CN103387249A - Method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials - Google Patents
Method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials Download PDFInfo
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- CN103387249A CN103387249A CN2013103303266A CN201310330326A CN103387249A CN 103387249 A CN103387249 A CN 103387249A CN 2013103303266 A CN2013103303266 A CN 2013103303266A CN 201310330326 A CN201310330326 A CN 201310330326A CN 103387249 A CN103387249 A CN 103387249A
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- thionizer
- magnesium oxide
- mgso
- doctor solution
- sulphur
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention relates to the field of production of inorganic chemical products and in particular relates to a method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials. The method is characterized in that sulfur atoms generated by a coke oven gas wet oxidation desulfurization (ammonia method) process are converted into SO2 through incineration; the SO2 reacts with magnesium oxide to generate magnesium sulfate; high-temperature flue gas generated by a combustion furnace is subjected to heat exchange by a waste heat boiler, conveyed to a desulfurization tower and subjected to spray cooling by MgSO4 mother liquid at a cooling section; the flue gas moves upwards to a desulfurization section and is subjected to countercurrent contact with desulfurization liquid; the SO2 in the flue gas is absorbed by the desulfurization liquid and reacts with Mg(OH)2 to generate MgSO3; the MgSO3 in the desulfurization liquid is oxidized to generate MgSO4; the MgSO4 is subjected to vacuum extraction to obtain MgSO4 crystals; the MgSO4 mother liquid at the bottom of the desulfurization tower is subjected to vacuum flashing and cooling by a flash tank. Compared with the prior art, the method has the advantages that the magnesium sulfate serving as an important chemical material and chemical fertilizer has wide market prospect and significant economic benefit.
Description
Technical field
The present invention relates to the inorganic chemistry goods and make field, particularly sulphur slurry and the magnesium oxide of coke-oven gas Wet-type oxidation sweetening technique (ammonia process) generation are the method for raw material production sal epsom.
Background technology
Coke oven contains NH in the thick coke-oven gas that process of coking produces
3, H
2The impurity such as S and HCN, thick coke-oven gas obtains clean coke-oven gas through purifying treatment.Remove NH
3, H
2The clean coke-oven gas of the impurity such as S and HCN uses as industrial fuel or industrial chemicals.The coal gas desulfurization Technology is the important component part of fine purification technique for coke oven gas, in fine purification technique for coke oven gas, has multiple sulfur removal technology technology to be employed at present.Wherein Wet-type oxidation sweetening (ammonia process) process application is extensive, and the advantage of this technique is that desulfuration efficiency is high, need not exogenously added alkali, and process cost is low; Shortcoming is H in coal gas
2S, HCN are converted into by absorption, the oxidation regeneration of doctor solution the sulphur slurry that contains sulphur, ammonium thiosulfate and ammonium thiocyanate, water content in the sulphur slurry reaches weight percent 30 ~ 60%, sulphur slurry treatment process generally adopts and melts sulphur method and the concentrated salt technique of putting forward, the product of this technique is low-purity sulphur and mixing salt, exist production cost high, the deficiency that the production operation environmental pollution is serious, and produce market sales difficulty.
Summary of the invention
The purpose of this invention is to provide a kind of method take sulphur slurry and magnesium oxide as raw material production sal epsom, produce broad-spectrum chemical fertilizer and industrial chemicals product---sal epsom with the sulphur slurry that coke-oven gas Wet-type oxidation sweetening (ammonia process) technique produces, solve the sulphur slurry and further separate the problem of processing, the produce market demand is large, makes the sulphur slurry obtain comprehensive utilization of resources.
For achieving the above object, the present invention is achieved through the following technical solutions,
A kind of method take sulphur slurry and magnesium oxide as raw material production sal epsom, by burning, the sulphur atom during the sulphur that coke-oven gas Wet-type oxidation sweetening (ammonia process) technique is produced is starched is converted into SO
2, then with magnesium oxide, react and generate sal epsom, its detailed process is described below:
Sulphur slurry, coal gas and air are passed into roasting kiln burn, the high-temperature flue gas that roasting kiln produces is delivered to thionizer after by the waste heat boiler heat exchange; High-temperature flue gas enters the thionizer cooling section through MgSO
4The mother liquor spraying cooling, go upward to thionizer desulfurization section and doctor solution counter current contact, the SO in flue gas after flue gas is cooling
2Be desulfurized liquid and absorb, SO
2With Mg in doctor solution (OH)
2Reaction generates MgSO
3The doctor solution that thionizer is discharged is from flowing to the doctor solution medial launder, and the doctor solution in the doctor solution medial launder is delivered to the thionizer circulation through recycle pump and sprayed, and the partial desulfurization liquid in the doctor solution medial launder is from flowing to oxidation trough, blast air in oxidation trough, the MgSO in doctor solution
3Oxidized generation MgSO
4A part of MgSO in oxidation trough
4Mother liquor is sent back to thionizer cooling section spraying cooling flue gas, a part of MgSO
4Mother liquor send vacuum crystallization device to extract MgSO
4Crystallization; MgSO at the bottom of thionizer
4Mother liquor by tower at the bottom of mother liquor be pumped to flash drum vacuum flashing and return to oxidation trough after cooling; Magnesium oxide mixes in slurry tank with water, passes into the steam heating slaking and obtains Mg (OH)
2Slurries, deliver to the doctor solution medial launder through slush pump.
Main component in described sulphur slurry is sulphur, thiosulfuric acid ammonium salt, thiocyanate-and water.
Coefficient of excess air in described roasting kiln is 1.2 ~ 1.5, and in roasting kiln, temperature is 1100 ~ 1200 ℃.
