidleach gained acidleach residue in plasm scouring groove again with residue, the rare earth sulfate in acidleach residue is made to dissolve and enter liquid phase, it is then passed through filter, washing prepares eluate and the acidleach residue that Main Ingredients and Appearance is rare earth sulfate, eluate middle rare earth content is between 1-3g/L, send Extraction of rare eart operation for preparing rare-earth products；
The preparation of iron oxide red:
Step (1): step 2 gained neutralizer is returned former operation, with iron filings, iron sheet or reduced iron powder for reducing agent, carries out reduction reaction under 50 DEG C of-80 DEG C of conditions so that it is in Fe3+It is converted into Fe2+, solution after filtering the reduction that prepared Main Ingredients and Appearance is ferrous sulfate；
Step (2): send first class purification operation by part steps (1) gained copperas solution, be added thereto to ammonium hydrogen carbonate or ammonium carbonate, under 50 DEG C of-80 DEG C of conditions react 30-180min so that it is in rare earth be converted into carbonated rare earth precipitation；Add ammonium sulfide or hydrogen sulfide, under 50 DEG C of-80 DEG C of conditions, react 30-180min so that it is in the heavy metal such as cobalt be converted into sulfide precipitation；Reaction filter after terminating receive purify after copperas solution and precipitate that Main Ingredients and Appearance is carbonated rare earth, cobalt sulfide.Secondary purification operation is sent by copperas solution after purification, adding proper ammonia makes a small amount of ferrous iron be converted into ferrous hydroxide, make ferrous hydroxide by being converted into hydrated ferric oxide. with contacting of air simultaneously, insulation precipitation 30-180min under 50 DEG C of-80 DEG C of conditions, the rare earth of further adsorbent solution residual, cobalt foreign ion, reaction filters, after terminating, the copperas solution receiving pure and Main Ingredients and Appearance is the precipitate of hydrated ferric oxide., and first class purification and precipitate produced by secondary purification return acidleach operation and recycle；
Step (3): copperas solution pure for step (2) gained is combined in reactor in multifunctional oxygen and is diluted to 5-30g/L by the later stage eluate of iron oxide red preparation section institute output, control solution temperature 10 DEG C-25 DEG C, it is added thereto to theoretical amount 0.9-1.5 times of ammonia, control ph is 9-10.5, and then blowing air oxidation 30-90min prepares crystal seed that outward appearance is sundown, that have well suspended；
Step (4): add water and be in right amount combined in reactor to multifunctional oxygen crystal seed and be diluted, and with sulphuric acid adjust slip pH value be 3-4, after crystal seed slurry temperature is promoted to 80 DEG C-90 DEG C by and add solution and ammonia after the reduction of step (1) gained in the way of flowing, blowing air oxidation simultaneously, controlling co-current process pH value is 3-4, in slip, ferrous sulfate concentration is 10-20g/L, when coloured light stops the dropping of solution after reduction to standard sample time similar, continue blowing air oxidation, and control slip pH value for 3-4 with ammonia, when in slip, Fe concentration is less than 0.1g/L, reaction terminates；
Step (5): by step (4) gained iron oxide red slurry filtration, receive iron oxide red wet cake and Fe concentration less than 0.1g/L, rare-earth oxidation substrate concentration at more than 0.3g/L, cobalt concentration at the iron oxide red mother solution of more than 0.25g/L, gained iron oxide red mother solution is merged with the leaching of ferrum, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue and separating step (4) gained eluate and is sent to rare earth and cobalt abstraction process for preparing rare earth and cobalt product；
Step (6): step (5) gained iron oxide red wet cake is sent in pickling reactor and mixes with acid eluate, under normal temperature condition, control ph is between 1.5-3, filter after being sufficiently stirred for, receiving then through washing and to obtain pickling rear oxidation iron oxide red wet cake and containing the acid eluate of rare earth sulfate, acid eluate recycles to merge with the leaching of ferrum, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue and separating step (4) gained eluate when reaching more than 0.1g/L to rare earth concentration and is sent to rare earth and cobalt abstraction process for preparing rare earth and cobalt product；
Step (7): pickling rear oxidation iron oxide red wet cake mixes making beating with clear water, then with Filter Press and wash, prepares the sulphates content washing rear oxidation iron oxide red wet cake less than 0.05%；
Step (8): iron oxide red wet cake is sent drying system dry prepared iron oxide red finished product.
