CN105087945B - Method for utilizing zirconium oxychloride waste acid comprehensively - Google Patents
Method for utilizing zirconium oxychloride waste acid comprehensively Download PDFInfo
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Abstract
The invention discloses a method for utilizing zirconium oxychloride waste acid comprehensively. The phases of the zirconium oxychloride waste acid and a P extraction system are split into organic scandium-rich phases and aqueous phases through mixing; scandium precipitation enriched materials are generated by conducting washing and scandium return through alkali on the organic scandium-rich phases; the aqueous phases are subjected to pH value adjusting treatment, and zirconium titanium phosphate mixtures and rare earth solutions are generated by conducting precipitation treatment on the aqueous phases through phosphate or phosphoric acid respectively; the zirconium titanium phosphate mixtures are used for treating ammonia-nitrogen waste water after being treated; rare earth raw materials or rare earth oxide is dissolved through the acid in the rare earth solutions and enters a rare earth extraction and separation system; rare earth in the rare earth solutions forms the rare earth oxide, rare earth carbonate or rare earth hydroxide. By means of the method for utilizing the zirconium oxychloride waste acid comprehensively, the composite recovery rate of the zirconium element in a zirconium oxychloride production line is improved to 95%. Equipment is simple, the method is easy to control, applicable to industrialized production and low in cost, the ecological environment is protected, and the economic value is generated.
Description
Technical field
The present invention relates to technical field of wet metallurgy, the more particularly to method of the comprehensive utilization of zirconium oxychloride spent acid.
Background technology
Nowadays rare earth has become extremely important strategic resource.Rare earth is in oil, chemical industry, metallurgy, weaving, ceramics, glass
The fields such as glass, permanent magnet material are obtained for and are widely applied, with the progress and the continuous breakthrough of application technology of science and technology.Rare earth master
Originate is ion type rareearth ore, solitary stone ore and bastnasite.
Scia is mainly reclaimed in the comprehensive utilization of country's zirconium oxychloride spent acid at present, is all that list is obtained by extraction by multistep
Only Scia product；Such as：China Patent Publication No. CN104630489A, discloses one kind and oxygen is reclaimed from zirconium oxychloride mother solution
Change the method for scandium, China Patent Publication No. CN104232945A and disclose a kind of hydrochloric acid mother liquor preparation height by production zirconium oxychloride
The method of pure scandium oxide, China Patent Publication No. CN103318940A disclose one kind and refine from zirconium oxychloride spent acid
The method of Scia；But spent acid middle rare earth and other elements are not obtained by.
Zirconium oxychloride product purpose is the basic material of zirconium chemical industry extensively, the huge market demand；The country generally adopts alkali fusion
The zirconium oxychloride of technique productions can produce spent acid；In spent acid in addition to the zr element containing residual, also titanium, scandium, rare earth etc. are guarantee
The quality of zirconium oxychloride, most enterprise is not generally recycled or recycled and once processes into waste water station to spent acid.
According to statistics, often produce one ton of zirconium oxychloride and about generate 100 ~ 500L spent acid.
Rare earth oxide refers to 15 kinds of lanthanide oxides that period of element atom ordinal number is 57 to 71, and and lanthanum
The similar scandium of series elements chemical property（Sc）And yttrium（Y）The oxide of totally 17 kinds of elements.Rare earth in zirconium oxychloride spent acid is
With raw material association, mainly based on yttrium.Because the quantity that rare earth element is used is more and more more, other aspect rare earths are reclaimed
Resource, just becomes a vital task of Rare Earth Production enterprise.
Scia is a kind of exotic material, is grand strategy reserved resources, in national defence, metallurgy, space flight, medical treatment, health-promoting apparatus
The sophisticated technology such as material, superconductor, solid fuel cell field has irreplaceable important use.Due to without special scandium ore deposit
Hide, whole world scandium production almost all is extracted by way of comprehensive utilization, and yield very little, it is difficult to meet downstream industry
Need.It is reported that, about 2,000,000 tons of the commercial reserves of whole world scandium, China there are about 60 ~ 650,000 tons, account for world's total content
30% or so；At present the source of scandium is mainly from synthetical recovery in the side-product for processing the ore deposits such as titanium, aluminum, tungsten, stannum, uranium, rare earth, such as
Titanium white waste liquid, red mud, wolframic acid slag etc..Scia content is between 0.4 ~ 1.2g/L in basic zirconium chloride spent acid.
