CN104445432A - Method for producing ferric oxide red by using acidic wastewater generated in titanium dioxide industry - Google Patents
Method for producing ferric oxide red by using acidic wastewater generated in titanium dioxide industry Download PDFInfo
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- CN104445432A CN104445432A CN201410666494.7A CN201410666494A CN104445432A CN 104445432 A CN104445432 A CN 104445432A CN 201410666494 A CN201410666494 A CN 201410666494A CN 104445432 A CN104445432 A CN 104445432A
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Abstract
The invention discloses a method for producing ferric oxide red by using a ferrous sulfate solution. The method comprises the following steps of discharging raw acidic wastewater into a reaction tank; adding a ferric sheet and/or iron powder into the reaction tank; adding calcium oxide powder into the reaction kettle; after finishing the reaction, discharging the solution into a filter press for filter pressing to obtain ferrous sulfate wastewater and calcium sulfate residues; discharging the ferrous sulfate wastewater into a ferric oxide red seed crystal tank, adding an alkali solution into the ferric oxide red seed crystal tank through metering, controlling the pH value at 8.5-9.5, blasting air into the solution, and oxidizing to obtain a ferric oxide red seed crystal; adding the prepared ferric oxide red seed crystal solution into an oxidization tank, adding a ferric sheet and/or iron powder into the oxidization tank, quantitatively adding a ferrous sulfate solution into the solution, and introducing air to oxidize ferrous ions to obtain ferric ions until ending the oxidization reaction; and discharging the prepared ferric oxide red solution into the filter press to obtain a finished product of ferric oxide red powder, packaging and putting the finished product into storage. By using the method, the pollution-free treatment and resource recycling of the acidic wastewater generated in the titanium dioxide industry are realized.
Description
Technical field
The present invention relates to the production technique of red iron oxide, especially a kind of method of titanium dioxide industry acid waste water production red iron oxide.
Background technology
Ferric oxide, chemical name Fe
2o
3, also known as red iron oxide, for various pigment coloration and Protective substances, the method for domestic and international production red iron oxide is more, mainly contains green vitriol calcination method, liquid-phase precipitation method, bag core method etc.
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 be used for preparing red iron oxide.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of method providing titanium dioxide industry acid waste water production red iron oxide, achieves the nuisanceless disposal of the acid waste water that titanium dioxide industry is produced, and resource utilization is recycled.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method of titanium dioxide industry acid waste water production red iron oxide, 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 iron red crystal seed formation tank, in iron red crystal seed formation tank, metering adds alkali lye, and generate ferrous hydroxide, control ph 8.5-9.5, blasts atmospheric oxidation and obtain iron red crystal seed formation in solution, 2Fe (OH)
2+ 1/2O
2→ Fe
2o
3h
2o+H
2o;
6. will obtain iron red crystal seed formation solution drops in oxidation tank, iron sheet and/or iron powder is added to the iron red crystal seed formation solution in oxidation tank, quantitatively copperas solution is added in solution, steam heating solution is passed in the solution in oxidation tank, and pass into atmospheric oxidation ferrous ion and obtain iron ion, the hydroxide radical of iron ion in water is combined and is deposited on iron red crystal seed formation on the surface, form red iron oxide gradually, the hydrogen ion produced while oxidizing reaction and iron sheet and/or iron powder react, generate ferrous ion and be oxidized to iron ion again, until oxidizing reaction terminates;
7. obtained iron oxide red solution is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, press filtration again after the filter residue washing obtained after solid-liquid separation, drying operation is carried out after obtaining clean filter residue, after filter residue after oven dry is pulverized, obtain finished product red iron oxide powder and be packaged into storehouse.
Step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.
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. described in alkali lye be sodium hydroxide solution, occur FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4reaction.
In described sodium hydroxide solution, the mass percent of sodium hydroxide is 30%.
5. step carries out at the temperature of 20-30 DEG C.
Step keeps solution temperature 80-85 DEG C when 6. passing into steam.
Step 6. time keep the pH value of solution between 3.0-4.0.
The invention has the beneficial effects as follows, the method of titanium dioxide industry acid waste water production red iron oxide of the present invention achieves the nuisanceless disposal of the acid waste water that titanium dioxide industry is produced, resource utilization is recycled, and obtains calcium sulphate powders and red iron oxide powder, can be used for other industrial raw material.
Embodiment
The method of a kind of titanium dioxide industry acid waste water production red iron oxide of the present invention, 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 iron red crystal seed formation tank, in iron red crystal seed formation tank, metering adds alkali lye, and generate ferrous hydroxide, control ph 8.5-9.5, blasts atmospheric oxidation and obtain iron red crystal seed formation in solution, 2Fe (OH)
2+ 1/2O
2→ Fe
2o
3h
2o+H
2o;
6. will obtain iron red crystal seed formation solution drops in oxidation tank, iron sheet and/or iron powder is added to the iron red crystal seed formation solution in oxidation tank, quantitatively copperas solution is added in solution, steam heating solution is passed in the solution in oxidation tank, and pass into atmospheric oxidation ferrous ion and obtain iron ion, the hydroxide radical of iron ion in water is combined and is deposited on iron red crystal seed formation on the surface, form red iron oxide gradually, the hydrogen ion produced while oxidizing reaction and iron sheet and/or iron powder react, generate ferrous ion and be oxidized to iron ion again, until oxidizing reaction terminates;
7. obtained iron oxide red solution is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, press filtration again after the filter residue washing obtained after solid-liquid separation, drying operation is carried out after obtaining clean filter residue, after filter residue after oven dry is pulverized, obtain finished product red iron oxide powder and be packaged into storehouse.