Ferrum in neodymium iron boron waste material acid leaching residue, ferrum described in the leaching of rare earth and cobalt element and separating step one, rare earth and cobalt element leach and separation method: neodymium iron boron waste material acid leaching residue leaches in strong acid hot environment, make rare earth sulfuric acid salt solubility diminish and be enriched in acidleach residue, acidleach residue is mixed with water by the mode then adopting washing dissolution in plasm scouring groove again, make rare earth sulfate dissolution, the separated eluate receiving containing rare earth sulfate, when eluate middle rare earth concentration is less than 1.5g/L, eluate can return plasm scouring groove again recycle, until being sent to Extraction of rare eart operation again when eluate middle rare earth concentration is more than 2.0g/L.
The present invention proposes the method for comprehensive utilization of a kind of neodymium iron boron waste material acid leaching residue.In order to comprehensively utilize the valuable resource in neodymium iron boron waste material acid leaching residue, eliminate environmental pollution, achieve the comprehensive utilization of ferrum, trace rare-earth and cobalt resource in neodymium iron boron waste material acid leaching residue, prepare the iron oxide red commercial pigments of satisfactory quality and achieved efficiently separating and being enriched with its middle rare earth and cobalt element, comprehensively utilize for rare earth and the further of cobalt element, prepare rare earth oxide and cobalt compound is laid a good foundation.
Chemical reaction involved in the present invention:
Fe2O3+3H2SO4→Fe2(SO4)3+3H2O
RE2O3+3H2SO4+ (n-3) H2O→RE2(SO4)3·nH2O
CoO+H2SO4→CoSO4+H2O
RE2(SO4)3·nH2O+H2O→RE2(SO4)3+ (n+1) H2O
Reduction and purification:
Fe2(SO4)3+Fe→3FeSO4
RE2(SO4)3+6NH4HCO3→RE2(CO3)3+3(NH4)2SO4+3H2O+3CO2
CoSO4+(NH4)2S→CoS+(NH4)2SO4
4FeSO4+8NH3+10H2O+O2→4Fe(OH)3+4(NH4)2SO4
Prepared by iron oxide red:
FeSO4+2NH3·H2O→Fe(OH)2+(NH4)2SO4
4Fe(OH)2+O2+2H2O→4Fe(OH)3↓
H2SO4+2NH3→(NH4)2SO4
2Fe(OH)3→Fe2O3+3H2O
4FeSO4+O2+8NH3+4H2O→2Fe2O3+4(NH4)2SO4。
Accompanying drawing explanation
Below in conjunction with accompanying drawing, specific embodiments of the invention are described in further detail.
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
Embodiment 1:
Raw materials used composition: Fe2O353.54%；REO1.00%；Co0.65%.
Being mixed with 295kg acid leaching liquor in neutralization reactor by 100kg neodymium iron boron waste material acid leaching residue, controlling temperature is 70 DEG C of reaction 180min, and reaction is filtered after terminating, a small amount of water washing, receives to neutralize slag 69kg, neutralizer 355kg.Neutralizer is mainly composed of: Fe2(SO4)3131.3kg；REO0.4kg；Co0.62kg；
By in 69kg and residue in acid-leaching reaction device with 105kg iron oxide red later stage eluate mix and blend pulping, it is subsequently adding the concentrated sulphuric acid that 106kg concentration is 98%, under 70 DEG C of conditions, the response time is 240min, reaction is filtered after terminating under 70 DEG C of conditions, a small amount of water washing, receive to obtain acid leaching liquor 295kg, wet basis acidleach residue 27kg.
