CN105347436A - Recovery application method for titanium and zirconium in zirconium oxychloride waste acid - Google Patents
Recovery application method for titanium and zirconium in zirconium oxychloride waste acid Download PDFInfo
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- CN105347436A CN105347436A CN201510787936.8A CN201510787936A CN105347436A CN 105347436 A CN105347436 A CN 105347436A CN 201510787936 A CN201510787936 A CN 201510787936A CN 105347436 A CN105347436 A CN 105347436A
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- zirconium
- titanium phosphate
- ammonia nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
Abstract
The invention discloses a recovery method for titanium and zirconium in zirconium oxychloride waste acid. The method comprises performing acid-base value adjusting processing on the zirconium oxychloride waste acid by using sodium hydroxide, so as to obtain a titanium zirconium phosphate precipitate; washing the titanium zirconium phosphate precipitate with pure water, and filtering to obtain a titanium zirconium phosphate filter cake A; using water to prepare a slurry of the titanium zirconium phosphate filter cake A, adjusting the pH value by using an alkaline substance, and filtering, so as to obtain a titanium zirconium phosphate filter cake B; performing drying processing on the titanium zirconium phosphate filter cake B, so as to obtain a titanium zirconium phosphate semi-finished product; and performing crushing and granulating, so as to obtain the titanium zirconium phosphate product. The production technology flow and the equipment are simple, the method is easy to control, suitable for industrialized production and low in cost, ecological environment is protected and economic value is produced.
Description
Technical field
The present invention relates to zirconium oxychloride spent acid comprehensive application technology field, the titanium zirconium recycle method particularly in zirconium oxychloride spent acid.
Background technology
Zirconium oxychloride end-use is extensive, is the basic material of zirconium chemical industry, the huge market demand; The zirconium oxychloride of domestic usual employing alkali fusion explained hereafter can produce spent acid; Except containing except residual zr element in spent acid, also having titanium, scandium, rare earth etc., is the quality ensureing zirconium oxychloride, and most enterprise does not usually recycle spent acid or recycles and once enters waste water station and process.According to statistics, often produce one ton of zirconium oxychloride and about generate 100 ~ 500L spent acid.Zirconia content 10 ~ 30g/L in spent acid, titanium oxide content 10 ~ 20g/L.
Ammonia nitrogen is with free ammonia (NH
3) and ammonium ion (NH
4+) form is present in nitrogen in water, ammonia nitrogen is the principal element causing body eutrophication, can cause the algae in water body and microorganism amount reproduction, and the dissolved oxygen in water body is sharply declined, cause fish and other hydrobiont hypoxia deaths, water quality is caused and has a strong impact on.Ammonia nitrogen waste water commonly uses treatment process biological process, blow-off method, chemical precipitation method, break point chlorination, membrane separation process, ion exchange method, oxidation style etc.
Zirconium titanium phosphate is typical cationic lamellar compound, has the ion-exchange capacity as ion exchange resin; Zirconium titanium phosphate can directly and alkali substance reaction or it is protonated after ion-exchange again, with Ion Exchange Resin Phase ratio, have good stability.
Carried out reclaiming by titanium zr element in zirconium oxychloride spent acid and be applied in the ammonia nitrogen waste water process of ion exchange method, its technological process of production equipment is simple, and easy to control, be applicable to suitability for industrialized production, cost is low; Titanium zr element in zirconium oxychloride spent acid is reclaimed and applied, both protected ecotope, and created economic worth again.
China Patent Publication No. CN104342559A discloses one synthetical recovery multiple element method from zirconium oxychloride waste liquid, is extracted Scium trioxide and rare earth, has carried out enrichment to rare earth, titanium zirconium by multi-stage extracting process; The mode of extraction is used to be separated titanium, zr element; But its process CIMS is long, do not set forth the application method that titanium, zr element are follow-up yet.
Summary of the invention
Technical problem to be solved by this invention is, a kind of method reclaiming titanium zirconium in zirconium oxychloride spent acid is provided, by utilizing the titanium zr element in phosphoric acid or calcium phosphate precipitation process spent acid, obtain zirconium titanium phosphate throw out, thus obtain zirconium titanium phosphate product, and be applied in the ammonia nitrogen waste water process of ion exchange method.
