CN1114579C - 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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- CN1114579C CN1114579C CN 97106429 CN97106429A CN1114579C CN 1114579 C CN1114579 C CN 1114579C CN 97106429 CN97106429 CN 97106429 CN 97106429 A CN97106429 A CN 97106429A CN 1114579 C CN1114579 C CN 1114579C
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- ammonium sulphate
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Abstract
The present invention is characterized in that a sulfuric acid method is fully utilized to prepare acid containing waste water and green copperas as waste by-products in the production of titanium white powder so that the acid containing waste water and the green copperas are calculated and mixed according to a formula, and ammonia gas is continuously supplied into a reaction mixed solution in the state of stirring. Reaction temperature rises with the release of chemical heat, an end point of the reaction is controlled by reaction temperature regulation and a pH value to finally obtain an ammonium ferrous sulfate fertilizer. The whole process without three-waste discharge achieves the purposes that the 'three wastes' are comprehensively treated, and wastes are changed into valuables. The ammonium ferrous sulfate fertilizer can be directly used as a basal fertilizer, a seed fertilizer or an exroot fertilizer and can also be mixed with other fertilizers to become a compound fertilizer, and therefore, the ammonium ferrous sulfate fertilizer has the advantages of ferrum microfertilizer efficiency improvement and achievement of the effect of crop yield increase.
Description
The present invention belongs to recycle useless byproduct in the titanium white production, relates to a kind of preparation method of ferrous sulfate ammonium fertilizer, and this method is applicable to the comprehensive utilization of give up in the sulfuric acid legal system titanium white production byproduct and acid-bearing wastewater.
In prior art, the acid-bearing wastewater in the titanium white production is directly used in the acid washing rolled steel rust cleaning.By pickling, the ferric oxide of steel surface is generated ferrous sulfate by acid dissolving, when in the spent acid during ferrous sulfate concentrations build-up to 20%, just can adopt vacuum-evaporation and crystallisation by cooling method, makes ferrous sulfate become crystal and separates out and obtain separating.Obtain seven crystallines when vaporization temperature is lower than 50 ℃, vaporization temperature then obtains a crystalline greater than 50 ℃.But behind the acid washing rolled steel, contained other inorganic salt can be brought in iron vitriol and the ferrous sulfate monohydrate in the raffinate, make iron vitriol and ferrous sulfate monohydrate downgrade, thereby influence utility value.
The technology that titanium white Intelligence Newsletter No.2 in 1996 report Beyer Co., Ltd sulfate process titanium dioxide does not have useless byproduct is acid-bearing wastewater to be crossed through pre-concentration earlier handle, isolate metal sulfate after, further concentrated again, the concentrated vitriol that is generated turns back to hydrolysis procedure.The water vapor that produces in the two-stage concentration process is discharged in the atmosphere behind catalytic purification.Metal sulfates such as the ferrous sulfate of separating in the pre-concentration process and coal, pyrite one are reinstated fluidizing furnace and are carried out the catalysis method gas washing in SA production, and remaining ferric oxide can be used as valuable iron-bearing material.But cost of the useless byproduct for treatment scheme of this cover of exploitation and enforcement Beyer Co., Ltd is huge, and the expense in maintenance of the equipment and operation process also is expensive.
United States Patent (USP) 4163047 is to utilize spent acid and ferrous sulfate combined preparation sulfuric acid.Though this patent can obtain handling with satisfactory way on ecology under relatively low energy consumption saliferous spent acid and the high crystal water ferrous sulfate that produces, and still has the spissated filtrate of part can not be reused and discard.
The Shanghai titanium powder plant adopt the dirty and Wingdale of calcium carbide come in and acid-bearing wastewater, by-product Huangshi cream, though by calcium carbide dirt or Wingdale neutralize and atmospheric oxidation after, its pH of the water that filters out and COD can qualified discharges.But the Huangshi cream of filtration residue is with intractable.
Normally make at industrial ferrous ammonium sulphate with synthesis method.Add sulfuric acid again after ammonium sulfate, ferrous sulfate be dissolved in hot water, after filtration, concentrate, crystallization, centrifugation make ferrous ammonium sulphate.This operational path complexity, product cost is higher.
