CN104386764A - Method for producing iron oxide black by acid waste water in titanium-dioxide industry - Google Patents
Method for producing iron oxide black by acid waste water in titanium-dioxide industry Download PDFInfo
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- CN104386764A CN104386764A CN201410666782.2A CN201410666782A CN104386764A CN 104386764 A CN104386764 A CN 104386764A CN 201410666782 A CN201410666782 A CN 201410666782A CN 104386764 A CN104386764 A CN 104386764A
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- waste water
- iron oxide
- oxide black
- acid waste
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Abstract
The invention relates to a method for producing iron oxide black by acid waste water in the titanium-dioxide industry. The method comprises the following steps: discharging the raw acid waste water into a reaction groove; adding iron sheet and/or iron powder into the reaction groove; throwing calcium oxide powder into the reaction groove; discharging a solution after the reaction is finished into a filter press for pressing and filtering, preparing ferrous-sulfate waste water and calcium-sulfate waste residue and preparing into calcium-sulfate powder; discharging the ferrous-sulfate waste water into the reaction tank, adding a sodium hydroxide solution into the reaction tank and a generating ferrous hydroxide liquid; carrying out heating and oxidizing reaction, gradually forming mixed floccule and generating small-granule ferroferric oxide; carrying out solid-liquid separation, thus obtaining mother liquor water and filter residue, washing the dried filter residue, carrying out pressing and filtering again, thus obtaining pure ferroferric oxide filter residue, drying the pure ferroferric oxide filter residue by a baking box, crushing the dried filter residue, thus obtaining finished iron oxide black, packaging and warehousing. The method has the advantage that the pollution-free treatment and the resource recycling of the acid waste water produced by the titanium-dioxide industry are realized.
Description
Technical field
The present invention relates to the production method technical field of iron oxide black, especially a kind of titanium dioxide industry acid waste water produces the method for iron oxide black.
Background technology
Titanium powder plant adopts Production By Sulfuric Acid Process titanium dioxide pigment, is be (FeTiO with ilmenite
3) be raw material, use sulfuric acid decomposition ore, titanium and iron all become vitriol and dissolve, and after completing production titanium dioxide pigment major product and the ferrous by-product of reclaim(ed) sulfuric acid, still have a large amount of acid waste water containing ferrous sulfate to discharge.In this acid waste water, sulfur acid ferrous iron (FeSO
47H
2o) about 20% (200g/L), sulfuric acid are about 15-20% (average 18%), and other impurity is no more than 1.0% as Ti, Mn, Mg, Al etc.Acid waste water can not directly discharge, and pollutes the environment, and containing more useful matter.Acid waste water needs first to carry out pre-treatment ability further extraction useful matter wherein, and after carrying out pre-treatment, obtain a large amount of copperas solutions, ferrous sulfate has higher value, can make iron oxide black, and iron oxide black can be used for preparing pigment.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of titanium dioxide industry acid waste water to produce the method for iron oxide black, achieve the nuisanceless disposal of the acid waste water that titanium dioxide industry is produced, resource utilization is recycled.
The technical solution adopted for the present invention to solve the technical problems is: a kind of titanium dioxide industry acid waste water produces the method for iron oxide black, has following steps:
1. the raw material acid waste water containing ferrous sulfate and sulfuric acid is entered reactive tank;
2. in reactive tank, add iron sheet and/or iron powder, in reactive tank, pass into steam, acid waste water is heated, promote that iron sheet and/or iron powder and sulfuric acid carry out Fe+H
2sO
4→ FeSO
4+ H
2↑ reaction, produces more ferrous sulfate;
3. after question response for some time, in reactive tank, add lime powder, and CaO+H is carried out in stirring
2sO
4→ CaSO
4+ H
2o neutralization reaction, make the remaining sulfuric acid in acid waste water generate calcium sulfate precipitation thing, the pH value to reactive tank inner acidic waste water reaches 3-4 and namely stops adding lime powder;
4. after reaction being completed, solution enters pressure filter and carries out press filtration, obtain ferrous sulfate waste water and calcium sulfate waste residues after press filtration, the ferrous sulfate waste water after press filtration is entered purification tank for liquid waste, the calcium sulfate waste residues after press filtration enters oven for drying, waste residue after drying is pulverized, makes calcium sulphate powders;
5. the ferrous sulfate waste water in purification tank for liquid waste is entered retort, in retort, add sodium hydroxide solution, adjust ph is alkalescence extremely, FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4generate hydroxide ferrous solution;
6. add to solution and pass into air and steam, carry out heating oxidizing reaction, 4Fe (OH)
2+ O
2+ 2H
2o → 4Fe (OH)
3form ferrous hydroxide and other middle transition mixing floss gradually, after oxidizing reaction certain hour of heating, kinetics Fe (OH) gradually
2+ 2Fe (OH)
3→ Fe
3o
4+ 4H
2o, generates short grained Z 250;
7. the Z 250 solution of above-mentioned preparation is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, the filter residue obtained is washed, again carry out press filtration, obtain clean Z 250 filter residue by oven for drying, after being pulverized by the filter residue after oven dry, obtain finished product iron oxide black powder packaging warehouse-in.
