CN103253637A - Method for producing sulfuric acid and calcium oxide by utilizing gypsum - Google Patents
Method for producing sulfuric acid and calcium oxide by utilizing gypsum Download PDFInfo
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- CN103253637A CN103253637A CN2013102171753A CN201310217175A CN103253637A CN 103253637 A CN103253637 A CN 103253637A CN 2013102171753 A CN2013102171753 A CN 2013102171753A CN 201310217175 A CN201310217175 A CN 201310217175A CN 103253637 A CN103253637 A CN 103253637A
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- gypsum
- sulfuric acid
- gas
- rotary kiln
- calcium oxide
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Abstract
The invention relates to a method for producing sulfuric acid and calcium oxide by utilizing gypsum. The method comprises the following steps: (1) putting the gypsum with the purity greater than or equal to 96% and the lumpiness of 9.5 to 15mm into a rotary furnace; and rising the temperature to reach 1180 DEG C to 1220 DEG C; (2) guiding natural gas and air into a combustion chamber; enabling the natural gas to be burnt in the combustion chamber and thus obtaining the mixing gas of CO2, H2 and CO, wherein the volume concentration of the CO in the mixing gas is controlled to be less than or equal to 5% while the volume concentration of the CO2 is controlled to be greater than or equal to 15%; guiding the obtained mixing gas into the rotary furnace with the gypsum therein; and enabling calcium sulfate to react with the mixing gas in the rotary furnace; (3) performing dust removal, pickling purification, drying, conversion and absorption on the SO2-containing gas generated in the rotary furnace in the step (2), thereby obtaining a finished sulfuric acid product; (4) and obtaining solid burning slags from the rotary furnace, i.e., obtaining the calcium oxide generated by the decomposition of the calcium sulfate. As the method is used, the utilization rate of raw materials is improved; and the energy consumption is lowered. Therefore, the cost is lowered greatly.
Description
Technical field
The present invention relates to a kind of method of utilizing gypsum to produce sulfuric acid and calcium oxide.
Background technology
Along with the development of modern industrialization, the quantity discharged of China's industry by-product gypsum also increases greatly.
Industry by-product gypsum is that what to generate in some industrial production is the waste of main component with calcium sulfate.According to reports, the coal-fired average sulfur-bearing of China coal-fired plant is 1.23%, contains a large amount of SO in coal-fired plant's discharged flue gas
2, as not handling, certainly will cause very big harm to environment.National departments concerned stipulates that coal-fired plant must carry out desulfurization to the discharging flue gas and handle.At present, coal-fired plant's flue gas desulfurization mostly is lime-gypsum method, absorbs SO in the flue gas with lime
2, generating calcium sulfate, desulfurization degree can reach more than 95%, and its byproduct is desulfurated plaster.It is calculated that 98.8 tons of every 1MW installed capacity year discharging desulfurated plasters.
According to statistics, China's phosphogypsum quantity discharged in 2009 is 5,840 ten thousand tons, and the desulfurated plaster amount that accounts for 60%, 2010 year China coal-fired plant of industrial secondary gypsum reaches 41,700,000 tons.This shows that China's industry by-product gypsum annual emissions has surpassed 100,000,000 tons, account for 8% of the total industrial solid waste quantity discharged of China, so a large amount of trade wastes is not sought application approach, will cause very big influence to environment.At present, most of mode of burying that adopts is handled in the world, and China's sulphur natural resources shortage is devoted to develop gypsum producing sulfuric acid and jointly cement industry processed technology, for many years so that calcium sulfate (CaSO always
4) in Ca, S element be fully used, almost do not have trash discharge.But because the process complexity of this technology itself: adopt the raw material grinding through the technical process that the laggard calcined by rotary kiln of preheating decomposes, calcium sulfate is decomposed produce to conform with the SO that contains that produces the sulfuric acid requirement
2Kiln gas, the cement clinker that meets the requirements of output again, the technological process variable factor is many, and operation control difficulty is big, and this is one; It two is, raw materials for production are various, and it is strict to prepare burden, the hear rate height, and economic benefit is undesirable; The 3rd, because the controlling of production process variable factor is many, make kiln gas SO with being difficult to avoid
2Big and the cement clinker instability of fluctuation of concentration causes gas washing in SA production to be difficult to control unreliability with cement mark.So, this technology in actual production, apply and have many problems.