China Patent Publication No. CN104342559A discloses one kind from synthetical recovery multiple element in zirconium oxychloride waste liquid
Method, by multi-stage extracting process Scia and rare earth are extracted, but the zirconium, titanium elements in spent acid is not obtained by.
And the alkali fusion technique of current zirconium industry, zr element comprehensive recovery is 92%.Therefore, the synthetical recovery of zirconium oxychloride
Rate is relatively low not to be fully used, while being also unfavorable for environmental conservation.
The content of the invention
It is an object of the invention to provide a kind of method of zirconium oxychloride spent acid comprehensive utilization, using the acid of zirconium oxychloride spent acid
Scandium Element generation scandium precipitation enriched substance in dissolving rare earths material or rare earth oxide, spent acid, extracts the rare earth element in spent acid
With titanium zr element, so as to lift the comprehensive recovery of zirconium oxychloride production line zr element.
The present invention is achieved through the following technical solutions above-mentioned purpose.The method of the comprehensive utilization of zirconium oxychloride spent acid, its work
Skill step is as follows：
1）Simultaneously split-phase is organic rich scandium phase and water phase to the extraction blended with P extraction systems of zirconium oxychloride spent acid；It is described organic
Mutually scrubbed again and alkali returns scandium to rich scandium, generates scandium precipitation enriched substance；
2）The water phase acid adjustment basicity, and Jing phosphate or phosphoric acid precipitates are processed so as to the molal quantity of middle zirconium titanium elements:
Phosphoric acid or phosphatic molal quantity are 1:2～3, and when pH value reaches 1～5, as addition phosphoric acid or phosphatic terminal,
ZTP zirconium titanium phosphate mixture and earth solution are formed respectively；
3）By the ZTP zirconium titanium phosphate mixture, for ammonia nitrogen waste water process；
4）Using acid dissolving rare earths material or rare earth oxide in the earth solution, into rare earth extraction separation system
Or into rare earth extraction separation system together with the rare earth oxide after dissolving through diluted acid；
5）Rare earth oxide, rare earth carbonate or rare-earth hydroxide are formed respectively by the rare earth in the earth solution；
6）By step 5）In the rare earth oxide forming process：The earth solution is adjusted into pH values, with oxalic acid or
Soluble oxalate salt carries out rare-earth precipitation, obtains rare-earth oxalate precipitate, then drying and calcining form rare earth oxide；
7) by step 5）In the rare earth carbonate or rare-earth hydroxide forming process：By the earth solution
Rare-earth precipitation is carried out with soluble carbonate salt or hydroxide, the rare earth carbonate or rare-earth hydroxide is obtained；
8）By step 6）The rare earth oxide for producing and step 7）The rare earth carbonate for producing or rare earth hydrogen-oxygen
After compound is dissolved respectively with diluted acid, into rare earth extraction separation system.
Further, the water is mutually that zirconium oxychloride spent acid removes the waste acid liquor after scandium element.
Further, the soluble carbonate salt is sodium carbonate or sodium bicarbonate.
Further, the hydroxide is sodium hydroxide or ammonia.
After the present invention is by being enriched with Scia, to the solution without scandium using phosphoric acid or phosphate precipitation, by spent acid
Zirconium titanium and rare earth are separated, and obtain the solution of ZTP zirconium titanium phosphate mixture and enrichment rare earth, and the ZTP zirconium titanium phosphate mixture of recovery is used
In ammonia nitrogen waste water process, the acid in the earth solution of enrichment is used for the dissolving of rare earths material or rare earth oxide, reduces diluted acid
Usage amount, environmental issue is solved, while having reached the maximization of waste acid reuse；Rare earth in earth solution forms rare earth oxygen
Compound, rare earth carbonate or rare-earth hydroxide；ZTP zirconium titanium phosphate mixture has been reclaimed, the comprehensive of zirconium oxychloride production line zr element has been made
Close the response rate to improve to 95%.The method of the comprehensive utilization of zirconium oxychloride spent acid of the present invention, its technological process of production equipment is simple,
Easy to control, it is adaptable to industrialized production, low cost had both protected ecological environment, and economic worth is generated again.
Description of the drawings
Fig. 1 is the process chart of the present invention.
Specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described.Referring to Fig. 1, the comprehensive profit of zirconium oxychloride spent acid
Method, its processing step is as follows：
1）Simultaneously split-phase is organic rich scandium phase 103 and water phase to the extraction blended with P extraction systems 102 of zirconium oxychloride spent acid 101
105；Organic rich scandium phase 103 is scrubbed again and alkali returns scandium, generates scandium precipitation enriched substance 104；
2）To the acid adjustment basicity of the water phase 105, and Jing phosphate or phosphoric acid precipitates process 106 so as to middle zirconium titanium elements
Molal quantity:Phosphoric acid or phosphatic molal quantity are 1:2～3, and when pH value reaches 1～5, as addition phosphoric acid or phosphate
Terminal, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；
3）By the ZTP zirconium titanium phosphate mixture 107, for ammonia nitrogen waste water 108 are processed；
4）Using acid dissolving rare earths material or rare earth oxide 116 in the earth solution 109, into rare earth extraction point
It is in vitro that rare earth extraction separation system 110 is entered together with 110 or the rare earth oxide 113 after dissolving through diluted acid；
5）Rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively by the rare earth in the earth solution 109
Compound 115；
6）By step 5）In the rare earth oxide 113 forming process：The earth solution 109 is adjusted into pH values, is used
Oxalic acid or Soluble oxalate salt carry out rare-earth precipitation 111, obtain rare-earth oxalate precipitate 112, then drying and calcining are formed
Rare earth oxide 113；
7) by step 5）In the rare earth carbonate or rare-earth hydroxide 115 forming process：The rare earth is molten
Liquid 109 soluble carbonate salt or hydroxide carry out rare-earth precipitation 114, obtain the rare earth carbonate or rare-earth hydroxide
115；
8）By step 6）The rare earth oxide 113 for producing and step 7）The rare earth carbonate for producing or rare earth hydrogen
After oxide 115 is dissolved respectively with diluted acid, into rare earth extraction separation system 110.
The water phase 105 is that zirconium oxychloride spent acid removes the waste acid liquor after scandium element.The soluble carbonate salt is carbon
Sour sodium or sodium bicarbonate.The hydroxide is sodium hydroxide or ammonia.
The method of the comprehensive utilization of zirconium oxychloride spent acid of the present invention, its technical process is the scandium being enriched with zirconium oxychloride spent acid
Element, extracts the rare earth element in spent acid, and recycling zirconium titanium elements therein produce ZTP zirconium titanium phosphate mixture, ZTP zirconium titanium phosphate mixing
Thing is used for the process of ammonia nitrogen waste water.
The concrete operation step of the present invention is as follows：
1. the acid number of zirconium oxychloride spent acid 101 is that simultaneously split-phase is have to the blended extraction of 4.5 ~ 5.5N and P extraction systems 102
Machine richness scandium phase 103（Scandium extraction yield is up to more than 98%）With water phase 105；Organic rich scandium phase 103 low acid of Jing again（0.2N ~
3.5N hydrochloric acid system）Washing and aqueous slkali（0.5N ~ 6N sodium hydroxide systems）Scandium is returned, scandium precipitation enriched substance 104 is obtained；
2. the acid adjustment basicity of water phase 105 that will be reclaimed（2N ~ 0.2N）, and Jing phosphate or phosphoric acid precipitates process 106（It is heavy
Form sediment and process the molal quantity of zirconium titanium elements in 106:Phosphoric acid or phosphatic molal quantity are 1:2～3, when pH value reaches 1～5, as
Addition phosphoric acid or phosphatic terminal）, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；；
3. the ZTP zirconium titanium phosphate mixture 107 that phosphoric acid or calcium phosphate precipitation go out, for the process 108 of ammonia nitrogen waste water.