The objective of the invention is to seek a kind of more economical, easier method and all change into the ferrous sulfate ammonium fertilizer that contains several mineral materials containing soluble inorganic salt in acid-bearing wastewater and the acid-bearing wastewater.This preparation method makes full use of chemical reaction heat, cuts down the consumption of energy to reach, and has solved the problem of complex utilization of useless byproduct acid-bearing wastewater in the sulfuric acid legal system titanium white production, both to the comprehensive administration of three wastes in producing, has solved environmental protection, reaches the purpose that turns waste into wealth again.
In order to realize this purpose, the present invention utilizes the green vitriol of by-product in the sulfuric acid method titanium pigment production process and acid-bearing wastewater to make raw material.
Iron vitriol content is 80～100% (weight) in the green vitriol, be preferably in more than 90% (weight), otherwise the content of product ferrous ammonium sulphate can descend.Acid-bearing wastewater is made up of 18～22% (weight) sulfuric acid and 16～19% (weight) iron vitriol.
Iron vitriol to the sulfuric acid content that adds content＞80% (weight) is that 18～22% (weight) and iron vitriol content are to mix in the acid-bearing wastewater of 16～19% (weight), and its addition meets following chemical formula:
In the formula: D is the amount (g) of adding iron vitriol in every liter of acid-bearing wastewater;
A is a vitriolic content (g/L) in the acid-bearing wastewater;
B is the content (g/L) of iron vitriol in the acid-bearing wastewater;
C is the content % (weight) that adds iron vitriol in the ferrous sulfate;
K is a coefficient.
Under whipped state, in acid-bearing wastewater, ferrous sulfate mixed solution, directly feed ammonia, temperature of reaction raises along with the release of chemical reaction heat, progressively all dissolvings of ferrous sulfate crystal simultaneously, the pH value of solution value begins to rise.
When being raised to 80～100 ℃, pH, the reaction soln temperature is reaction end 2～7 the time.Best pH value is to be controlled at 2～3.5, at this moment, and (the NH in the solution
4)
2SO
4With FeSO
47H
2O is combined into (NH
4)
2Fe (SO
4)
26H
2O, MeSO
4All be converted into MeFe (SO
4)
2XH
2O, wherein Me is multiple metal ions such as Mn, Mg and Zn.Chemical equation is as follows:
＞80 ℃ reaction soln is directly carried out spraying drying, can obtain product of the present invention.Also can be with＞80 ℃ reaction soln, under stirring state, stirring velocity is 50～60 rev/mins, 25 ℃ of cool to room temperature or＜25 ℃, this moment, existing mass crystallization was separated out.Go out crystal by conventional centrifugation or isolated by vacuum filtration, promptly get the ferrous ammonium sulphate product through low temperature warm air drying (60～90 ℃), content＞90% (weight), filtrate is carried out vacuum concentration, cooling, crystallization, separation drying, can get remaining product again.So far almost 100% acid-bearing wastewater all changes into the ferrous sulfate ammonium fertilizer that contains several mineral materials.
COEFFICIENT K is to be controlled at 2.4～3.1, generates Fe (OH) when COEFFICIENT K is big easily
2, make darkening of product.COEFFICIENT K hour, product ferrous ammonium sulphate content can reduce, even content can not reach 90% (weight).
Mixed raw materials, logical while stirring ammonia, temperature of reaction raises with the release of chemical heat, and the ferrous sulfate crystal is all dissolvings progressively, and the pH value begins to rise.When the reaction of reaction soln limit heats up, also can cool off simultaneously, the ferrous sulfate crystalline ammonium is constantly separated out, be cooled to＜25 ℃, pH was at 2～7 o'clock, and best pH is controlled at 2～3.5, also can be reaction end.And then go out crystal by centrifugation or isolated by vacuum filtration, crystal through low temperature warm air drying (60～80 ℃) also ferrous ammonium sulphate, product content＞90% (weight).
Among the present invention, the control of the pH value of reaction end is most important.Ferrous sulfate and ammonium hydroxide can react the generation ferrous hydroxide when pH value was too high, and this is blackish green sticking colloid, can influence the outward appearance of product, simultaneously Fe (OH)
2Also easily be oxidized to Fe (OH)
3And even Fe
2O
3, be the compound of indissoluble, plant can't be absorbed.Acidity was too big when the pH value was low excessively, and product will be influential to farm crop.
