CN1200364A - Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide - Google Patents
Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide Download PDFInfo
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Abstract
The present invention utilizes the waste by-products acid containing waste water and green vitriol in the prodn. of titanium dioxide by sulfuric acid method and mixes the two by-products according to calculated furmula, adds ammonia gas into the reacting mixed solution with constant stirring, chemical heat is liberated during reaction so that reaction temp. is raised, by regulating temp. and pH to control the end point of reaction so as to obtain ammonium ferrous sulfate fertilizer. This technology has no three wastes liberated so that there is no pollutant to environment.
Description
The invention belongs to the field of recycling waste byproducts in titanium dioxide production, and relates to a preparation method of a ferrous ammonium sulfate fertilizer, which is suitable for comprehensive utilization of waste byproducts and acid-containing wastewater in the production of titanium dioxide by a sulfuric acid method.
In the prior art, acid-containing wastewater in titanium dioxide production is directly used for steel acid pickling and rust removal. Through acid washing, ferric oxide on the surface of the steel is dissolved by acid to generate ferrous sulfate, and when the concentration of the ferrous sulfate in waste acid is accumulated to 20%, a vacuum evaporation and cooling crystallization method can be adopted to separate the ferrous sulfate into crystals. When the evaporation temperature is lower than 50 ℃, heptahydrate is obtained, and when the evaporation temperature is higher than 50 ℃, monohydrate is obtained. However, after the steel is acid-washed, other inorganic salts contained in the residual liquid can be brought into the ferrous sulfate heptahydrate and the ferrous sulfate monohydrate, so that the quality of the ferrous sulfate heptahydrate and the ferrous sulfate monohydrate is reduced, and the utilization value is influenced.
Titanium dioxide information communication 1996 No.2 reports that Bayer company sulfuric acid method titanium dioxide waste-free byproduct technology is that acid-containing wastewater is subjected to pre-concentration treatment, metal sulfate is separated out, then the acid-containing wastewater is further concentrated, and the generated concentrated sulfuric acid is returned to an acidolysis process. The water vapor generated in the two-stage concentration process is discharged into the atmosphere after being catalyzed and purified. The metal sulfates such as ferrous sulfate and the like separated in the pre-concentration process are used together with coal and pyrite for sulfuric acid production by a catalytic method by using a fluidized bed furnace, and the remaining ferric oxide can be used as a valuable iron-containing raw material. The cost of developing and implementing the bayer process set of waste byproduct treatment schemes is significant, as is the cost of maintaining and operating the equipment.
Us patent 4163047 describes the combined production of sulphuric acid from spent acid and ferrous sulphate. Although the saline waste acid produced and the high crystal water ferrous sulphate can be disposed of in an ecologically satisfactory manner at a relatively low energy consumption, a portion of the concentrated filtrate cannot be reused and discarded.
The Shanghai titanium dioxide factory adopts calcium carbide dirt and limestone to neutralize acid-containing wastewater, and a byproduct of yellow gypsum is generated, although after the calcium carbide dirt or the limestone is neutralized and air is oxidized, the pH and COD of the filtered water can reach the discharge standard. But the yellow gypsum remaining from the filtration is difficult to handle.
Commercially, ferrous ammonium sulfate is usually produced synthetically. Dissolving ammonium sulfate and ferrous sulfate in hot water, adding sulfuric acid, filtering, concentrating, crystallizing, and centrifuging to obtain ammonium ferrous sulfate. The process route is complex and the product cost is high.
The invention aims to find a more economical and simpler method for converting acid-containing wastewater and soluble inorganic salts contained in the acid-containing wastewater into ammonium ferrous sulfate fertilizer containing multiple mineral substances. The preparation method fully utilizes the chemical reaction heat to reduce energy consumption, solves the problem of comprehensive utilization of waste byproduct acid-containing wastewater in the production of titanium dioxide by a sulfuric acid method, comprehensively treats three wastes in production, solves the problem of environmental protection, and achieves the aim of changing waste into valuable.
