CN101224874A - Method for producing sulfuric acid with by-product of calcium sulfate under low temperature - Google Patents
Method for producing sulfuric acid with by-product of calcium sulfate under low temperature Download PDFInfo
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- CN101224874A CN101224874A CNA2008100081817A CN200810008181A CN101224874A CN 101224874 A CN101224874 A CN 101224874A CN A2008100081817 A CNA2008100081817 A CN A2008100081817A CN 200810008181 A CN200810008181 A CN 200810008181A CN 101224874 A CN101224874 A CN 101224874A
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- phosphoric acid
- reaction
- gypsum
- ammonium sulfate
- acid
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Abstract
The invention provides a method for producing sulphuric acid at low temperature by using gypsum, especially the gypsum that is a by-product (including phosphate gypsum, fluorgypsum, flue gas desulfurization gypsum and so on). The gypsum is firstly prepared into ammonium sulfate, and then the phosphoric acid is used as reaction intermediate to decompose the ammonium sulfate into sulfuric anhydride and sulphuric acid. The phosphoric acid and ammonia can be recycled. The invention is low in equipment investment, the cost of the sulphuric acid produced by the method is far less than that of the sulfuric acid made by sulphur, which finds a good way for the large amount of gypsum that is a by-product; the invention avoids the environmental pollution and guarantees the sound development of the phosphate chemical industry.
Description
Technical field the present invention relates to a kind ofly utilize gypsum under cold condition, produces the vitriolic method at by-product gypsum (comprising phosphogypsum, fluorgypsum, desulfurized gesso of flue gas etc.) especially.
The technical background phosphogypsum is the waste residue that the Wet-process Phosphoric Acid Production project produces, and the waste residue main component is CaSO
22H
2Material such as O and phosphoric acid salt if store up for a long time, causes certain pollution hidden trouble to underground water.Because phosphogypsum slag does not also have the rational and effective disposal options at home, before not developing comprehensive utilization, the waste residue that Wet-process Phosphoric Acid Production enterprise produces is only taked to store up mode in the open, accumulates over a long period, now piled many a dense mass of mountains, very big to environmental influence.Fluorgypsum is a kind of of chemical gypsum, and being Calcium Fluoride (Fluorspan) produces residue behind the hydrofluoric acid with vitriolization, uses in the lime again and the excessive resulting waste residue of sulfuric acid, does not also well utilize at present.Desulfurized gesso of flue gas is also increasing in the quantity of China, and situation about utilizing neither be very desirable at present.
On the other hand, China needs a large amount of sulphur of import to produce sulfuric acid every year, nearly 1,000 ten thousand tons of China's imported sulphur in 2007, three/the last one that accounts for world wide production.The price one tunnel of sulphur is expected to rise, and having seriously influenced the downstream is the benefit of raw material enterprise with sulfuric acid.
Therefore produce sulfuric acid with by-product gypsum, not only saved valuable resource; Administered environmental pollution; Safety to the Economic development of country plays a protective role simultaneously.
Summary of the invention the invention provides and a kind ofly utilizes gypsum under cold condition, produces the vitriolic method at by-product gypsum (comprising phosphogypsum, fluorgypsum, desulfurized gesso of flue gas etc.) especially.
The present invention realizes by the following method:
One, at first utilize gypsum (comprising phosphogypsum, fluorgypsum, desulfurized gesso of flue gas etc.) to produce ammonium sulfate:
1. gypsum and carbon ammonium reaction (also can use the mixing solutions reaction of ammonia and carbonic acid gas) generates lime carbonate and ammonium sulfate mixing solutions; Filtering separation precipitation of calcium carbonate and other contamination precipitation can be used as the raw material that generates cement and use; Filtered liquid is the feed liquid of sulfur acid ammonium;
2. the feed liquid of filtering sulfur acid ammonium can evaporation concentration, ammonium sulfate content be ammonium sulfate feed liquid or the liquid-solid mixed liquor of 30%--90%;
3. the feed liquid of the sulfur acid ammonium after filtering also can evaporation concentration, and crystallisation by cooling gets ammonium sulfate solids;
Two, be reaction intermediate with phosphoric acid, decomposing ammonia sulfate system sulphur trioxide and sulfuric acid:
1. add phosphoric acid, reaction formula containing in the feed liquid of ammonium sulfate:
2H3PO4+(NH4)2SO4→2NH4H2PO4+SO3↑+H2O
Temperature of reaction is controlled at 40 ℃--between-100 ℃; The phosphoric acid that adds and the mol ratio of ammonium sulfate are 2-2.5: 1; The amount of phosphoric acid is convenient to the ammonium sulfate reaction and is changed into monoammonium phosphate more than the theory demands amount; The concentration of phosphoric acid that adds is between the 30%---100%; The sulphur trioxide that reaction is emitted absorbs through dilute sulphuric acid and makes the technical grade vitriol oil;
2. reaction end postcooling gets crystal, and filtering separation gets the monoammonium phosphate solid; Filter and recycle after feed liquid adds phosphoric acid and ammonium sulfate feed liquid again;