The present invention is to be sulfuric acid concentration 18～22% acid-bearing wastewater, can all be converted into the ferrous sulfate ammonium fertilizer that contains several mineral materials after calculating prescription and chemical reaction, fully recycles give up in the sulfuric acid legal system titanium white production byproduct and acid-bearing wastewater.Can produce the ferrous sulfate ammonium fertilizer that contains several mineral materials about 1 ton with 500 kilograms of left and right sides iron vitriols of 1 cubic metre of acid-bearing wastewater consumption.What discharge in the whole technology is water vapor only, does not have three waste discharge, the purpose that reach comprehensive administration of three wastes, turns waste into wealth.
What the present invention generated is the ferrous sulfate ammonium fertilizer, and iron fertilizer is one of trace element fertilizer, and iron is the composition of many enzymes in the plant materials, and it can promote plant fully to absorb nitrogen and phosphorus element, and the intravital redox processes of plant is had regulating effect.Iron also is the requisite element of synthesize chlorophyll (chl).But that the plant absorbing utilization is Fe
2+With chelating attitude iron, Fe
3+The compound that often is utmost point indissoluble exists, and plant can't be absorbed.Alkaline soil tends to make Fe
2+Be oxidized to Fe
3+And, the usefulness of iron is reduced by soil fixing.The ferrous sulfate ammonium fertilizer that the present invention generates is because be slightly acidic, so can prevent Fe
2+Be oxidized to Fe
3+, (NH in addition
4)
2SO
4With micro Mg SO
4Be the stablizer of ferrous sulfate, improved the usefulness of the little fertilizer of iron.Ferrous ammonium sulphate can directly be used as base manure, seed manure or foliage fertilization, also can be mixed into compound manure with other fertilizer.The multiple fertilizer that uses 10% ammonium sulfate, 40% ferrous sulfate and 50% plant ash to make imposes on and can make spring paddy volume increase 37.1%, corn yield increasing 14.9～19.6% in the soil.
Also contain elements such as trace magnesium, manganese, zinc in the ferrous ammonium sulphate product of the present invention, also can promote plant growth, magnesium is again chlorophyllous core texture integral part, and is extremely beneficial to the growth of farm crop.
Illustrate the present invention with embodiment below, but and do not mean that restriction the present invention.
Embodiment 1:
Raw material: ferrous sulfate contains FeSO
47H
2O 86.44%
The chemical composition of acid-bearing wastewater is: H
2SO
4245.18g/L
FeSO
4·7H
2O 233.32g/L
In the porcelain enamel barrel of containing 5000 milliliters of acid-bearing wastewaters, add ferrous sulfate 3050 grams (K=3.1), reaction slowly adds ammonia under whipped state while stirring, makes ferrous sulfate progressively all dissolvings under chemical reaction heat, along with the continuous adding of ammonia, the reaction soln temperature rises gradually.Regulate the pH value, when temperature of reaction reaches 82 ℃, pH finishes reaction in 4～5 o'clock, continue again to stir, cool to room temperature, mass crystallization is precipitated out from solution, separate with whizzer, with mother liquid obtained continuation evaporation concentration, crystal that obtains and filter cake dry up dry with 60～70 ℃ of warm airs, obtain 5300 gram ferrous sulfate ammonium fertilizers.Main composition ferrous ammonium sulphate (NH
4)
2Fe (SO
4)
26H
2O content is 90.55% (weight).
Embodiment 2:
Raw material: ferrous sulfate contains FeSO
47H
2O 86.18%
The chemical composition of acid-bearing wastewater is: H
2SO
4237.9g/L
FeSO
4·7H
2O 203.4g/L
In the porcelain enamel barrel of containing 10000 milliliters of acid-bearing wastewaters, add ferrous sulfate 5370 grams (K=2.8), reaction slowly adds ammonia under whipped state while stirring, makes ferrous sulfate progressively all dissolvings under chemical reaction heat, along with the continuous adding of ammonia, the reaction soln temperature rises gradually.Regulate pH value, when temperature of reaction reaches the reaction end 2～3 time of 84 ℃, pH.Continue again to stir, cool to room temperature, mass crystallization is precipitated out from solution, separates with whizzer, and with mother liquid obtained continuation evaporation concentration, crystal that obtains and filter cake dry up dry with 60～70 ℃ of warm airs, obtain 9400 gram ferrous sulfate ammonium fertilizers.Main composition ferrous ammonium sulphate (NH
4)
2Fe (SO
4)
26H
2O content is 93.97% (weight).
