CN101244811A - Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate - Google Patents
Method for improving SO2 concentration in acid making technique with decomposition of calcium sulphate Download PDFInfo
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- CN101244811A CN101244811A CN 200810058186 CN200810058186A CN101244811A CN 101244811 A CN101244811 A CN 101244811A CN 200810058186 CN200810058186 CN 200810058186 CN 200810058186 A CN200810058186 A CN 200810058186A CN 101244811 A CN101244811 A CN 101244811A
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Abstract
The invention relates to a method for improving the concentration of the SO2 in decomposing the calcium sulfate to acid craft and a chemical manufacturing technique of sulphuric acid and cement clinker, in particular to a manufacturing technique of sulphuric acid and cement clinker made from calcium sulfate. The procedures of the invention are as follows: a, under the function of the strong reduction medium, the calcium sulfate is produced into calcium vulcanization in the reactor; b, the reduction product of a procedure is the compound of the calcium vulcanization and the unreacted calcium sulfate; c, the reduction product is transferred to another reaction directly and under the high temperature, the calcium vulcanization and the calcium sulfate react and make into the SO2 and the clinker. The method has the advantages that: the concentration of the SO2 in gas is increased; the production system of sulfate is more stable and the extensive use of phosphogypsum is possible.
Description
Technical field
The present invention relates to the Chemical Manufacture technology of a kind of sulfuric acid and cement clinker, particularly adopt calcium sulfate to produce the production technique of sulfuric acid and cement clinker.
Background technology
Phosphogypsum is the waste material that produces with the sulfuric acid decomposing phosphate rock in the Chemical Manufacture, its quantity is very big, deal with improperly environmental influence very big, major part is taked the mode of burying in the world, China is because of the sulphur resource shortage, the someone is devoted to develop phosphogypsum jointly producing cement technology always for many years, according to this technology, the waste material phosphogypsum of producing the phosphoric acid generation is used for producing cement and sulfuric acid, sulfuric acid is used for producing phosphoric acid again, and circulation does not almost have waste material repeatedly, but because also there is a large amount of problems in the complicacy of this technology itself in actual the applying of production.From external situation, as far back as 1916, just utilize the hollow rotary kiln to produce cement and vitriolic example abroad, but because of hear rate higher, therefore this technology now is in superseded state substantially, the sixties in last century, development along with the cement dry method production technology, generally adopt the kiln tail preheating technology of low hear rate and the precal cination technique of low-consumption high-efficiency to produce Portland cement in the world, under this background, Austrian Lin Ci company has developed shaft preheater as heat exchanger, and the raw material phosphogypsum promptly mixes with auxiliary material behind first drying, enters the laggard kiln decomposing and calcining of shaft preheater preheating then, compare with original technology, can reduce hear rate, but since the production control difficulty, SO in the gas
2Reasons such as content instability, slower development, in recent years, owing to the inspiration of fluidization technology and cement kiln external decomposition technology and the further understanding of phosphogypsum being decomposed rule, phosphogypsum fluidised bed decomposition new technology, novel process are produced keen interest both at home and abroad, done a large amount of work.China uses gypsum decomposition jointly producing cement and this technology of sulfuric acid is started late, at present proven technique is the pulverulent material after the oven dry to be cooperated with other raw material enter the hollow rotary kiln through grinding and carry out decomposing and calcining, kiln atmosphere is difficult to control, be easy to generate in the kiln problems such as oxygen level is higher, can make the carbon part ground and the oxygen generation combustion reactions that add in the raw material, cause the required carbon deficiency of phosphogypsum decomposition reaction, rate of decomposition and desulfurization degree reduce.The hollow rotary kiln is poor because of its heat-transfer effect in addition, and the high consumption of coal has belonged to superseded technology at China's cement industry.From production status, existing apparatus all is not very desirable, mainly is reflected in the following aspects: 1. the existing mode of production all is that calcium sulfate is directly resolved into SO under weak oxide atmosphere or the two atmosphere of redox
2And calcium oxide, actual decomposition temperature is all more than 1000 ℃, and the inaccessible industrial requirement of the refractory life in the separating device is chosen difficulty, does not have the outer decomposer of kiln of industrialization to go into operation so far.2. calcium sulfate reduction decomposition and oxidation are all carried out in a decomposing furnace or kiln in the existing production technique, and operational condition control is complicated, and poor stability is difficult for realizing, and hear rate is bigger, the SO of generation
2When entering convertor, concentration has only 3-5%, causes the sulfuric acid apparatus production capacity to reduce, and invert point is difficult to guarantee that operation and management difficulty are big.3. being difficult to realizes maximizing produces.Analyze above several respects problem, its major cause is that Production Flow Chart is long, and equipment is many, the energy consumption height, and investment is big, the production cost height;
Chinese patent application numbers 200610022146.1 discloses a kind of phosphogypsum combines relieving haperacidity connection and jointly producing cement with sulphur technology.98124985.X disclose a kind of improving one's methods of producing sulfuric acid and jointly cement of making, all be to produce SO by adding sulphur
2Improve SO
2Concentration is to improve the stability of sulfate system.So just make the whole production control process complicated more, investment increases.While method of admixture sulphur in raw material also may cause the reduction of calcium sulfate rate of decomposition.