In order to realize the purpose, the invention uses the copperas and the acid-containing wastewater which are byproducts in the production process of the titanium dioxide by the sulfuric acid method as raw materials.
The ferrous sulfate heptahydrate content in the copperas is 80-100 wt%, preferably above 90 wt%, otherwise the content of the product ferrous ammonium sulfate will be reduced. The acid-containing wastewater consists of 18-22 percent (by weight) of sulfuric acid and 16-19 percent (by weight) of ferrous sulfate heptahydrate.
Adding more than 80% (weight) of ferrous sulfate heptahydrate into acid-containing wastewater with the sulfuric acid content of 18-22% (weight) and the ferrous sulfate heptahydrate content of 16-19% (weight), and mixing, wherein the addition amount of the ferrous sulfate heptahydrate meets the following chemical formula:
in the formula: d is the amount (g) of ferrous sulfate heptahydrate added in each liter of acid-containing wastewater;
a is the content (g/L) of sulfuric acid in the acid-containing wastewater;
b is the content (g/L) of ferrous sulfate heptahydrate in the acid-containing wastewater;
c is the content (weight) of ferrous sulfate heptahydrate in the added ferrous sulfate;
k is a coefficient.
Under the stirring state, ammonia gas is directly introduced into the mixed solution of the acid-containing wastewater and the ferrous sulfate, the reaction temperature is increased along with the release of chemical reaction heat, simultaneously, ferrous sulfate crystals are gradually and completely dissolved, and the pH value of the solution begins to rise.
When the temperature of the reaction solution rises to 80-100 ℃ and the pH value is 2-7, the reaction end point is obtained. The pH value is optimally controlled to be 2-3.5, and at the moment, (NH) in the solution4)2SO4With FeSO4·7H2O complex to (NH)4)2Fe(SO4)2·6H2O。MeSO4All conversion to MeFe (SO)4)2·xH2And O, wherein Me is various metal ions such as Mn, Mg, Zn and the like. The chemical reaction equation is as follows:
the reaction solution with the temperature higher than 80 ℃ is directly sprayed and dried to obtain the product of the invention. Or the reaction solutionwith the temperature higher than 80 ℃ can be stirred at the stirring speed of 50-60 r/min and cooled to the room temperature of 25 ℃ or lower than 25 ℃, and a large amount of crystals are separated out. Separating out crystals by conventional centrifugal separation or vacuum filtration, drying with hot air at low temperature (60-90 ℃) to obtain an ammonium ferrous sulfate product with the content of more than 90 percent (weight), and carrying out vacuum concentration, cooling, crystallization, separation and drying on the filtrate to obtain the residual product. So far, almost 100 percent of acid-containing wastewater is completely converted into ammonium ferrous sulfate fertilizer containing various minerals.
The coefficient K is controlled to be 2.4-3.1, and when the coefficient K is large, Fe (OH) is easily generated2To darken the color of the product. When the coefficient K is small, the content of the ferrous ammonium sulfate product can be reduced, even the content can not reach 90 percent (weight).
The mixed raw materials are stirred and ammonia gas is introduced, the reaction temperature is increased along with the release of chemical heat, ferrous sulfate crystals are gradually and completely dissolved, and the pH value begins to rise. When the reaction solution is heated during the reaction, the reaction solution can be cooled simultaneously to ensure that ammonium ferrous sulfate crystals are continuously separated out, the temperature is cooled to be less than 25 ℃, and when the pH is 2-7, the optimal pH is controlled to be 2-3.5, and the reaction can also be the end point. Then centrifugal separation or vacuum filtration is carried out to separate out crystals, and the crystals are dried by hot air at low temperature (60-80 ℃) to obtain the ammonium ferrous sulfate with the product content being more than 90 percent (weight).