4. using the acid dissolving rare earths material or rare earth oxide 116 of earth solution 109, and separate into rare earth extraction
System 110, or enter rare earth extraction separation system 110 together with the rare earth oxide 113 Jing after diluted acid dissolving；
5. or by the rare earth in earth solution 109 rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively
Compound 115；
6. the forming process of rare earth oxide 113 is：Earth solution 109 is adjusted into pH=3.5 ~ 9, with oxalic acid or solubility grass
Hydrochlorate carries out rare-earth precipitation 111, and obtains rare-earth oxalate precipitate 112, then drying and calcining form rare earth oxide
113；
7. the forming process of rare earth carbonate or rare-earth hydroxide 115 is：By the solubility carbonic acid of earth solution 109
Salt（Sodium bicarbonate, sodium carbonate, carbonate）Or hydroxide（Sodium hydroxide, ammonia）Rare-earth precipitation 114 is carried out, and obtains rare earth
Carbonate or rare-earth hydroxide 115,
8. rare earth oxide 113 and rare earth carbonate or rare-earth hydroxide 115 are used into respectively diluted acid（0.05N ~ 2N salt
Acid）After dissolving, into rare earth extraction separation system 110.
Embodiment 1:One better embodiment of the present invention introduced below.
1. the acid number of zirconium oxychloride spent acid 101 is（It is 15.7 g/L that acid number is 4.8N zirconia contents）With P extraction systems
Simultaneously split-phase is organic rich scandium phase 103 for 102 blended extractions（Scandium extraction yield is up to more than 98%）With water phase 105；Organic rich scandium
The low acid of Jing again of phase 103（1.2N hydrochloric acid system）Washing and aqueous slkali（2.1 sodium hydroxide systems）Scandium is returned, scandium precipitation enriched substance is obtained
104；Then water phase 105 is reclaimed；
2. by the acid adjustment basicity of water phase 105 for reclaiming to 0.8N, and Jing phosphate or phosphoric acid precipitates process 106（Precipitation process
The molal quantity of zirconium titanium elements in 106:Phosphoric acid or phosphatic molal quantity are 1:2.3, when pH value reaches 1.3, as addition phosphoric acid
Or phosphatic terminal）, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；
3. the ZTP zirconium titanium phosphate mixture 107 that phosphoric acid or calcium phosphate precipitation go out, for the process 108 of ammonia nitrogen waste water；
4. using the acid dissolving rare earths material or rare earth oxide 116 of earth solution 109, and separate into rare earth extraction
System 110, or enter rare earth extraction separation system 110 together with the rare earth oxide 113 Jing after diluted acid dissolving；
5. or by the rare earth in earth solution 109 rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively
Compound 115；
6. the forming process of rare earth oxide 113 is：Earth solution 109 is adjusted into pH=5.9, with oxalic acid or Soluble oxalate
Salt carries out rare-earth precipitation 111, and obtains rare-earth oxalate precipitate 112, then drying and calcining form rare earth oxide 113；
7. the forming process of rare earth carbonate or rare-earth hydroxide 115 is：By the solubility carbonic acid of earth solution 109
Salt（Sodium bicarbonate, sodium carbonate, carbonate）Or hydroxide（Sodium hydroxide, ammonia）Rare-earth precipitation 114 is carried out, and obtains rare earth
Carbonate or rare-earth hydroxide 115；
8. rare earth oxide 113 and rare earth carbonate or rare-earth hydroxide 115 are used into respectively diluted acid（1.5N hydrochloric acid）It is molten
Xie Hou, into rare earth extraction separation system 110.
Embodiment 2:Another better embodiment of the present invention introduced below.
1. the acid number of zirconium oxychloride spent acid 101 is（It is 19.3 g/L that acid number is 4.5N zirconia contents）With P extraction systems
Simultaneously split-phase is organic rich scandium phase 103 for 102 blended extractions（Scandium extraction yield is up to more than 98%）With water phase 105；Organic rich scandium
The low acid of Jing again of phase 103（1.8N hydrochloric acid system）Washing and aqueous slkali（2.1 sodium hydroxide systems）Scandium is returned, scandium precipitation enriched substance is obtained
104；Then water phase 105 is reclaimed；
2. by the acid adjustment basicity of water phase 105 for reclaiming to 0.4N, and Jing phosphate or phosphoric acid precipitates process 106（Precipitation process
The molal quantity of zirconium titanium elements in 106:Phosphoric acid or phosphatic molal quantity are 1:2.5, when pH value reaches 2.7, as addition phosphoric acid
Or phosphatic terminal）, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；
3. the ZTP zirconium titanium phosphate mixture 107 that phosphoric acid or calcium phosphate precipitation go out, for the process 108 of ammonia nitrogen waste water；
4. using the acid dissolving rare earths material or rare earth oxide 116 of earth solution 109, and separate into rare earth extraction
System 110, or enter rare earth extraction separation system 110 together with the rare earth oxide 113 Jing after diluted acid dissolving；
5. or by the rare earth in earth solution 109 rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively
Compound 115；
6. the forming process of rare earth oxide 113 is：Earth solution 109 is adjusted into pH=5.9, with oxalic acid or Soluble oxalate
Salt carries out rare-earth precipitation 111, and obtains rare-earth oxalate precipitate 112, then drying and calcining form rare earth oxide 113；
7. the forming process of rare earth carbonate or rare-earth hydroxide 115 is：By the solubility carbonic acid of earth solution 109
Salt（Sodium bicarbonate, sodium carbonate, carbonate）Or hydroxide（Sodium hydroxide, ammonia）Rare-earth precipitation 114 is carried out, and obtains rare earth
Carbonate or rare-earth hydroxide 115；
8. rare earth oxide 113 and rare earth carbonate or rare-earth hydroxide 115 are used into respectively diluted acid（1.5N hydrochloric acid）It is molten
Xie Hou, into rare earth extraction separation system 110.