The present invention is achieved through the following technical solutions above-mentioned purpose.Titanium zirconium recycle method in zirconium oxychloride spent acid, its processing step is as follows:
1) sodium hydroxide is used to carry out the process of acid adjustment basicity to zirconium oxychloride waste acid liquor, adjustment acidity is 2N ~ 0.2N, and through phosphoric acid or calcium phosphate precipitation process, the Mo Er number ︰ phosphoric acid of wherein titanium zr element or phosphatic mole number is made to be 1 ︰ 2 ~ 3, and when pH value reaches 1 ~ 5, as interpolation phosphoric acid or phosphatic terminal, obtain zirconium titanium phosphate throw out;
2) zirconium titanium phosphate throw out pure water step 1) obtained, according to solid-to-liquid ratio 1 ︰ 2 ~ 3, washs 4 ~ 5 times, and filtration obtains zirconium titanium phosphate filter cake A;
3) by described zirconium titanium phosphate filter cake A, size mixing to solid-to-liquid ratio through pure water and be 1 ︰ 2 ~ 3, and use alkaline matter adjust pH to 6 ~ 9, filter to obtain zirconium titanium phosphate filter cake B;
4) by described zirconium titanium phosphate filter cake B, drying process, dry temperature is 30 ~ 270 DEG C, obtains zirconium titanium phosphate work in-process;
5) by described zirconium titanium phosphate work in-process, through pulverizing, granulation, zirconium titanium phosphate product is obtained; The tap density of described zirconium titanium phosphate product is 0.6 ~ 1.2g/cm
3, described zirconium titanium phosphate product is containing titanium oxide and zirconium white amount 38 ~ 42%;
6) described zirconium titanium phosphate product is passed through dynamic adsorption or static adsorption method, for the ammonia nitrogen waste water process of ion exchange method, make the ammonia nitrogen ion in described zirconium titanium phosphate product absorption waste water; After the absorption of described zirconium titanium phosphate product is saturated, carry out returning with acid and wash multiplexing, the ammonia nitrogen waste water treatment method of the solution high density of the full ammonia nitrogen of absorption processes;
Described dynamic adsorption refers to and adopts ion exchange column to be filled by described zirconium titanium phosphate product, fills up sealing, then carries out adsorption treatment with ammonia nitrogen waste water from the mode of bottom in and top out in ion exchange column;
Described Static Adsorption refers to the ammonia nitrogen dropping into zirconium titanium phosphate product and carry out in whip attachment waste water in large-scale effluent storage pond, and described Static Adsorption saturated capacity is 30 ~ 50mg/g; And after treatment, the ammonia nitrogen concentration in waste water is less than 15g/m
3.
The diameter of described ion exchange column and pillar height ratio are 1 ︰ 0.5 ~ 3;
Described ion exchange column fills zirconium titanium phosphate product dynamic adsorption saturated capacity 17 ~ 19mg/g; And after treatment, the ammonia nitrogen concentration in waste water is less than 15g/m
3.
Further, the described equipment filtering employing is whizzer or plate-and-frame filter press.
Further, described alkaline matter is sodium carbonate, sodium bicarbonate or sodium hydroxide.
Further, the mode of described drying treatment comprises that natural drying is air-dry, oven drying, expansion drying or spraying dry.
Further, described acid is hydrochloric acid, nitric acid or both mixtures.
Further, described zirconium titanium phosphate product is applicable to the ammonia nitrogen waste water process of inorganic, organic ammonia nitrogen and high content of salt.