In the present invention, the pH control at the endof the reaction is important. When the pH value is too high, ferrous sulfate and ammonium hydroxide can react to generate ferrous hydroxide which is dark green sticky colloid and can influence the appearance of the product, and simultaneously Fe (OH)2Also readily oxidized to Fe (OH)3Or even Fe2O3They are poorly soluble compounds and cannot be absorbed by plants. Too low a pH value leads to too high an acidity, which affects the crop.
The invention relates to a method for fully recycling waste by-products and acid-containing wastewater in the production of titanium dioxide by a sulfuric acid method, wherein acid-containing wastewater with the sulfuric acid concentration of 18-22% can be completely converted into ammonium ferrous sulfate fertilizer containing multiple mineral substances through calculation formula and chemical reaction. About 1 ton of ferrous ammonium sulfate fertilizer containing various mineral substances can be produced by using about 500 kg of ferrous sulfate heptahydrate consumed by 1 cubic meter of acid-containing wastewater. Only water vapor is discharged in the whole process, and three wastes are not discharged, so that the aims of comprehensively treating the three wastes and changing waste into valuable are fulfilled.
The invention produces ferrous ammonium sulfate fertilizer, iron fertilizer is one of trace element fertilizer, iron is the component of many enzymes in plant body, it can promote plant to fully absorb and utilize nitrogen and phosphorus, and has regulating effect on the oxidation-reduction process in plant body. Iron is also an essential element for the synthesis of chlorophyll. But Fe is absorbed and utilized by plants2+And chelated iron, Fe3+The compounds which are often very insoluble exist and cannot be absorbed by plants. Alkaline soil tends to causeFeIs oxidized into Fe3+And is fixed by the soil, reducing the efficiency of the iron. The ferrous ammonium sulfate fertilizer produced by the invention is weakly acidic, so thatPrevention of Fe2+Is oxidized into Fe3+In addition to (NH)4)2SO4And trace MgSO4Is a stabilizer of ferrous sulfate, and improves the efficiency of the iron micro-fertilizer. The ferrous ammonium sulfate can be directly used as a base fertilizer, a seed fertilizer or an extra-root fertilizer, and can also be mixed with other fertilizers to form a compound fertilizer. The compound fertilizer prepared from 10% of ammonium sulfate, 40% of ferrous sulfate and 50% of plant ash is applied to soil, so that the yield of spring millet is increased by 37.1%, and the yield of corn is increased by 14.9-19.6%.
The ammonium ferrous sulfate product of the invention also contains trace elements such as magnesium, manganese, zinc and the like, can promote the growth of crops, and the magnesium is a core structure component of chlorophyll and is very beneficial to the growth of the crops.
The following examples illustrate the invention but are not meant to limit the invention.
Example 1:
raw materials: ferrous sulfate contains FeSO4·7H2O 86.44％
The chemical components of the acid-containing wastewater are as follows: h2SO4245.18g/L
FeSO4·7H2O 233.32g/L
3050 g (K is 3.1) of ferrous sulfate is added into an enamel barrel containing 5000 ml of acid-containing wastewater, the reaction is carried out while stirring, ammonia gas is slowly added under the stirring state, the ferrous sulfate is gradually and completely dissolved under the chemical reaction heat, and thetemperature of the reaction solution is gradually increased along with the continuous addition of the ammonia. And adjusting the pH value, when the reaction temperature reaches 82 ℃ and the pH is 4-5, finishing the reaction, continuing stirring, cooling to room temperature, precipitating a large amount of crystals from the solution, separating by using a centrifugal machine, continuing evaporating and concentrating the obtained mother liquor, drying the obtained crystals and filter cakes by using hot air at the temperature of 60-70 ℃ to obtain 5300 g of ferrous ammonium sulfate fertilizer. Ferrous ammonium sulfate (NH) as a main component4)2Fe(SO4)2·6H2The O content was 90.55% by weight.