Summary of the invention
Purpose of the present invention is intended to overcome the defective of prior art, provides a kind of reaction conditions to be easy to control, and can improve SO in the acid making technique with decomposition of calcium sulphate
2The method of concentration
SO in a kind of raising acid making technique with decomposition of calcium sulphate of the present invention
2The method of concentration, its step is as follows:
A. with calcium sulfate in reactor, under the effect of strong reducing medium, generate sulfurated lime, its chemical reaction is one or two combination in the following reaction;
CaSO
4+2C＝CaS+2CO
2↑
CaSO
4+4CO＝CaS+4CO
2↑
CaSO
4+4H
2＝CaS+4H
2O↑；
B. step a gained reduzate is sulfurated lime and unreacted mixture of calcium sulfate;
C. reduzate is directly transferred in another reactor, sulfurated lime and calcium sulfate react and make SO in reactor
2And cement clinker, its chemical reaction is the one or more combinations in the following reaction:
CaS+2O
2→CaSO
4
2CaS+3O
2→2CaO+2SO2↑
CaS+3CaSO
4→4CaO+4SO2↑
The described reactor of step a is one or both in pillar suspension reactor or the rotary kiln.
Among the step a, SO in the waste gas that reduction-sulfurization calcium produces
2Concentration is low, is used for treated discharging behind the drying material.
Among step a, the c, be interconnected by passage between the solid product, gas passage is two separate systems.
The SO that contains the 8-17% high density in the gas that step c produces
2Gas is used to produce sulfuric acid.
Reactor described in the step c is a rotary kiln.
SO in a kind of raising acid making technique with decomposition of calcium sulphate of the present invention
2The method of concentration, be a kind of be the material of major ingredient with calcium sulfate, as chemical gypsums such as the plaster of paris, phosphogypsum, desulfurated plaster, fluorgypsums, the CO, the H that under oxygen deprivation, burn and produce with C in raw coal or the coke or coal
2As reductive agent, be sulfurated lime with calcium sulfate reduction decomposition under the condition of high temperature, reacting in another reactor B makes SO again
2Gas is used to produce sulfuric acid, and solid is used to produce the new process of production of cement clinker.This technology can make phosphogypsum reduction decomposition furnace temperature reduce to below 1000 ℃, can adopt the outer resolving device of the sophisticated kiln of manufacture of cement, produces a large amount of SO
2Atmosphere does not have strict control requirement in the reactor of gas, and stable production process can realize scale operation.The present invention can improve SO in the gas
2Concentration, make sulfuric acid production system more stable, make a large amount of utilizations of phosphogypsum become possibility.
Prior art SO
2Concentration is generally 6-8%, and this technology can improve SO in the gas
2Concentration 2-10%
Description of drawings
Fig. 1 is a schema of the present invention.
Among the figure: 1-rotary kiln, 2-kiln tail airduct, 3-decomposing furnace, 4-feed-pipe, 5-tornado preheater, 6-whirlwind separator, 7-calcium sulfate raw materials mouth, 8-drying crusher.
Embodiment
The present invention is described further below in conjunction with embodiment, but be not limited to embodiment.