Sulfuric acid is industrial application basic chemical industry raw material more widely, and preparing sulfuric acid usually is raw material with sulphur, China's sulphur shortage of resources, but China's anhydrite (main component calcium sulfate) reserves the first in the world is the potential raw material of producing sulfuric acid.Calcium oxide is good siccative, also is the main raw material of construction substrate, and is of many uses.At present, domestic manufacturer is many to be major ingredient with the anhydrite, cooperates coke and other auxiliary materials to prepare producing sulfuric acid and jointly cement, yet only produces sulfuric acid under some situation, does not produce cement, will cause the waste of calcium oxide like this, to such an extent as to cost improves.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, and a kind of cost method that low calcium sulfate is produced sulfuric acid and calcium oxide is provided.
The technical scheme that the present invention solves its technical problem employing is that a kind of calcium sulfate is produced the method for sulfuric acid and calcium oxide, may further comprise the steps:
(1) is the gypsum of the 9.5-19 millimeter rotary kiln of packing into purity 〉=96%, lumpiness, is warming up to 1180 ℃～1220 ℃ (preferred 1200 ℃);
(2) Sweet natural gas and air are imported in the combustion chamber, make Sweet natural gas in the combustion chamber internal combustion, obtain CO
2, H
2With the mixed gas of CO, CO volumetric concentration≤5% in the control mixed gas, CO
2Volumetric concentration 〉=15%; The gained mixed gas is imported the rotary kiln that gypsum is housed, calcium sulfate is in rotary kiln and mixed gas reaction again, and reaction formula is as follows: CaSO
4+ CO → CaO+SO
2+ CO
2CaSO4+H
2→ CaO+SO
2+ H
2O;
Temperature of reaction is preferably 1200 ℃, will cause the material sintering if temperature is too high, will produce side reaction and temperature is too low, generates sulfurated lime, and the side reaction reaction formula is as follows: CaSO
4+ 4CO → CaS+4CO
2CaSO
4+ 4H
2→ CaS+4H
2O
In order to prevent sulfide, the carbon monoxide volumetric concentration in the gas phase must be reduced to below 5%, gas concentration lwevel is remained on above more than 3 times of carbon monoxide concentration, the reaction aspect carbon monoxide concentration at this moment is monomolecular;
(3) with the SO that contains that produces in step (2) rotary kiln
2Gas through dedusting, acid-scrubbing cleaning, drying transforms, and absorbs, and makes finished product sulfuric acid;
(4) solid that comes out in the rotary kiln burns slag, is calcium sulfate and decomposes the calcium oxide that generates.
The condition of complete desulfurization is done than the back proof, when higher and gas concentration lwevel increases in temperature, CO:CaSO
4Initial scale effect less.
Among the present invention, gypsum is periodically in (preferably every the 15 minutes) rotary kiln of packing into.Layer temperature in the device regulated with the gaseous mixture that cooling enters it, and measures with the chromium line-nickel wire thermocouple of sintering metal protection of pipe.
The present invention can improve raw material availability, cuts down the consumption of energy, thereby reduces cost greatly.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment
Present embodiment may further comprise the steps:
(1) with purity be 96%, lumpiness is 15 ± 1 millimeters the gypsum rotary kiln of packing into, is warming up to 1200 ℃;
(2) Sweet natural gas and air are imported in the combustion chamber, make Sweet natural gas in the combustion chamber internal combustion, obtain CO
2, H
2With the mixed gas of CO, the CO volumetric concentration in the control mixed gas is 5%, CO
2Volumetric concentration is 16%; The gained mixed gas is imported the rotary kiln that gypsum is housed, calcium sulfate is in rotary kiln and mixed gas reaction again, and reaction formula is as follows: CaSO
4+ CO → CaO+SO
2+ CO
2CaSO4+H
2→ CaO+SO
2+ H
2O;
(3) with the SO that contains that produces in step (2) rotary kiln
2Gas through dedusting, acid-scrubbing cleaning, drying transforms, and absorbs, and makes finished product sulfuric acid;
(4) solid that comes out in the rotary kiln burns slag, is calcium sulfate and decomposes the calcium oxide that generates.