Step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.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. described in alkali lye be sodium hydroxide solution, occur FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4reaction.In described sodium hydroxide solution, the mass percent of sodium hydroxide is 30%.5. step carries out at the temperature of 20-30 DEG C.
Step keeps solution temperature 80-85 DEG C when 6. passing into steam.Step 6. time keep the pH value of solution between 3.0-4.0.
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 (9)
1. a method for titanium dioxide industry acid waste water production red iron oxide, 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 iron red crystal seed formation tank, in iron red crystal seed formation tank, metering adds alkali lye, and generate ferrous hydroxide, control ph 8.5-9.5, blasts atmospheric oxidation and obtain iron red crystal seed formation in solution, 2Fe (OH)
2+ 1/2O
2→ Fe
2o
3h
2o+H
2o;
6. will obtain iron red crystal seed formation solution drops in oxidation tank, iron sheet and/or iron powder is added to the iron red crystal seed formation solution in oxidation tank, quantitatively copperas solution is added in solution, steam heating solution is passed in the solution in oxidation tank, and pass into atmospheric oxidation ferrous ion and obtain iron ion, the hydroxide radical of iron ion in water is combined and is deposited on iron red crystal seed formation on the surface, form red iron oxide gradually, the hydrogen ion produced while oxidizing reaction and iron sheet and/or iron powder react, generate ferrous ion and be oxidized to iron ion again, until oxidizing reaction terminates;
7. obtained iron oxide red solution is entered in pressure filter, carry out solid-liquid separation, obtain mother liquid coming and filter residue, press filtration again after the filter residue washing obtained after solid-liquid separation, drying operation is carried out after obtaining clean filter residue, after filter residue after oven dry is pulverized, obtain finished product red iron oxide powder and be packaged into storehouse.
2. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 1, is characterized in that:
Step 2. in reactive tank, pass into steam, make acid waste water be heated to 50-60 DEG C.
3. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 1 or 2, 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. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 1, 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. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 1, is characterized in that: step 5. described in alkali lye be sodium hydroxide solution, there is FeSO
4+ 2NaOH → Fe (OH)
2+ Na
2sO
4reaction.
6. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 5, is characterized in that: in described sodium hydroxide solution, the mass percent of sodium hydroxide is 30%.
7. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 5, is characterized in that: 5. step carries out at the temperature of 20-30 DEG C.
8. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 1, is characterized in that: keep solution temperature 80-85 DEG C when 6. step passes into steam.
9. the method for titanium dioxide industry acid waste water production red iron oxide as claimed in claim 8, is characterized in that: step 6. time keep the pH value of solution between 3.0-4.0.
Priority Applications (1)
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|---|---|---|---|
| CN201410666494.7A CN104445432A (en) | 2014-11-20 | 2014-11-20 | Method for producing ferric oxide red by using acidic wastewater generated in titanium dioxide industry |
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|---|---|---|---|
| CN201410666494.7A CN104445432A (en) | 2014-11-20 | 2014-11-20 | Method for producing ferric oxide red by using acidic wastewater generated in titanium dioxide industry |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115793A (en) * | 2016-06-21 | 2016-11-16 | 阳山景润陶瓷色料实业有限公司 | A kind of ferric oxide red colorant and preparation method thereof |
| CN112279303A (en) * | 2020-11-26 | 2021-01-29 | 江苏宇星工贸有限公司 | Iron oxide red pigment and preparation method thereof |
| CN116040687A (en) * | 2022-11-01 | 2023-05-02 | 攀枝花末微环保科技有限公司 | Comprehensive utilization method of sulfuric acid process titanium dioxide waste acid and sulfuric acid process titanium dioxide production process |
-
2014
- 2014-11-20 CN CN201410666494.7A patent/CN104445432A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115793A (en) * | 2016-06-21 | 2016-11-16 | 阳山景润陶瓷色料实业有限公司 | A kind of ferric oxide red colorant and preparation method thereof |
| CN112279303A (en) * | 2020-11-26 | 2021-01-29 | 江苏宇星工贸有限公司 | Iron oxide red pigment and preparation method thereof |
| CN116040687A (en) * | 2022-11-01 | 2023-05-02 | 攀枝花末微环保科技有限公司 | Comprehensive utilization method of sulfuric acid process titanium dioxide waste acid and sulfuric acid process titanium dioxide production process |
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Application publication date: 20150325 |