Further, as preferably, step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.
Further, step 2. in stop adding iron sheet and/or iron powder when sulfuric acid content is reduced to below 10% in reactive tank.
Further, reduce acid waste gas discharge, step 2. in when passing into steam in reactive tank, with water vapor volatilization sulfuric acid mist waste gas carry out centralized collection after enter alkali lye spray absorber.
Step 5. in sodium hydroxide solution the massfraction of sodium hydroxide be 30%.
Step 5. in solution is adjusted to pH value is 9 ± 0.5.
Step 6. middle control solution temperature is 80 ± 5 DEG C.
Step 6. in oxidation time of heating be 3-4 hour.
The invention has the beneficial effects as follows, the method of titanium dioxide industry acid waste water production iron oxide black of the present invention achieves the nuisanceless disposal of the acid waste water that titanium dioxide industry is produced, resource utilization is recycled, and reaches calcium sulphate powders and iron oxide black powder, can be used for other industrial raw material.
Embodiment
A kind of titanium dioxide industry acid waste water of the present invention produces the method for iron oxide black, has following steps:
1. the raw material acid waste water containing ferrous sulfate and sulfuric acid is entered reactive tank;
2. in reactive tank, add iron sheet and/or iron powder, in reactive tank, pass into steam, acid waste water is heated, promote that iron sheet and/or iron powder and sulfuric acid carry out Fe+H
2sO
4→ FeSO
4+ H
2↑ reaction, produces more ferrous sulfate;
3. after question response for some time, in reactive tank, add lime powder, and CaO+H is carried out in stirring
2sO
4→ CaSO
4+ H
2o neutralization reaction, make the remaining sulfuric acid in acid waste water generate calcium sulfate precipitation thing, the pH value to reactive tank inner acidic waste water reaches 3-4 and namely stops adding lime powder;
4. after reaction being completed, solution enters pressure filter and carries out press filtration, obtain ferrous sulfate waste water and calcium sulfate waste residues after press filtration, the ferrous sulfate waste water after press filtration is entered purification tank for liquid waste, the calcium sulfate waste residues after press filtration enters oven for drying, waste residue after drying is pulverized, makes calcium sulphate powders;
5. the ferrous sulfate waste water in purification tank for liquid waste is entered retort, in retort, add sodium hydroxide solution, adjust ph is alkalescence extremely, FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4generate hydroxide ferrous solution;
6. add to solution and pass into air and steam, carry out heating oxidizing reaction, 4Fe (OH)
2+ O
2+ 2H
2o → 4Fe (OH)
3form ferrous hydroxide and other middle transition mixing floss gradually, after oxidizing reaction certain hour of heating, kinetics Fe (OH) gradually
2+ 2Fe (OH)
3→ Fe
3o
4+ 4H
2o, generates short grained Z 250;
7. the Z 250 solution of above-mentioned preparation is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, the filter residue obtained is washed, again carry out press filtration, obtain clean Z 250 filter residue by oven for drying, after being pulverized by the filter residue after oven dry, obtain finished product iron oxide black powder packaging warehouse-in.
Step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.Temperature too low reaction speed is slow, and temperature is too high has too much sulfuric acid mist generation, atmosphere pollution.
Step 2. in stop adding iron sheet and/or iron powder when sulfuric acid content is reduced to below 10% in reactive tank.
Step 2. in when passing into steam in reactive tank, with water vapor volatilization sulfuric acid mist waste gas carry out centralized collection after enter alkali lye spray absorber.
Step 5. in sodium hydroxide solution the massfraction of sodium hydroxide be 30%.
Step 5. in solution is adjusted to pH value is 9 ± 0.5.
Step 6. middle control solution temperature is 80 ± 5 DEG C.