Embodiment 1:
With the heap that obtains in the Wet-process Phosphoric Acid Production in the phosphogypsum of slag field, as contain the phosphogypsum of free moisture 9-13%, directly in the revolution hammer drying crusher 8 that adding cement mill grog is used always in burning till from charging opening 7, with after pipeline and preheater 6 carry out heat exchange, enter cyclonic separator 7 from the waste gas below 1000 ℃ of decomposing furnace 3, material after the separation enters in the decomposing furnace 3, the CO that produces with coal dust firing is a reductive agent, is sulfurated lime with the calcium sulfate reduction decomposition; Solid materials after cyclonic separator 6 separates all enters in the rotary kiln 1, is mixed into rotary kiln with distribute the calcium sulfate that enters after the preheating of kiln series preheater from cyclonic separator 5, obtains SO at the kiln internal reaction
2Gas and CaO, solid materials react through further elevated temperature decomposition and at 1300-1450 ℃ and obtain cement clinker.The gas that goes out decomposing furnace, rotary kiln carries out heat exchange through suspended preheater and drying crusher and raw material, and gas temperature is reduced to 120-200 ℃, and through dedusting, purifying treatment, the stove serial gas discharges, and kiln series contains 8-15%SO
2Gas by replenishing air, regulate oxygen sulphur than and drying after enter convertor, be SO through catalyzed oxidation
3, obtain sulfuric acid with the concentrated acid absorption.
Embodiment 2:
In embodiment 1,3-decomposing furnace and 6-whirlwind separator replace with rotary kiln, and other is with embodiment 1.
Embodiment 3:
Calcium sulfate oven dry made to add other behind calcium sulphate hemihydrate or the anhydrous calciumsulphate be that the raw material that satisfies the requirement of the cement clinker prescription back that is mixed adds among 1 or 2 embodiment, realize with increasing the method that one or more tornado preheaters 5 replace drying crushers 8.
Claims (6)
1, SO in a kind of raising acid making technique with decomposition of calcium sulphate
2The method of concentration is characterized in that, step is as follows:
A. with calcium sulfate in reactor, under the effect of strong reducing medium, generate sulfurated lime, its chemical reaction is one or two combination in the following reaction;
CaSO
4+2C＝CaS+2CO
2↑
CaSO
4+4CO＝CaS+4CO
2↑
CaSO
4+4H
2＝CaS+4H
2O↑；
B. step a gained reduzate is sulfurated lime and unreacted mixture of calcium sulfate;
C. reduzate is directly transferred in another reaction, at high temperature sulfurated lime and calcium sulfate react and make SO
2And cement clinker, produce SO
2Chemical reaction be one or more combinations in the following reaction:
CaS+2O
2→CaSO
4
2CaS+3O
2→2CaO+2SO2↑
CaS+3CaSO
4→4CaO+4SO2↑；
2, SO in a kind of raising acid making technique with decomposition of calcium sulphate according to claim 1
2The method of concentration is characterized in that, the described reactor of step a is one or both in pillar suspension reactor or the rotary kiln.
3, SO in a kind of raising acid making technique with decomposition of calcium sulphate according to claim 1
2The method of concentration is characterized in that, among the step a, and SO in the waste gas that reduction-sulfurization calcium produces
2Concentration is low, is used for treated discharging behind the drying material.
4, SO in a kind of raising acid making technique with decomposition of calcium sulphate according to claim 1
2The method of concentration is characterized in that, among step a, the c, is interconnected by passage between the solid product, and gas passage is two separate systems.
5, SO in a kind of raising acid making technique with decomposition of calcium sulphate according to claim 1
2The method of concentration is characterized in that, contains the SO of 8-17% high density in the gas that step c produces
2Gas is used to produce sulfuric acid.
6, SO in a kind of raising acid making technique with decomposition of calcium sulphate according to claim 1
2The method of concentration is characterized in that, the reactor described in the step c is a rotary kiln.