Beneficial effect of the present invention is, its technological process of production equipment is simple, and easy to control, be applicable to suitability for industrialized production, cost is low, both protects ecotope, creates economic worth again.In zirconium oxychloride spent acid, the rate of recovery of titanium zr element reaches 88 ~ 92%, and recovering effect is remarkable.Ammonia nitrogen in waste water concentration through zirconium titanium phosphate adsorption treatment is less than 15g/m
3, meet the primary standard of ammonia nitrogen in standard GB/T 8978-1996; Process waste water absorption ammonia nitrogen Be very effective.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.See Fig. 1, the recycle method of titanium zirconium in zirconium oxychloride spent acid, its processing step is as follows:
1. zirconium oxychloride spent acid 101 solution acid adjustment basicity, and through phosphoric acid or calcium phosphate precipitation process, obtain zirconium titanium phosphate throw out 102; In described zirconium oxychloride spent acid 101, the Mo Er number ︰ phosphoric acid of titanium zr element or phosphatic mole number are 1 ︰ 2 ~ 3, and when pH value reaches 1 ~ 5, as interpolation phosphoric acid or phosphatic terminal;
2. zirconium titanium phosphate throw out described in is through washing, filtering to obtain zirconium titanium phosphate filter cake; Filter available whizzer or plate-and-frame filter press, obtain zirconium titanium phosphate filter cake A;
3. couple described zirconium titanium phosphate filter cake A to size mixing 103 (solid-to-liquid ratio is 1 ︰ 2 ~ 3) through pure water, and uses alkaline matter (sodium carbonate, sodium bicarbonate, sodium hydroxide) adjust pH (being adjusted to pH=6 ~ 9), after filtration zirconium titanium phosphate filter cake B104;
4. zirconium titanium phosphate filter cake B104 described in, is the drying treatment of 50 ~ 270 DEG C through temperature, obtains zirconium titanium phosphate work in-process 105; Dry available oven equipment, flash drying equipment, spray drying device or natural drying are air-dry;
5. zirconium titanium phosphate work in-process 105 described in, through pulverizing, granulation, obtain zirconium titanium phosphate product 106;
6. zirconium titanium phosphate product 106 described in, for the ammonia nitrogen waste water process 107 of ion exchange method; And carry out dynamic adsorption and multiplexing or Static Adsorption by ion exchange column.
Described dynamic adsorption refers to that fill with described zirconium titanium phosphate product, fill up sealing, the mode of ammonia nitrogen waste water bottom in and top out carries out adsorption treatment with ion exchange column (diameter and pillar height ratio are 1 ︰ 0.5 ~ 3); Diameter 1m, highly for 1m ion exchange column can fill zirconium titanium phosphate product 600kg; Zirconium titanium phosphate 600kg can adsorb ammonia nitrogen 10.2 ~ 11.4kg, and the ammonia nitrogen concentration after adsorption treatment in waste water is less than 15g/m
3; Dynamic adsorption saturated capacity 17 ~ 19mg/g;
After the absorption of described zirconium titanium phosphate product is saturated, carry out returning with acid (hydrochloric acid, nitric acid) and wash multiplexing, the method for the ammonia nitrogen waste water process of the solution high density of the full ammonia nitrogen of absorption processes.
Described Static Adsorption refers in large-scale effluent storage pond, and the ratio dropping into 600kg zirconium titanium phosphate product according to ammonia nitrogen 18 ~ 30kg in waste water is carried out, and the time is the whip attachment of 5 ~ 48 hours, and Static Adsorption saturated capacity is 30 ~ 50mg/g.
Described zirconium titanium phosphate product may be used for all ammonia nitrogen waste water process, comprises the ammonia nitrogen waste water process of the high content of salt that inorganic, organic ammonia nitrogen and biological process cannot process.
embodiment 1:the recycle method of titanium zirconium in zirconium oxychloride spent acid, its processing step is as follows:
1. zirconium oxychloride spent acid 101 solution acid adjustment basicity, and through phosphoric acid or calcium phosphate precipitation process, obtain zirconium titanium phosphate throw out 102; In described zirconium oxychloride spent acid 101, the Mo Er number ︰ phosphoric acid of titanium zr element or phosphatic mole number are 1 ︰ 2.5, and when pH value reaches 1.3, as interpolation phosphoric acid or phosphatic terminal;
2. zirconium titanium phosphate throw out is through washing, filtering to obtain zirconium titanium phosphate filter cake; Filter available whizzer or plate-and-frame filter press;
3. couple described zirconium titanium phosphate filter cake A is 1 ︰ 3 through pure water 103(solid-to-liquid ratio of sizing mixing), adjust pH (using alkaline matter: sodium carbonate, sodium bicarbonate, sodium hydroxide, be adjusted to pH=6.8), filters to obtain zirconium titanium phosphate filter cake B104
4. zirconium titanium phosphate filter cake B104, through oven drying process (120 DEG C), obtains zirconium titanium phosphate work in-process 105;
5. zirconium titanium phosphate work in-process 105, through pulverizing, granulation, obtain zirconium titanium phosphate product 106;
6. product zirconium titanium phosphate product 106; , for the ammonia nitrogen waste water process 107 of ion exchange method; And undertaken adsorbing and multiplexing or Static Adsorption by dynamic ion exchange post.