Claims (2)
1. a method of utilizing gypsum to produce sulfuric acid and calcium oxide is characterized in that, may further comprise the steps:
(1) is the gypsum of the 9.5-19 millimeter rotary kiln of packing into purity 〉=96%, lumpiness, is warming up to 1180 ℃～1220 ℃;
(2) Sweet natural gas and air are imported in the combustion chamber, make Sweet natural gas in the combustion chamber internal combustion, obtain CO
2, H
2With the mixed gas of CO, CO volumetric concentration≤5% in the control mixed gas, CO
2Volumetric concentration 〉=15%; The gained mixed gas is imported the rotary kiln that gypsum is housed, calcium sulfate is in rotary kiln and mixed gas reaction again, and reaction formula is as follows: CaSO
4+ CO → CaO+SO
2+ CO
2CaSO4+H
2→ CaO+SO
2+ H
2O;
(3) with the SO that contains that produces in step (2) rotary kiln
2Gas through dedusting, acid-scrubbing cleaning, drying transforms, and absorbs, and makes finished product sulfuric acid;
(4) solid that comes out in the rotary kiln burns slag, is calcium sulfate and decomposes the calcium oxide that generates.
2. the method for utilizing gypsum to produce sulfuric acid and calcium oxide according to claim 1 is characterized in that, in the step (1), gypsum packed into is warming up to 1200 ℃ behind the rotary kiln.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102171753A CN103253637A (en) | 2013-06-04 | 2013-06-04 | Method for producing sulfuric acid and calcium oxide by utilizing gypsum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102171753A CN103253637A (en) | 2013-06-04 | 2013-06-04 | Method for producing sulfuric acid and calcium oxide by utilizing gypsum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103253637A true CN103253637A (en) | 2013-08-21 |
Family
ID=48957920
Family Applications (1)
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|---|---|---|---|
| CN2013102171753A Pending CN103253637A (en) | 2013-06-04 | 2013-06-04 | Method for producing sulfuric acid and calcium oxide by utilizing gypsum |
Country Status (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482586A (en) * | 2013-09-06 | 2014-01-01 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| CN111566051A (en) * | 2017-11-22 | 2020-08-21 | Ocp有限公司 | Phosphogypsum decomposition method |
| CN113603126A (en) * | 2021-09-17 | 2021-11-05 | 中国科学院过程工程研究所 | Method for preparing calcium oxide by using industrial byproduct gypsum |
| CN114249335A (en) * | 2021-11-22 | 2022-03-29 | 国能(山东)能源环境有限公司 | Reaction system and method for resource utilization of desulfurized gypsum |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696073A (en) * | 2005-03-23 | 2005-11-16 | 湖南湘福新型建材有限责任公司 | Method for producing sulfuric acid associated with high Belite cement through anhydrite |
| CN102442650A (en) * | 2011-10-18 | 2012-05-09 | 中国石油化工集团公司 | Method for producing sulfuric acid and co-producing calcium carbide by phosphogypsum |
-
2013
- 2013-06-04 CN CN2013102171753A patent/CN103253637A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696073A (en) * | 2005-03-23 | 2005-11-16 | 湖南湘福新型建材有限责任公司 | Method for producing sulfuric acid associated with high Belite cement through anhydrite |
| CN102442650A (en) * | 2011-10-18 | 2012-05-09 | 中国石油化工集团公司 | Method for producing sulfuric acid and co-producing calcium carbide by phosphogypsum |
Non-Patent Citations (2)
| Title |
|---|
| 刘觉民等: "《无机化工三废综合治理》", 31 May 1990, article "无机化工三废综合治理", pages: 156-157 * |
| 胡道和: "《胡道和水泥工程科研论文集》", 30 June 2010, article "胡道和水泥工程科研论文集", pages: 471-474 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482586A (en) * | 2013-09-06 | 2014-01-01 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| CN103482586B (en) * | 2013-09-06 | 2015-01-28 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| CN111566051A (en) * | 2017-11-22 | 2020-08-21 | Ocp有限公司 | Phosphogypsum decomposition method |
| CN113603126A (en) * | 2021-09-17 | 2021-11-05 | 中国科学院过程工程研究所 | Method for preparing calcium oxide by using industrial byproduct gypsum |
| CN114249335A (en) * | 2021-11-22 | 2022-03-29 | 国能(山东)能源环境有限公司 | Reaction system and method for resource utilization of desulfurized gypsum |
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Application publication date: 20130821 |