27kg acidleach residue is added in plasm scouring groove again eluate135kg, filters after stirring pulping, obtains the eluate that rare-earth oxidation substrate concentration is 2.9g/L, then utilize the washing function of pressure filter self, wash with iron oxide red later stage eluate, receive to obtain eluate135kg, rare-earth oxidation substrate concentration is 0.8g/L, returns dispensing in stock tank again, is cycled to used in the washing of acidleach residue.
Neutralizer 355kg is returned former operation, adds iron filings, under 50 DEG C of-80 DEG C of conditions, carry out reduction reaction so that it is in Fe3+It is converted into Fe2+, solution 520kg after filtering and preparing reduction, containing FeSO4150.1kg, REO0.4kg；Co0.62kg；
After being reduced by 16kg, solution send first class purification operation, it is added thereto to ammonium hydrogen carbonate, after reacting 30min under 50 DEG C of conditions, add ammonium sulfide solution, maintain this temperature and continue reaction 30min, reaction is filtered after terminating and is received to obtain copperas solution 16kg and the precipitate 0.1kg that Main Ingredients and Appearance is carbonated rare earth, cobalt sulfide.
After being purified by 16kg, copperas solution send secondary purification operation, adds 0.1kg ammonia under stirring condition, then insulation precipitation 30min under 80 DEG C of conditions.Reaction filters, after terminating, the copperas solution 16kg receiving pure, and Main Ingredients and Appearance is the precipitate 0.05kg of hydrated ferric oxide..The 0.15kg altogether of precipitate produced by first class purification and secondary purification is returned acidleach operation recycle.
Copperas solution pure for 16kg is combined in reactor in multifunctional oxygen and is diluted to 5g/L by iron oxide red later stage eluate, control solution temperature 10 DEG C, it is added thereto to 0.9 times of ammonia of theoretical amount, control ph is 9.0, then blowing air oxidation 30min, prepares crystal seed slip that outward appearance is sundown, that have well suspended.
Adding sulphuric acid in crystal seed slip, to adjust pH value be 3, is subsequently adding solution after reduction, and adjusting ferrous sulfate concentration in slip is 20g/L, after crystal seed slurry temperature is promoted to 80 DEG C by and add solution and ammonia, simultaneously blowing air oxidation after reduction in the way of flowing.Control co-current process pH value be 3, ferrous sulfate concentration is 20g/L in slip.Stop the dropping of solution after reducing when coloured light is similar to 130# standard sample, continue blowing air oxidation, and control slip pH value for 3 with ammonia.When in slip, Fe concentration is less than 0.1g/L, reaction terminates.Filter, separate receive iron oxide red mother solution 1300kg(wherein containing Fe0.10kg, rare earth oxide 0.34kg, cobalt 0.57kg), iron oxide red wet cake 160kg.
Iron oxide red wet cake being sent in pickling reactor and mix with acid eluate, under normal temperature condition, control ph, 1.5, filters after stirring, washs, and receives and to obtain pickling rear oxidation iron oxide red wet cake 160kg and the acid eluate containing rare earth sulfate.Acid eluate is recycled and reaches more than 0.1g/L to rare earth concentration, stop recycling, often process 100kg neodymium iron boron waste material, on average can output acid eluate 90kg, containing rare earth oxide 0.01kg, cobalt 0.01kg.Iron oxide red acid eluate and iron oxide red mother solution and eluateSend rare earth and cobalt abstraction process after merging, extract rare earth therein, cobalt and prepare into corresponding compound products.
160kg pickling rear oxidation iron oxide red wet cake is mixed with clear water making beating, then with Filter Press and wash, preparing the sulphates content washing rear oxidation iron oxide red wet cake less than 0.05%, send drying system to dry prepared iron oxide red finished product 82kg, product meets GB/T1863-2008 iron oxide red product standard.