Dynamic adsorption refers to ion exchange column (diameter and pillar height ratio are 1 ︰ 0.5 ~ 3), fills, fill up sealing with described zirconium titanium phosphate product, and ammonia nitrogen waste water bottom in and top out ground mode carries out adsorption treatment; Diameter 1m, highly for 1m ion exchange column can fill zirconium titanium phosphate product 600kg; Process ammonia nitrogen solubility 600g/m
3waste water 17.5m
3; Ammonia nitrogen concentration after adsorption treatment in waste water is less than 15g/m
3; Adsorption treatment ammonia nitrogen 10.5kg; Dynamic adsorption saturated capacity 17.5mg/g.
After the absorption of this zirconium titanium phosphate product is saturated, carry out returning with certain density acid (hydrochloric acid, nitric acid) and wash multiplexing, the method for the ammonia nitrogen waste water process of the solution high density of the full ammonia nitrogen of absorption processes.
Static Adsorption refers to that large-scale effluent storage pond is dropped into zirconium titanium phosphate product and carried out whip attachment.Ammonia nitrogen in waste water solubility 600g/m
3waste water 35.3m
3, the ammonia nitrogen concentration after treatment in waste water is less than 15g/m
3; 600kg zirconium titanium phosphate product can adsorb ammonia nitrogen 21.18kg; Ammonia nitrogen Static Adsorption saturated capacity is 35.3mg/g.
Zirconium titanium phosphate product may be used for all ammonia nitrogen waste water process, comprises the ammonia nitrogen waste water process of the high content of salt that inorganic, organic ammonia nitrogen and biological process cannot process.
embodiment 2:the recycle method of titanium zirconium in zirconium oxychloride spent acid, its processing step is as follows:
1. zirconium oxychloride spent acid 101 solution acid adjustment basicity, and through phosphoric acid or calcium phosphate precipitation process, obtain zirconium titanium phosphate throw out 102; In described zirconium oxychloride spent acid 101, the Mo Er number ︰ phosphoric acid of titanium zr element or phosphatic mole number are 1 ︰ 2.2, and when pH value reaches 2.7, as interpolation phosphoric acid or phosphatic terminal;
2. zirconium titanium phosphate throw out is through washing, filtering to obtain zirconium titanium phosphate filter cake; Filter available whizzer or plate-and-frame filter press;
3. couple described zirconium titanium phosphate filter cake A is 1 ︰ 2.8 through pure water 103(solid-to-liquid ratio of sizing mixing), adjust pH (using alkaline matter: sodium carbonate, sodium bicarbonate, sodium hydroxide, be adjusted to pH=7.5), filters to obtain zirconium titanium phosphate filter cake B104
4. zirconium titanium phosphate filter cake B104, through the air-dry process of natural drying, obtains zirconium titanium phosphate work in-process 105.
5. zirconium titanium phosphate work in-process 105, through pulverizing, granulation, obtain zirconium titanium phosphate product 106.
6. product zirconium titanium phosphate product 106, for the ammonia nitrogen waste water process 107 of ion exchange method; And undertaken adsorbing and multiplexing or Static Adsorption by dynamic ion exchange post.
Dynamic adsorption refers to ion exchange column (diameter and pillar height ratio are 1 ︰ 0.5 ~ 3), fills, fill up sealing with described zirconium titanium phosphate product, and ammonia nitrogen waste water bottom in and top out ground mode carries out adsorption treatment; Diameter 1 meter is highly that 1 meter of ion exchange column can fill zirconium titanium phosphate product 600kg; Process ammonia nitrogen solubility 600g/m
3waste water 18.3m
3; Ammonia nitrogen concentration after adsorption treatment in waste water is less than 15g/m
3; Adsorption treatment ammonia nitrogen 10.98kg; Dynamic adsorption saturated capacity 18.3mg/g.