Embodiment 3:3rd better embodiment of the present invention introduced below：
1. the acid number of zirconium oxychloride spent acid 101 is（It is 18.0 g/L that acid number is 4.3N zirconia contents）With P extraction systems
Simultaneously split-phase is organic rich scandium phase 103 for 102 blended extractions（Scandium extraction yield is up to more than 98%）With water phase 105；Organic rich scandium
The low acid of Jing again of phase 103（1.2N hydrochloric acid system）Washing and aqueous slkali（2.1 sodium hydroxide systems）Scandium is returned, scandium precipitation enriched substance is obtained
104；Then water phase 105 is reclaimed；
2. by the acid adjustment basicity of water phase 105 for reclaiming to 0.8N, and Jing phosphate or phosphoric acid precipitates process 106（Precipitation process
The molal quantity of zirconium titanium elements in 106:Phosphoric acid or phosphatic molal quantity are 1:2.7, when pH value reaches 3.6, as addition phosphoric acid
Or phosphatic terminal）, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；
3. the ZTP zirconium titanium phosphate mixture 107 that phosphoric acid or calcium phosphate precipitation go out, for the process 108 of ammonia nitrogen waste water.
4. using the acid dissolving rare earths material or rare earth oxide 116 of earth solution 109, and separate into rare earth extraction
System 110, or enter rare earth extraction separation system 110 together with the rare earth oxide 113 Jing after diluted acid dissolving；
5. or by the rare earth in earth solution 109 rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively
Compound 115；
6. the forming process of rare earth oxide 113 is：Earth solution 109 is adjusted into pH=5.3, with oxalic acid or Soluble oxalate
Salt carries out rare-earth precipitation 111, and obtains rare-earth oxalate precipitate 112, then drying and calcining form rare earth oxide 113；
7. the forming process of rare earth carbonate or rare-earth hydroxide 115 is：By the solubility carbonic acid of earth solution 109
Salt（Sodium bicarbonate, sodium carbonate, carbonate）Or hydroxide（Sodium hydroxide, ammonia）Rare-earth precipitation 114 is carried out, and obtains rare earth
Carbonate or rare-earth hydroxide 115；
8. rare earth oxide 113 and rare earth carbonate or rare-earth hydroxide 115 are used into respectively diluted acid（1.2N hydrochloric acid）It is molten
Xie Hou, into rare earth extraction separation system 110.
Embodiment 4:4th better embodiment of the present invention is as follows：
1. the acid number of zirconium oxychloride spent acid 101 is（It is 29.0 g/L that acid number is 5.5N zirconia contents）With P extraction systems
Simultaneously split-phase is organic rich scandium phase 103 for 102 blended extractions（Scandium extraction yield is up to more than 98%）With water phase 105；Organic rich scandium
The low acid of Jing again of phase 103（3.5N hydrochloric acid system）Washing and aqueous slkali（6N sodium hydroxide systems）Scandium is returned, scandium precipitation enriched substance is obtained
104；Then water phase 105 is reclaimed；
2. by the acid adjustment basicity of water phase 105 for reclaiming to 0.8N, and Jing phosphate or phosphoric acid precipitates process 106（Precipitation process
The molal quantity of zirconium titanium elements in 106:Phosphoric acid or phosphatic molal quantity are 1:2.8, when pH value reaches 4.8, as addition phosphoric acid
Or phosphatic terminal）, ZTP zirconium titanium phosphate mixture 107 and earth solution 109 are formed respectively；
3. the ZTP zirconium titanium phosphate mixture 107 that phosphoric acid or calcium phosphate precipitation go out, for the process 108 of ammonia nitrogen waste water.