Example 2:
raw materials: ferrous sulfate contains FeSO4·7H2O 86.18％
The chemical components of the acid-containing wastewater are as follows: h2SO4237.9g/L
FeSO4·7H2O 203.4g/L
5370 g (K is 2.8) of ferrous sulfate is added into an enamel barrel containing 10000 ml of acid-containing wastewater, the mixture is stirred and reacted, ammonia gas is slowly added under the stirring state, the ferrous sulfate is gradually and completely dissolved under the chemical reaction heat, and the temperature of the reaction solution is gradually increased along with the continuous addition of the ammonia. And adjusting the pH value, and finishing the reaction when the reaction temperature reaches 84 ℃ and the pH value is 2-3. And then continuously stirring, cooling to room temperature, precipitating a large amount of crystals from the solution, separating by using a centrifugal machine, continuously evaporating and concentrating the obtained mother liquor, and drying the obtained crystals and filter cakes by using hot air at the temperature of 60-70 ℃ to obtain 9400 g of ferrous ammonium sulfate fertilizer. Ferrous ammonium sulfate (NH) as a main component4)2Fe(SO4)2·6H2The O content was 93.97% by weight.
Example 3:
raw materials: ferrous sulfate contains FeSO4·7H2O 92.46％
The chemical components of the acid-containing wastewater are as follows: h2SO4229.5g/L
FeSO4·7H2O 258.56g/L
Adding 31.6 g (K is 2.4) of ferrous sulfate into 100 ml of acid-containing wastewater, slowly adding ammonia gas under the stirring state, reacting while stirring to completely dissolve the raw materials, stopping introducing ammonia when the reaction temperature reaches 86 ℃ and the pH value of the solution reaches 6-7, and stopping the reaction. And then cooling the reaction solution by using an ice bath, when the temperature is reduced to 10 ℃, precipitating a large amount of crystals, separating the crystals by using a centrifugal machine, and drying the crystals by using hot air at the temperature of 60-70 ℃ to obtain 49.6 g of the ferrous ammonium sulfate fertilizer. Evaporating and concentrating the green mother liquor, pouring all the green mother liquor into an enamel tray when the green mother liquor becomes pasty slurry, and completely crystallizing and drying the green mother liquor by using hot air at the temperature of 60-70 DEG C31.3 g of ammonium ferrous sulfate fertilizer is obtained. In this example, a total of 80.9 grams of ferrous ammonium sulfate fertilizer, which is ferrous ammonium sulfate (NH), was obtained4)2Fe(SO4)2·6H2The O content is 80% (by weight)
Claims (7)
1. A method for preparing a ferrous ammonium sulfate fertilizer by using sulfuric acid method titanium dioxide acid-containing wastewater is characterized by comprising the following steps:
(1) adding more than 80 percent (by weight) of ferrous sulfate heptahydrate into acid-containing wastewater with 18 to 22 percent (by weight) of sulfuric acid and 16 to 19 percent (by weight) of ferrous sulfate heptahydrate, and mixing, wherein the addition amount of the ferrous sulfate heptahydrate meets the following chemical formula:
in the formula: d is the amount (g) of ferrous sulfate heptahydrate added in each liter of acid-containing wastewater
A is the content (g/L) of sulfuric acid in the acid-containing wastewater
B is the content (g/L) of ferrous sulfate heptahydrate in the acid-containing wastewater
C is the content percent (by weight) of ferrous sulfate heptahydrate in the ferrous sulfate
K is a coefficient for the number of,
(2) ammonia gas is directly introduced into the mixed solution while stirring, the reaction temperature is raised along with the release of chemical reaction heat,
(3) the ferrous sulfate crystals are gradually and completely dissolved, the pH value begins to rise,
(4) when the temperature of the reaction solution rises to 80-100 ℃ and the pH value is 2-7, the reaction end point is obtained, and the reaction solution is dried to obtain an ammonium ferrous sulfate product, (NH)4)2Fe(SO4)2·6H2The O content is greater than 90% by weight.
2. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: the coefficient K is 2.4-3.1.
3. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: the optimal pH value is controlled to be 2-3.5.
4. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: the content of added ferrous sulfate heptahydrate is preferably>90% by weight.
5. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: and (3) directly carrying out spray drying on the reaction solution with the temperature of more than 80 ℃ at the end of the reaction to obtain the ammonium ferrous sulfate product.
6. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: at the end of the reaction, cooling the reaction solution with the temperature of more than 80 ℃ to less than 25 ℃, centrifugally separating ferrous ammonium sulfate crystals, and drying the crystals by low-temperature hot air to obtain a ferrous ammonium sulfate product.
7. The method for preparing ammonium ferrous sulfate according to claim 1, which is characterized by comprising the following steps: and (3) heating and cooling the reaction solution in the step (4) while reacting, continuously separating out ammonium ferrous sulfate crystals, cooling to a temperature of less than 25 ℃, wherein the pH value is 2-7, namely the reaction end point, centrifugally separating out ammonium ferrous sulfate crystals, and drying the crystals by low-temperature hot air to obtain an ammonium ferrous sulfate product.
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| CN 97106429 CN1114579C (en) | 1997-05-22 | 1997-05-22 | Method for preparing ferrous ammonium sulfate by using waste water from sulfuric acid method prodn. of titanium dioxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034921A1 (en) | 2006-09-18 | 2008-03-27 | Fertinagro Nutrientes, S.L. | Process for obtaining fertilizers from tio2 subproducts, and products obtained in this manner |
| CN101935071A (en) * | 2010-07-23 | 2011-01-05 | 河南佰利联化学股份有限公司 | Novel crystallization method for recycling thermal-sensitive dissolving solution-containing medium |
| CN102060335A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry |
| CN102115206A (en) * | 2010-12-31 | 2011-07-06 | 谢善情 | Method for producing ferrous carbonate and sodium sulfate from waste acid generated during titanium dioxide production through sulfuric acid method |
| CN102556981A (en) * | 2010-12-24 | 2012-07-11 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN111847520A (en) * | 2020-08-07 | 2020-10-30 | 攀枝花学院 | Preparation method of ammonium ferrous sulfate |
| CN112299491A (en) * | 2019-07-30 | 2021-02-02 | 中冶长天国际工程有限责任公司 | Method for synthesizing ferrous ammonium sulfite |
-
1997
- 1997-05-22 CN CN 97106429 patent/CN1114579C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008034921A1 (en) | 2006-09-18 | 2008-03-27 | Fertinagro Nutrientes, S.L. | Process for obtaining fertilizers from tio2 subproducts, and products obtained in this manner |
| CN101935071A (en) * | 2010-07-23 | 2011-01-05 | 河南佰利联化学股份有限公司 | Novel crystallization method for recycling thermal-sensitive dissolving solution-containing medium |
| CN102060335A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry |
| CN102060335B (en) * | 2010-10-29 | 2012-12-05 | 华南理工大学 | Method for preparing ammonium ferrous sulfate from waste ferrous slag in sulfuric acid process titanium dioxide industry |
| CN102556981A (en) * | 2010-12-24 | 2012-07-11 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN102556981B (en) * | 2010-12-24 | 2013-10-09 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN102115206A (en) * | 2010-12-31 | 2011-07-06 | 谢善情 | Method for producing ferrous carbonate and sodium sulfate from waste acid generated during titanium dioxide production through sulfuric acid method |
| CN112299491A (en) * | 2019-07-30 | 2021-02-02 | 中冶长天国际工程有限责任公司 | Method for synthesizing ferrous ammonium sulfite |
| CN111847520A (en) * | 2020-08-07 | 2020-10-30 | 攀枝花学院 | Preparation method of ammonium ferrous sulfate |
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