After the absorption of this zirconium titanium phosphate product is saturated, carry out returning with acid (hydrochloric acid, nitric acid) and wash multiplexing, the method for the ammonia nitrogen waste water process of the solution high density of the full ammonia nitrogen of absorption processes.
Static Adsorption refers to that the whip attachment that a certain amount of zirconium titanium phosphate product carries out certain hour is dropped in large-scale effluent storage pond.Ammonia nitrogen in waste water solubility 600g/m
3waste water 48.2m
3, the ammonia nitrogen concentration after treatment in waste water is less than 15g/m
3; Adsorption treatment ammonia 600kg zirconium titanium phosphate product can adsorb ammonia nitrogen 28.92kg; Ammonia nitrogen Static Adsorption saturated capacity is 48.2mg/g.
Zirconium titanium phosphate product may be used for all ammonia nitrogen waste water process, comprises the ammonia nitrogen waste water process of the high content of salt that inorganic, organic ammonia nitrogen and biological process cannot process.
embodiment 3:the recycle method of titanium zirconium in zirconium oxychloride spent acid, its processing step is as follows:
1. zirconium oxychloride spent acid 101 solution acid adjustment basicity, and through phosphoric acid or calcium phosphate precipitation process, obtain zirconium titanium phosphate throw out 102; In described zirconium oxychloride spent acid 101, the Mo Er number ︰ phosphoric acid of titanium zr element or phosphatic mole number are 1 ︰ 2.7, and when pH value reaches 3.6, as interpolation phosphoric acid or phosphatic terminal.
2. zirconium titanium phosphate throw out is through washing, filtering to obtain zirconium titanium phosphate filter cake; Filter available whizzer or plate-and-frame filter press.
3. couple described zirconium titanium phosphate filter cake A is 1 ︰ 2.2 through pure water 103(solid-to-liquid ratio of sizing mixing), adjust pH (using alkaline matter: sodium carbonate, sodium bicarbonate, sodium hydroxide, be adjusted to pH=8.2), filters to obtain zirconium titanium phosphate filter cake B104.
4. zirconium titanium phosphate filter cake B104, through expansion drying process (270 DEG C), obtains zirconium titanium phosphate work in-process 105.
5. zirconium titanium phosphate work in-process 105, through pulverizing, granulation, obtain zirconium titanium phosphate product 106.
6. product zirconium titanium phosphate product 106, for the ammonia nitrogen waste water process 107 of ion exchange method; And undertaken adsorbing and multiplexing or Static Adsorption by dynamic ion exchange post.
Dynamic adsorption refers to ion exchange column (diameter and pillar height ratio are 1 ︰ 0.5 ~ 3), fills, fill up sealing with described zirconium titanium phosphate product, and ammonia nitrogen waste water bottom in and top out ground mode carries out adsorption treatment; Diameter 1m, highly for 1m ion exchange column can fill zirconium titanium phosphate product 600kg; Process ammonia nitrogen solubility 600g/m
3waste water 18.7m
3; Ammonia nitrogen concentration after adsorption treatment in waste water is less than 15g/m
3; Adsorption treatment ammonia nitrogen 11.23kg; Dynamic adsorption saturated capacity 18.7mg/g.
After the absorption of this zirconium titanium phosphate product is saturated, carry out returning with acid (hydrochloric acid, nitric acid) and wash multiplexing, this returns washing lotion and can process by the method for the ammonia nitrogen waste water process of high density.
Static Adsorption refers to that large-scale effluent storage pond is dropped into zirconium titanium phosphate product and carried out whip attachment.Ammonia nitrogen in waste water solubility 600g/m
3waste water 37.5m
3, the ammonia nitrogen concentration after treatment in waste water is less than 15g/m
3; 600kg zirconium titanium phosphate product can adsorb ammonia nitrogen 22.5kg; Static Adsorption saturated capacity is 37.5mg/g.