Embodiment 2
Raw materials used composition: Fe2O367.53%；REO0.85%；
Being mixed with 3410kg acid leaching liquor in neutralization reactor by 1000kg neodymium iron boron waste material acid leaching residue, controlling temperature is 100 DEG C, and the time is 360min, and reaction is filtered after terminating under 90 DEG C of conditions, a small amount of water washing, receives to neutralize slag 600kg, neutralizer 3850kg.Neutralizer is mainly composed of: Fe2(SO4)31665kg；REO3.80kg；
By in 600kg and residue in acid-leaching reaction device with 1500kg iron oxide red later stage eluate mix and blend pulping, it is subsequently adding the concentrated sulphuric acid that 1560kg concentration is 98%, under 90 DEG C of conditions, the response time is 180min, reaction is filtered after terminating under 100 DEG C of conditions, a small amount of water washing, receive to obtain acid leaching liquor 3410kg, wet basis acidleach residue 250kg.
250kg acidleach residue is added in plasm scouring groove again eluate300kg, filters after stirring pulping, obtains the eluate that rare-earth oxidation substrate concentration is 1.5g/L, then utilize the washing function of pressure filter self, wash with iron oxide red later stage eluate, receive to obtain eluate300kg, rare-earth oxidation substrate concentration is 0.3g/L, returns dispensing in stock tank again, is cycled to used in the washing of acidleach residue.
Neutralizer 3850kg is returned former operation, adds iron sheet, under 50 DEG C of-80 DEG C of conditions, carry out reduction reaction so that it is in Fe3+It is converted into Fe2+, solution 6500kg after filtering and preparing reduction, containing FeSO41900kg, REO3.80kg；
After being reduced by 260kg, solution send first class purification operation, it is added thereto to ammonium carbonate, after reacting 120min under 80 DEG C of conditions, add ammonium sulfide solution, maintain this temperature and continue reaction 180min, reaction is filtered after terminating and is received to obtain copperas solution 260kg and the precipitate 1.90kg that Main Ingredients and Appearance is carbonated rare earth, cobalt sulfide.
After being purified by 260kg, copperas solution send secondary purification operation, adds 2.0kg ammonia under stirring condition, then insulation precipitation 180min under 50 DEG C of conditions.Reaction filters, after terminating, the copperas solution 260kg receiving pure, and Main Ingredients and Appearance is the precipitate 1.0kg of hydrated ferric oxide..The 2.90kg altogether of precipitate produced by first class purification and secondary purification is returned acidleach operation recycle.
Copperas solution pure for 260kg is combined in reactor in multifunctional oxygen and is diluted to 30g/L by iron oxide red later stage eluate, control solution temperature 25 DEG C, it is added thereto to 1.1 times of ammonia of theoretical amount, control ph is 10.5, then blowing air oxidation 90min, prepares crystal seed slip that outward appearance is sundown, that have well suspended.
Adding sulphuric acid in crystal seed slip, to adjust pH value be 4, is subsequently adding solution after reduction, and adjusting ferrous sulfate concentration in slip is 10g/L, after crystal seed slurry temperature is promoted to 90 DEG C by and add solution and ammonia, simultaneously blowing air oxidation after reduction in the way of flowing.Control co-current process pH value be 4, ferrous sulfate concentration is 10g/L in slip.Stop the dropping of solution after reducing when coloured light is similar to 190# standard sample, continue blowing air oxidation, and control slip pH value for 4 with ammonia.When in slip, Fe concentration is less than 0.1g/L, reaction terminates.Filter, separate receive iron oxide red mother solution 9000kg(wherein containing Fe0.75kg, rare earth oxide 3.44kg), iron oxide red wet cake 2000kg.
Iron oxide red wet cake being sent in pickling reactor and mix with acid eluate, under normal temperature condition, control ph, 3, filters after being sufficiently stirred for, washs, and receives and to obtain pickling rear oxidation iron oxide red wet cake 2000kg and the acid eluate containing rare earth sulfate.Acid eluate is recycled and reaches 0.12g/L to rare earth concentration, stop recycling, often process 1000kg neodymium iron boron waste material, on average can output acid eluate 850kg, containing rare earth oxide 0.102kg.Iron oxide red acid eluate and iron oxide red mother solution and eluateSend rare earth and cobalt abstraction process after merging, extract rare earth therein, cobalt and prepare into corresponding compound products.