3. also can use strong phosphoric acid (concentration 85%--100%) and solid ammonium sulfate reaction, temperature of reaction is controlled at 40 ℃--and between-90 ℃, the phosphoric acid of adding and the mol ratio of ammonium sulfate are 2-2.5: 1; The amount of phosphoric acid is convenient to the ammonium sulfate reaction and is changed into monoammonium phosphate more than the theory demands amount; The sulphur trioxide that reaction is emitted absorbs through dilute sulphuric acid and makes the technical grade vitriol oil;
Three, the recycle of phosphoric acid and ammonia:
1. the filtering separation monoammonium phosphate solid thermal degradation of coming out is decomposed more than 190 ℃ the time and is lost ammonia and water when being heated to the monoammonium phosphate melting temperature, resolves into phosphoric acid and ammonium metaphosphate; Phosphoric acid resolves into tetra-sodium losing 1/2 water more than 213 ℃; Ammonium metaphosphate generates metaphosphoric acid and emits ammonia 220 ℃～440 ℃ scopes; Temperature of reaction can be controlled at (preferred temperature is controlled between 220 ℃～300 ℃) between 190 ℃----440 ℃; Be used for gypsum after the ammonia that reaction is emitted reclaims and produce ammonium sulfate; Phosphoric acid, tetra-sodium and metaphosphoric acid that decomposition obtains and water are back to decomposing ammonia sulfate system sulphur trioxide after forming phosphoric acid;
2. strong phosphoric acid (concentration 85%--100%) and solid ammonium sulfate reaction is emitted after the sulphur trioxide reaction finishes, and continues elevated temperature, and controlled temperature is between 190 ℃----440 ℃ (preferred temperature is controlled between 220 ℃～300 ℃); Be used for gypsum after the ammonia that reaction is emitted reclaims and produce ammonium sulfate; Phosphoric acid, tetra-sodium and metaphosphoric acid that decomposition obtains and water are back to decomposing ammonia sulfate system sulphur trioxide after forming phosphoric acid;
Advantage of the present invention:
1. facility investment is low;
2. produce the cost of vitriolic cost well below the sulphur process for preparing sulfuric acid;
3. found desirable outlet for a large amount of by-product gypsums; Avoided environmental pollution; Ensure the sound development of phosphorous chemical industry industry.
Claims (7)
1. one kind is utilized gypsum under cold condition, produces the vitriolic method at by-product gypsum (comprising phosphogypsum, fluorgypsum, desulfurized gesso of flue gas etc.) especially, it is characterized in that with phosphoric acid being reaction intermediate, decomposing ammonia sulfate system sulphur trioxide and sulfuric acid.Phosphoric acid and ammonia recycle.The concentration of phosphoric acid that adds is between the 30%---100%, and the phosphoric acid of adding and the mol ratio of ammonium sulfate are 2-2.5: 1.
2. as right 1 described method, it is characterized in that temperature of reaction is controlled at 40 ℃--between-100 ℃, the sulphur trioxide that reaction is emitted absorbs through dilute sulphuric acid and makes the technical grade vitriol oil.
3. as right 1 described method, reaction finishes postcooling and gets crystal, and filtering separation gets the ammonium phosphate solid, filters to recycle after feed liquid adds phosphoric acid and ammonium sulfate feed liquid again.
4. the method for claim 1 is characterized in that the ammonium phosphate solid thermal degradation that filtering separation is come out, and temperature of reaction can be controlled between 190 ℃----440 ℃.
5. the method for claim 1 is used for gypsum after the ammonia that reaction is emitted reclaims and produces ammonium sulfate.Phosphoric acid, tetra-sodium and metaphosphoric acid that decomposition obtains and water are back to decomposing ammonia sulfate system sulphur trioxide after forming phosphoric acid.
6. the method for claim 1 is characterized in that with strong phosphoric acid (concentration 85%--100%) and solid ammonium sulfate reaction.
7. the method for claim 1 is characterized in that strong phosphoric acid (concentration 85%--100%) and solid ammonium sulfate reaction, emits after the sulphur trioxide reaction finishes, and continues elevated temperature, and controlled temperature is between 190 ℃----440 ℃.Be used for gypsum after the ammonia that reaction is emitted reclaims and produce ammonium sulfate; Phosphoric acid, tetra-sodium and metaphosphoric acid that decomposition obtains and water are back to decomposing ammonia sulfate system sulphur trioxide after forming phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100081817A CN101224874A (en) | 2008-02-18 | 2008-02-18 | Method for producing sulfuric acid with by-product of calcium sulfate under low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100081817A CN101224874A (en) | 2008-02-18 | 2008-02-18 | Method for producing sulfuric acid with by-product of calcium sulfate under low temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101224874A true CN101224874A (en) | 2008-07-23 |
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ID=39857115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100081817A Pending CN101224874A (en) | 2008-02-18 | 2008-02-18 | Method for producing sulfuric acid with by-product of calcium sulfate under low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101224874A (en) |
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2008
- 2008-02-18 CN CNA2008100081817A patent/CN101224874A/en active Pending
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| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080723 |