Zirconium titanium phosphate product may be used for all ammonia nitrogen waste water process, comprises the ammonia nitrogen waste water process of the high content of salt that inorganic, organic ammonia nitrogen and biological process cannot process.
embodiment 4:the recycle method of titanium zirconium in zirconium oxychloride spent acid, its processing step is as follows:
1. zirconium oxychloride spent acid 101 solution acid adjustment basicity, and through phosphoric acid or calcium phosphate precipitation process, obtain zirconium titanium phosphate throw out 102; In described zirconium oxychloride spent acid 101, the Mo Er number ︰ phosphoric acid of titanium zr element or phosphatic mole number are 1 ︰ 2.9, and when pH value reaches 4.8, as interpolation phosphoric acid or phosphatic terminal.
2. zirconium titanium phosphate throw out is through washing, filtering to obtain zirconium titanium phosphate filter cake; Filter available whizzer or plate-and-frame filter press.
3. couple described zirconium titanium phosphate filter cake A is 1 ︰ 2.5 through pure water 103(solid-to-liquid ratio of sizing mixing), adjust pH (using alkaline matter: sodium carbonate, sodium bicarbonate, sodium hydroxide, be adjusted to pH=8.8), filters to obtain zirconium titanium phosphate filter cake B104.
4. zirconium titanium phosphate filter filter cake B104, spray-dried process (180 DEG C), obtains zirconium titanium phosphate work in-process 105.
5. zirconium titanium phosphate work in-process 105, through pulverizing, granulation, obtain zirconium titanium phosphate product 106.
6. product zirconium titanium phosphate product 106, for the ammonia nitrogen waste water process 107 of ion exchange method; And undertaken adsorbing and multiplexing or Static Adsorption by dynamic ion exchange post.
Dynamic adsorption refers to ion exchange column (diameter and pillar height ratio are 1 ︰ 0.5 ~ 3), fills, fill up sealing with described zirconium titanium phosphate product, ammonia nitrogen waste water bottom in and top out carry out adsorption treatment; Diameter 1m, highly for 1m ion exchange column can fill zirconium titanium phosphate product 600kg; Process ammonia nitrogen solubility 600g/m
3waste water 19m
3; Ammonia nitrogen concentration after adsorption treatment in waste water is less than 15g/m
3; Adsorption treatment ammonia nitrogen 11.4kg; Dynamic adsorption saturated capacity 19mg/g.
After the absorption of this zirconium titanium phosphate product is saturated, carry out returning with acid (hydrochloric acid, nitric acid) and wash multiplexing, the method for the ammonia nitrogen waste water process of the solution high density of the full ammonia nitrogen of absorption processes.
Static Adsorption refers to that large-scale effluent storage pond is dropped into zirconium titanium phosphate product and carried out whip attachment.Ammonia nitrogen in waste water solubility 600g/m
3waste water 50m
3, the ammonia nitrogen concentration after treatment in waste water is less than 15g/m
3; 600kg zirconium titanium phosphate product can adsorb ammonia nitrogen 30kg; Static Adsorption saturated capacity is 50mg/g.
Zirconium titanium phosphate product may be used for all ammonia nitrogen waste water process, comprises the ammonia nitrogen waste water process of the high content of salt that inorganic, organic ammonia nitrogen and biological process cannot process.
The performance analysis of titanium zirconium recycle in zirconium oxychloride spent acid:
Produce 1 ton of zirconium oxychloride, produce the spent acid 300L containing titanium oxide 15g/L and zirconium white 20g/L;
Adopt method of the present invention, zirconium titanium phosphate product 23.6kg can be produced, titanium oxide and zirconic content about 40% in zirconium titanium phosphate product, the total yield of titanium zr element about 90% in zirconium oxychloride spent acid, Static Adsorption ammonia nitrogen 1.18kg, Static Adsorption saturated capacity is 50mg/g, and can process solubility is 600g/m
3ammonia nitrogen waste water 1.96m
3.