4. using the acid dissolving rare earths material or rare earth oxide 116 of earth solution 109, and separate into rare earth extraction
System 110, or enter rare earth extraction separation system 110 together with the rare earth oxide 113 Jing after diluted acid dissolving；
5. or by the rare earth in earth solution 109 rare earth oxide 113, rare earth carbonate or rare earth hydrogen-oxygen are formed respectively
Compound 115；
6. the forming process of rare earth oxide 113 is：Earth solution 109 is adjusted into pH=4.2, with oxalic acid or Soluble oxalate
Salt carries out rare-earth precipitation 111, and obtains rare-earth oxalate precipitate 112, then drying and calcining form rare earth oxide 113；
7. the forming process of rare earth carbonate or rare-earth hydroxide 115 is：By the solubility carbonic acid of earth solution 109
Salt（Sodium bicarbonate, sodium carbonate, carbonate）Or hydroxide（Sodium hydroxide, ammonia）Rare-earth precipitation 114 is carried out, and obtains rare earth
Carbonate or rare-earth hydroxide 115；
8. rare earth oxide 113 and rare earth carbonate or rare-earth hydroxide 115 are used into respectively diluted acid（1.2N hydrochloric acid）It is molten
Xie Hou, into rare earth extraction separation system 110.
The indices of above-described embodiment 1 to 4 such as following table：
The response rate of scandium is 88-90.2%；Zirconium oxychloride production line zr element comprehensive recovery is 94-95%；Rare earth recovery
Rate is 91-93%.
Claims (4)
1. the method for the comprehensive utilization of zirconium oxychloride spent acid, it is characterised in that its processing step is as follows：
1）Simultaneously split-phase is organic rich scandium phase and water phase to the extraction blended with P extraction systems of zirconium oxychloride spent acid；Organic rich scandium
Mutually scrubbed again and alkali returns scandium, generates scandium precipitation enriched substance；
2）The water phase acid adjustment basicity, and Jing phosphate or phosphoric acid precipitates are processed so as to the molal quantity of middle zirconium titanium elements:Phosphoric acid
Or phosphatic molal quantity is 1:2～3, and when pH value reaches 1～5, as addition phosphoric acid or phosphatic terminal, difference
Form ZTP zirconium titanium phosphate mixture and earth solution；
3）By the ZTP zirconium titanium phosphate mixture, for ammonia nitrogen waste water process；
4）Using the acid dissolving rare earths material or rare earth oxide in the earth solution, into rare earth extraction separation system or with
Rare earth oxide after diluted acid dissolving enters together rare earth extraction separation system；
5）Rare earth oxide, rare earth carbonate or rare-earth hydroxide are formed respectively by the rare earth in the earth solution；
6）By step 5）In the rare earth oxide forming process：The earth solution is adjusted into pH values, with oxalic acid or solvable
Property oxalates carry out rare-earth precipitation, obtain rare-earth oxalate precipitate, then drying and calcining form rare earth oxide；
7) by step 5）In the rare earth carbonate or rare-earth hydroxide forming process：The earth solution is used can
Soluble carbonate or hydroxide carry out rare-earth precipitation, obtain the rare earth carbonate or rare-earth hydroxide；
8）By step 6）The rare earth oxide for producing and step 7）The rare earth carbonate for producing or rare-earth hydroxide
After being dissolved with diluted acid respectively, into rare earth extraction separation system.
2. the method for the comprehensive utilization of zirconium oxychloride spent acid according to claim 1, it is characterised in that the water is mutually oxygen
Change zirconium spent acid and remove the waste acid liquor after scandium element.
3. the method for the comprehensive utilization of zirconium oxychloride spent acid according to claim 1, it is characterised in that the soluble carbon
Hydrochlorate is sodium carbonate or sodium bicarbonate.
4. the method for the comprehensive utilization of zirconium oxychloride spent acid according to claim 1, it is characterised in that the hydroxide
It is sodium hydroxide or ammonia.
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