2000kg pickling rear oxidation iron oxide red wet cake is mixed with clear water making beating, then with Filter Press and wash, prepare the sulphates content washing rear oxidation iron oxide red wet cake less than 0.05%, sending drying system to dry prepared iron oxide red finished product 1050kg, product meets GB/T1863-2008 iron oxide red product standard.
Claims (3)
1. the method for comprehensive utilization of a neodymium iron boron waste material acid leaching residue, it is characterised in that sequentially include the following steps:
The leaching of ferrum, rare earth and cobalt element and separation in neodymium iron boron waste material acid leaching residue:
Step (1): neodymium iron boron waste material acid leaching residue is mixed with from the neodymium iron boron waste material acid leaching residue acid leaching liquor obtained by acidleach, separation circuit in neutralization reactor, controlling neutral temperature is 70 DEG C-100 DEG C, the neutralization response time is 180-360min, reaction end pH value is 0.25-0.5, making the free acid in acid leaching liquor be consumed, ferrum in neodymium iron boron waste material acid leaching residue, rare earth and cobalt element obtain preliminary dissolution；
Step (2): the slip in neutralization reactor is filtered under 70 DEG C of-100 DEG C of conditions and receives to obtain neutralizer and neutralization residue, the Main Ingredients and Appearance of neutralizer is the sulfate of ferrum and cobalt, it is used as the raw material of preparation iron oxide red, neutralizes the cobalt that residue Main Ingredients and Appearance is silicon dioxide, ferrum oxide, rare earth oxide, rare earth sulfate and trace；
Step (3): send acidleach operation by neutralization residue, with the later stage eluate of iron oxide red preparation section institute output by solid-to-liquid ratio 1:1.5-1:2.5 mixing in acid-leaching reaction device, then add concentrated sulphuric acid by 1.5-1.9 times of theoretical amount under 70 DEG C of-100 DEG C of conditions, carry out acid-leaching reaction, the control acid-leaching reaction time is 180-360min, the further dissolution of ferrum therein, rare earth and cobalt, reaction is made to terminate to receive to obtain the acid leaching liquor that Main Ingredients and Appearance is ferrum and cobalt sulfate and acidleach residue through filtration；Gained acid leaching liquor is stored and is used as to neutralize proportion liquid；
Step (4): step one, course of reaction described in three is strong acid hot environment, rare earth sulfuric acid salt solubility is relatively low with this understanding, major part is composed with the form of soluble-salt and is stored in residue, step 2 gained will mix under normal temperature condition and makes pulping with the later stage eluate of iron oxide red preparation section institute output with residue gained acidleach residue after step 3 acidleach in plasm scouring groove again, the rare earth sulfate in acidleach residue is made to dissolve and enter liquid phase, it is then passed through filter, washing prepares eluate and the acidleach residue that Main Ingredients and Appearance is rare earth sulfate, eluate middle rare earth content is between 1-3g/L, send Extraction of rare eart operation for preparing rare-earth products；
The preparation of iron oxide red:
Step (1): step 2 gained neutralizer is returned former operation, with iron filings, iron sheet or reduced iron powder for reducing agent, carries out reduction reaction under 50 DEG C of-80 DEG C of conditions so that it is in Fe3+It is converted into Fe2+, solution after filtering the reduction that prepared Main Ingredients and Appearance is ferrous sulfate；
Step (2): send first class purification operation by part steps (1) gained copperas solution, be added thereto to ammonium hydrogen carbonate or ammonium carbonate, under 50 DEG C of-80 DEG C of conditions react 30-180min so that it is in rare earth be converted into carbonated rare earth precipitation；Add ammonium sulfide or hydrogen sulfide, under 50 DEG C of-80 DEG C of conditions, react 30-180min so that it is in the heavy metal such as cobalt be converted into sulfide precipitation；Reaction filter after terminating receive purify after copperas solution and precipitate that Main Ingredients and Appearance is carbonated rare earth, cobalt sulfide.