Embodiment 3:
Raw material: ferrous sulfate contains FeSO
47H
2O 92.46%
The chemical composition of acid-bearing wastewater is: H
2SO
4229.5g/L
FeSO
4·7H
2O 258.56g/L
Add ferrous sulfate 31.6 grams (K=2.4) in 100 milliliters of acid-bearing wastewaters, slowly add ammonia under whipped state, reaction is dissolved raw material fully while stirring, stops logical ammonia, reaction terminating when temperature of reaction to 86 ℃, pH value of solution to 6～7.With ice bath reaction soln is cooled off then, when temperature drops to 10 ℃, have mass crystallization to settle down, isolate crystallization and crystallization is dried up with whizzer and promptly obtain 49.6 and restrain the ferrous sulfate ammonium fertilizers with 60～70 ℃ of warm airs.Green mother liquor carries out evaporation concentration, when treating that it becomes pasty slurry, all pours in the enamel tray, with 60～70 ℃ of warm airs its whole crystallizing and dryings ferrous sulfate ammonium fertilizer 31.3 of getting back is restrained.Present embodiment obtains 80.9 gram ferrous sulfate ammonium fertilizers, its ferrous ammonium sulphate (NH altogether
4)
2Fe (SO
4)
26H
2O content is 80% (weight).
Claims (6)
1, a kind ofly prepare the method for ferrous sulfate ammonium fertilizer, it is characterized in that with the sulfate process titanium dioxide acid-bearing wastewater:
(1) iron vitriol to the sulfuric acid content of interpolation content＞80% (weight) is that 18～22% (weight) and iron vitriol content are in the acid-bearing wastewater of 16～19% (weight), mixes, and its addition meets following chemical formula:
In the formula: D is the amount (g) of adding iron vitriol in every liter of acid-bearing wastewater
A is a vitriolic content (g/L) in the acid-bearing wastewater
B is the content (g/L) of iron vitriol in the acid-bearing wastewater
C is the content % (weight) that adds iron vitriol in the ferrous sulfate
K is a coefficient, and the K value is 2.4～3.1,
(2) stir on one side, to above-mentioned mixed solution in directly feed ammonia on one side, temperature of reaction raises with the release of chemical reaction heat,
(3) progressively all dissolvings of ferrous sulfate crystal, the pH value begins to rise,
(4) be reaction end when the reaction soln temperature is raised to 80～100 ℃, pH 2～7 the time, reaction soln is drying to obtain ferrous ammonium sulphate product, (NH
4)
2Fe (SO
4)
26H
2O content is greater than 90% (weight).
2, the method for preparing ferrous ammonium sulphate according to claim 1, it is characterized in that: the pH value is controlled at 2～3.5.
3, the method for preparing ferrous ammonium sulphate according to claim 1 is characterized in that: the content of the iron vitriol that is added is＞90% (weight).
4, the method for preparing ferrous ammonium sulphate according to claim 1 is characterized in that: during reaction end, will directly carry out spraying drying greater than 80 ℃ reaction soln and get the ferrous ammonium sulphate product.
5, the method for preparing ferrous ammonium sulphate according to claim 1, it is characterized in that: during reaction end, to be cooled to greater than 80 ℃ reaction soln＜25 ℃, go out the ferrous ammonium sulphate crystal through centrifugation, crystal gets the ferrous ammonium sulphate product through the low temperature warm air drying again.
6, the method for preparing ferrous ammonium sulphate according to claim 1, it is characterized in that: with the reaction intensification of reaction soln limit, the limit cooling of (4), the ferrous sulfate crystalline ammonium is constantly separated out, be cooled to＜25 ℃, pH was reaction end at 2～7 o'clock, go out the ferrous ammonium sulphate crystal through centrifugation, crystal gets the ferrous ammonium sulphate product through the low temperature warm air drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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|---|---|
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| CN1114579C true CN1114579C (en) | 2003-07-16 |
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|---|---|---|---|
| CN 97106429 Expired - Fee Related 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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| 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 |
| CN101935071B (en) * | 2010-07-23 | 2012-05-02 | 河南佰利联化学股份有限公司 | Crystallization method for recovering medium containing temperature-sensitive dissolving solution |
| 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 |
| 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 |
| CN102115206B (en) * | 2010-12-31 | 2012-06-06 | 谢善情 | Method for producing ferrous carbonate and sodium sulfate by using waste acid obtained in production of titanium dioxide by sulfuric acid process |
| CN112299491B (en) * | 2019-07-30 | 2023-01-24 | 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 | A kind of preparation method of ferrous ammonium sulfate |
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1997
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