Step 6. in oxidation time of heating be 3-4 hour.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (8)
1. titanium dioxide industry acid waste water produces a method for iron oxide black, it is characterized in that having following steps:
1. the raw material acid waste water containing ferrous sulfate and sulfuric acid is entered reactive tank;
2. in reactive tank, add iron sheet and/or iron powder, in reactive tank, pass into steam, acid waste water is heated, promote that iron sheet and/or iron powder and sulfuric acid carry out Fe+H
2sO
4→ FeSO
4+ H
2↑ reaction, produces more ferrous sulfate;
3. after question response for some time, in reactive tank, add lime powder, and CaO+H is carried out in stirring
2sO
4→ CaSO
4+ H
2o neutralization reaction, make the remaining sulfuric acid in acid waste water generate calcium sulfate precipitation thing, the pH value to reactive tank inner acidic waste water reaches 3-4 and namely stops adding lime powder;
4. after reaction being completed, solution enters pressure filter and carries out press filtration, obtain ferrous sulfate waste water and calcium sulfate waste residues after press filtration, the ferrous sulfate waste water after press filtration is entered purification tank for liquid waste, the calcium sulfate waste residues after press filtration enters oven for drying, waste residue after drying is pulverized, makes calcium sulphate powders;
5. the ferrous sulfate waste water in purification tank for liquid waste is entered retort, in retort, add sodium hydroxide solution, adjust ph is alkalescence extremely, FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4generate hydroxide ferrous solution;
6. add to solution and pass into air and steam, carry out heating oxidizing reaction, 4Fe (OH)
2+ O
2+ 2H
2o → 4Fe (OH)
3form ferrous hydroxide and other middle transition mixing floss gradually, after oxidizing reaction certain hour of heating, kinetics Fe (OH) gradually
2+ 2Fe (OH)
3→ Fe
3o
4+ 4H
2o, generates short grained Z 250;
7. the Z 250 solution of above-mentioned preparation is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, the filter residue obtained is washed, again carry out press filtration, obtain clean Z 250 filter residue by oven for drying, after being pulverized by the filter residue after oven dry, obtain finished product iron oxide black powder packaging warehouse-in.
2. titanium dioxide industry acid waste water as claimed in claim 1 produces the method for iron oxide black, it is characterized in that: step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.
3. titanium dioxide industry acid waste water as claimed in claim 1 or 2 produces the method for iron oxide black, it is characterized in that: step 2. in stop adding iron sheet and/or iron powder when sulfuric acid content is reduced to below 10% in reactive tank.
4. titanium dioxide industry acid waste water as claimed in claim 1 produces the method for iron oxide black, it is characterized in that: step 2. in when passing into steam in reactive tank, enter alkali lye spray absorber after carrying out centralized collection with the sulfuric acid mist waste gas of water vapor volatilization.
5. titanium dioxide industry acid waste water as claimed in claim 1 produces the method for iron oxide black, it is characterized in that: step 5. in sodium hydroxide solution the massfraction of sodium hydroxide be 30%.
6. titanium dioxide industry acid waste water as claimed in claim 1 produces the method for iron oxide black, it is characterized in that: step 5. in solution is adjusted to pH value is 9 ± 0.5.
7. titanium dioxide industry acid waste water as claimed in claim 1 produces the method for iron oxide black, it is characterized in that: step 6. middle control solution temperature is 80 ± 5 DEG C.
8. titanium dioxide industry acid waste water as described in claim 1 or 7 produces the method for iron oxide black, it is characterized in that: step 6. in oxidation time of heating be 3-4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410666782.2A CN104386764A (en) | 2014-11-20 | 2014-11-20 | Method for producing iron oxide black by acid waste water in titanium-dioxide industry |
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|---|---|---|---|
| CN201410666782.2A CN104386764A (en) | 2014-11-20 | 2014-11-20 | Method for producing iron oxide black by acid waste water in titanium-dioxide industry |
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|---|---|
| CN104386764A true CN104386764A (en) | 2015-03-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850951A (en) * | 2019-04-01 | 2019-06-07 | 中钢集团南京新材料研究院有限公司 | A method of iron oxide black is prepared using titanium white by product object |
| CN115872433A (en) * | 2022-09-26 | 2023-03-31 | 浙江天川环保科技有限公司 | Method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid |
-
2014
- 2014-11-20 CN CN201410666782.2A patent/CN104386764A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850951A (en) * | 2019-04-01 | 2019-06-07 | 中钢集团南京新材料研究院有限公司 | A method of iron oxide black is prepared using titanium white by product object |
| CN115872433A (en) * | 2022-09-26 | 2023-03-31 | 浙江天川环保科技有限公司 | Method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid |
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