Claims (6)
1. the titanium zirconium recycle method in zirconium oxychloride spent acid, it is characterized in that, its processing step is as follows:
1) sodium hydroxide is used to carry out the process of acid adjustment basicity to zirconium oxychloride waste acid liquor, adjustment acidity is 2N ~ 0.2N, and through phosphoric acid or calcium phosphate precipitation process, the Mo Er number ︰ phosphoric acid of wherein titanium zr element or phosphatic mole number is made to be 1 ︰ 2 ~ 3, and when pH value reaches 1 ~ 5, as interpolation phosphoric acid or phosphatic terminal, obtain zirconium titanium phosphate throw out;
2) zirconium titanium phosphate throw out pure water step 1) obtained, according to solid-to-liquid ratio 1 ︰ 2 ~ 3, washs 4 ~ 5 times, and filtration obtains zirconium titanium phosphate filter cake A;
3) by described zirconium titanium phosphate filter cake A, size mixing to solid-to-liquid ratio through pure water and be 1 ︰ 2 ~ 3, and use alkaline matter adjust pH to 6 ~ 9, filter, obtain zirconium titanium phosphate filter cake B;
4) by described zirconium titanium phosphate filter cake B, drying process, dry temperature is 50 ~ 270 DEG C, obtains zirconium titanium phosphate work in-process;
5) by described zirconium titanium phosphate work in-process, through pulverizing, granulation, zirconium titanium phosphate product is obtained; The tap density of described zirconium titanium phosphate product is 0.6 ~ 1.2g/cm
3;
6) described zirconium titanium phosphate product is passed through dynamic adsorption or static adsorption method, for the ammonia nitrogen waste water process of ion exchange method, make the ammonia nitrogen ion in described zirconium titanium phosphate product absorption waste water; After the absorption of described zirconium titanium phosphate product is saturated, carry out returning with acid and wash multiplexing, the method for adsorbing the ammonia nitrogen waste water process of the solution high density of saturated ammonia nitrogen processes;
Described dynamic adsorption refers to and adopts ion exchange column to be filled by described zirconium titanium phosphate product, fills up sealing, then carries out adsorption treatment with ammonia nitrogen waste water from the mode of bottom in and top out in ion exchange column;
Described Static Adsorption refers to that large-scale effluent storage pond input zirconium titanium phosphate product carries out the ammonia nitrogen in whip attachment waste water, and described Static Adsorption saturated capacity is 30 ~ 50mg/g;
The diameter of described ion exchange column and pillar height ratio are 1 ︰ 0.5 ~ 3;
Described ion exchange column fills zirconium titanium phosphate product dynamic adsorption saturated capacity 17 ~ 19mg/g; And after treatment, the ammonia nitrogen concentration in waste water is less than 15g/m
3.
2. the titanium zirconium recycle method in zirconium oxychloride spent acid according to claim 1, is characterized in that, the described equipment filtering employing is whizzer or plate-and-frame filter press.
3. the titanium zirconium recycle method in zirconium oxychloride spent acid according to claim 1, it is characterized in that, described alkaline matter is sodium carbonate, sodium bicarbonate or sodium hydroxide.
4. the titanium zirconium recycle method in zirconium oxychloride spent acid according to claim 1, is characterized in that, the mode of described drying treatment comprises that natural drying is air-dry, oven drying, expansion drying or spraying dry.
5. the titanium zirconium recycle method in zirconium oxychloride spent acid according to claim 1, is characterized in that, described acid is hydrochloric acid, nitric acid or both mixtures.
6. the titanium zirconium recycle method in zirconium oxychloride spent acid according to claim 1, is characterized in that, described zirconium titanium phosphate product is applicable to the ammonia nitrogen waste water process of inorganic, organic ammonia nitrogen and high content of salt.
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| CN104342559A (en) * | 2014-10-17 | 2015-02-11 | 湖南稀土金属材料研究院 | Method for comprehensively recovering multiple elements from zirconium oxychloride liquid waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110885930A (en) * | 2019-11-18 | 2020-03-17 | 中国科学院过程工程研究所 | Resource utilization method of zirconium oxychloride crystallization mother liquor |
| CN110885930B (en) * | 2019-11-18 | 2021-03-09 | 中国科学院过程工程研究所 | Resource utilization method of zirconium oxychloride crystallization mother liquor |
| CN114873773A (en) * | 2022-03-28 | 2022-08-09 | 青岛天尧新材料有限公司 | Method for treating phosphorus-containing wastewater |
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