2. send secondary purification operation by copperas solution after purification, adding proper ammonia makes a small amount of ferrous iron be converted into ferrous hydroxide, make ferrous hydroxide by being converted into hydrated ferric oxide. with contacting of air simultaneously, insulation precipitation 30-180min under 50 DEG C of-80 DEG C of conditions, the rare earth of further adsorbent solution residual, cobalt foreign ion, reaction filters, after terminating, the copperas solution receiving pure and Main Ingredients and Appearance is the precipitate of hydrated ferric oxide., and first class purification and precipitate produced by secondary purification return acidleach operation and recycle；
Step (3): copperas solution pure for step (2) gained is combined in reactor in multifunctional oxygen and is diluted to 5-30g/L by the later stage eluate of iron oxide red preparation section institute output, control solution temperature 10 DEG C-25 DEG C, it is added thereto to theoretical amount 0.9-1.5 times of ammonia, control ph is 9-10.5, and then blowing air oxidation 30-90min prepares crystal seed that outward appearance is sundown, that have well suspended；
Step (4): add water and be in right amount combined in reactor to multifunctional oxygen crystal seed and be diluted, and with sulphuric acid adjust slip pH value be 3-4, after crystal seed slurry temperature is promoted to 80 DEG C-90 DEG C by and add solution and ammonia after the reduction of step (1) gained in the way of flowing, blowing air oxidation simultaneously, controlling co-current process pH value is 3-4, in slip, ferrous sulfate concentration is 10-20g/L, when coloured light stops the dropping of solution after reduction to standard sample time similar, continue blowing air oxidation, and control slip pH value for 3-4 with ammonia, when in slip, Fe concentration is less than 0.1g/L, reaction terminates；
Step (5): by step (4) gained iron oxide red slurry filtration, receive iron oxide red wet cake and Fe concentration less than 0.1g/L, rare-earth oxidation substrate concentration at more than 0.3g/L, cobalt concentration at the iron oxide red mother solution of more than 0.25g/L, gained iron oxide red mother solution is merged with the leaching of ferrum, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue and separating step (4) gained eluate and is sent to rare earth and cobalt abstraction process for preparing rare earth and cobalt product；
Step (6): step (5) gained iron oxide red wet cake is sent in pickling reactor and mixes with acid eluate, under normal temperature condition, control ph is between 1.5-3, filter after being sufficiently stirred for, receiving then through washing and to obtain pickling rear oxidation iron oxide red wet cake and containing the acid eluate of rare earth sulfate, acid eluate recycles to merge with the leaching of ferrum, rare earth and cobalt element in neodymium iron boron waste material acid leaching residue and separating step (4) gained eluate when reaching more than 0.1g/L to rare earth concentration and is sent to rare earth and cobalt abstraction process for preparing rare earth and cobalt product；
Step (7): pickling rear oxidation iron oxide red wet cake mixes making beating with clear water, then with Filter Press and wash, prepares the sulphates content washing rear oxidation iron oxide red wet cake less than 0.05%；
Step (8): iron oxide red wet cake is sent drying system dry prepared iron oxide red finished product.
3. the method for comprehensive utilization of neodymium iron boron waste material acid leaching residue according to claim 1, it is characterised in that
Ferrum in neodymium iron boron waste material acid leaching residue, ferrum described in the leaching of rare earth and cobalt element and separating step one, rare earth and cobalt element leach and separation method: neodymium iron boron waste material acid leaching residue leaches in strong acid hot environment, make rare earth sulfuric acid salt solubility diminish and be enriched in acidleach residue, acidleach residue is mixed with water by the mode then adopting washing dissolution in plasm scouring groove again, make rare earth sulfate dissolution, the separated eluate receiving containing rare earth sulfate, when eluate middle rare earth concentration is less than 1.5g/L, eluate can return plasm scouring groove again recycle, until being sent to Extraction of rare eart operation again when eluate middle rare earth concentration is more than 2.0g/L.
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