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| CN101244811B CN101244811B (en) | 2014-08-27 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844748A (en) * | 2010-05-18 | 2010-09-29 | 云南创兴建材新技术有限公司 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
| CN103030165A (en) * | 2012-11-27 | 2013-04-10 | 刘立文 | Method for treating waste generated in process of producing calcium oxide from calcium sulfate |
| CN103288056A (en) * | 2013-01-30 | 2013-09-11 | 昆明隆青化工有限公司 | Method for decomposing phosphogypsum to produce SO2 |
| CN103496861A (en) * | 2013-09-24 | 2014-01-08 | 龚家竹 | Production method for co-producing cement and sulfuric acid by using gypsum |
| CN103663388A (en) * | 2013-12-06 | 2014-03-26 | 云南创兴建材新技术有限公司 | Method and reactor for preparing high concentration SO2 flue gas by using phosphogypsum through CaS |
| CN109650345A (en) * | 2018-04-09 | 2019-04-19 | 西南科技大学 | Method for respectively utilizing sulfur and calcium resources in gypsum |
| CN111170348A (en) * | 2019-11-29 | 2020-05-19 | 四川大学 | Method for preparing calcium oxide and co-producing sulfuric acid by using titanium gypsum |
| CN113148961A (en) * | 2021-03-31 | 2021-07-23 | 云南云天化环保科技有限公司 | System and process for preparing high-concentration sulfur dioxide flue gas by using phosphogypsum |
-
2008
- 2008-03-17 CN CN200810058186.0A patent/CN101244811B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844748B (en) * | 2010-05-18 | 2011-08-24 | 云南创兴建材新技术有限公司 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
| CN101844748A (en) * | 2010-05-18 | 2010-09-29 | 云南创兴建材新技术有限公司 | Method for preparing high-concentration SO2 flue gas and active CaO by using phosphogypsum and decomposing furnace |
| CN103030165A (en) * | 2012-11-27 | 2013-04-10 | 刘立文 | Method for treating waste generated in process of producing calcium oxide from calcium sulfate |
| CN103288056B (en) * | 2013-01-30 | 2015-10-14 | 昆明隆青化工有限公司 | A kind of decomposing phosphogypsum prepares SO 2method |
| CN103288056A (en) * | 2013-01-30 | 2013-09-11 | 昆明隆青化工有限公司 | Method for decomposing phosphogypsum to produce SO2 |
| CN103496861A (en) * | 2013-09-24 | 2014-01-08 | 龚家竹 | Production method for co-producing cement and sulfuric acid by using gypsum |
| CN103496861B (en) * | 2013-09-24 | 2015-10-28 | 龚家竹 | A kind of gypsum produces the production method of cement joint production sulfuric acid |
| CN103663388B (en) * | 2013-12-06 | 2015-04-22 | 云南创兴建材新技术有限公司 | Method and reactor for preparing high concentration SO2 flue gas by using phosphogypsum through CaS |
| CN103663388A (en) * | 2013-12-06 | 2014-03-26 | 云南创兴建材新技术有限公司 | Method and reactor for preparing high concentration SO2 flue gas by using phosphogypsum through CaS |
| CN109650345A (en) * | 2018-04-09 | 2019-04-19 | 西南科技大学 | Method for respectively utilizing sulfur and calcium resources in gypsum |
| CN111170348A (en) * | 2019-11-29 | 2020-05-19 | 四川大学 | Method for preparing calcium oxide and co-producing sulfuric acid by using titanium gypsum |
| CN111170348B (en) * | 2019-11-29 | 2022-04-26 | 四川大学 | Method for preparing calcium oxide and co-producing sulfuric acid by using titanium gypsum |
| CN113148961A (en) * | 2021-03-31 | 2021-07-23 | 云南云天化环保科技有限公司 | System and process for preparing high-concentration sulfur dioxide flue gas by using phosphogypsum |
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| Publication number | Publication date |
|---|---|
| CN101244811B (en) | 2014-08-27 |
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Effective date of registration: 20200901 Address after: 650228 No. 1417, Dianchi Road, Xishan District, Yunnan, Kunming Patentee after: YUNNAN YUNTIANHUA Co.,Ltd. Address before: 650000 No. 1417, Dianchi Road, Xishan District, Yunnan, Kunming Patentee before: YUNNAN YUNTIANHUA INTERNATIONAL CHEMICAL Co.,Ltd. |
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