After described waste heat boiler heat exchange, flue-gas temperature is 280 ~ 350 ℃.
The structure of described thionizer is two sections, and hypomere is cooling section, and epimere is desulfurization section, and the below of thionizer top vent is provided with flutters the mist layer.
Compared with prior art, the invention has the beneficial effects as follows:
The sulphur slurry that this technique produces take coke-oven gas Wet-type oxidation sweetening (ammonia process) technique and magnesium oxide, as raw material production sal epsom product, have solved low-quality sulphur slurry and have further separated the problem of processing, make sulphur, the sulphur in salt of sulphur in starching finally be converted into SO
4Radical ion, sal epsom has wide market as important industrial chemicals and chemical fertilizer, and remarkable in economical benefits is fully utilized sulphur slurry resource.
Description of drawings
Fig. 1 is process flow diagram of the present invention.
In figure: at the bottom of 1-roasting kiln 2-waste heat boiler 3-thionizer 4-blower fan 5-recycle pump 6-tower, mother liquor pump 7-doctor solution medial launder 8-oxidation trough 9-mother liquor pump 10-slush pump 11-slurry tank 12-flash drum 13-flutters the mist layer
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further:
Seeing Fig. 1, is a kind of method process flow sheet take sulphur slurry and magnesium oxide as raw material production sal epsom of the present invention, and the present invention is by burning, and the sulphur atom during the sulphur that coke-oven gas Wet-type oxidation sweetening (ammonia process) technique is produced is starched is converted into SO
2, then with magnesium oxide, react and generate sal epsom, the main component in sulphur slurry of the present invention is sulphur, thiosulfuric acid ammonium salt, thiocyanate-and water, and wherein water content (wt%) is 30 ~ 60%, and its detailed process is described below:
Sulphur slurry, coal gas and air are passed into roasting kiln 1 burn, in the sulphur slurry, sulphur atom is converted into SO
2, the coefficient of excess air in roasting kiln is 1.2 ~ 1.5, and temperature is 1100 ~ 1200 ℃ in roasting kiln, and the high-temperature flue gas that roasting kiln 1 produces is delivered to thionizer 3 after by waste heat boiler 2 heat exchange, and after the waste heat boiler heat exchange, high-temperature flue-gas is 280 ~ 350 ℃; High-temperature flue gas enters the thionizer cooling section through MgSO
4Mother liquor spraying cooling, the SO in flue gas at this moment
2Concentration is 5 ~ 8%, and cooling rear flue gas goes upward to thionizer desulfurization section and doctor solution counter current contact, the SO in flue gas
2Be desulfurized liquid and absorb, SO
2With Mg in doctor solution (OH)
2Reaction generates MgSO
3The doctor solution that thionizer 3 is discharged is from flowing to doctor solution medial launder 7, thionizer 3 top exits are connected with blower fan 4, doctor solution in doctor solution medial launder 7 is delivered to thionizer 3 circulations through recycle pump 5 and is sprayed, partial desulfurization liquid in doctor solution medial launder 7 is from flowing to oxidation trough 8, blast air in oxidation trough 8, the MgSO in doctor solution
3Oxidized generation MgSO
4A part of MgSO in oxidation trough 8
4Mother liquor is sent back to thionizer 3 cooling section spraying cooling flue gases, a part of MgSO
4Mother liquor send vacuum crystallization device to extract MgSO
4Crystallization; The MgSO at 3 ends of thionizer
4Mother liquor by tower at the bottom of mother liquor pump 6 deliver to flash drum 12 vacuum flashings and return to oxidation trough 8 after cooling, the flash-off steam that flash drum 12 produces is connected to vacuum system, flash drum 12 makes the MgSO that heats up at the bottom of thionizer on the one hand
4Mother liquor obtains cooling, also makes simultaneously MgSO
4Mother liquid evaporation is concentrated; Magnesium oxide mixes in slurry tank 11 with water, passes into the steam heating slaking and obtains Mg (OH)
2Slurries, deliver to doctor solution medial launder 7 through slush pump 10.
The structure of thionizer 3 is two sections, and hypomere is cooling section, and epimere is desulfurization section, and the below of thionizer top vent is provided with flutters mist layer 13, and flue gas removes SO
2Flutter the mist layer by the desulfurization tower top and flutter mist, after demist, flue gas drains into blower fan 4 by tower top, through pressurization, drains into atmosphere.
In technique of the present invention, the main chemical reactions formula of sulphur slurry burning in roasting kiln 1 is as follows:
S+O
2=SO
2
NH
4SCN+3O
2=N
2+CO
2+SO
2+2H
2O
2(NH
4)
2S
2O
3+5O
2=2N
2+4SO
2+8H
2O
2H
2+O
2=2H
2O
2CO+O
2=2CO
2
Main chemical reactions in slurry tank 11 is:
MgO+H
2O=Mg(OH)
2
Main chemical reactions in thionizer 3:
Mg(OH)
2+SO
2=MgSO
3+H
2O
Main chemical reactions in oxidation trough 8 is:
2MgSO
3+O
2=2Mg?SO
4?。
Claims (5)
1. one kind take sulphur slurry and magnesium oxide as the method for raw material production sal epsom, it is characterized in that, by burning, the sulphur atom during the sulphur that coke-oven gas Wet-type oxidation sweetening (ammonia process) technique is produced is starched is converted into SO
2, then with magnesium oxide, react and generate sal epsom, its detailed process is described below:
Sulphur slurry, coal gas and air are passed into roasting kiln burn, the high-temperature flue gas that roasting kiln produces is delivered to thionizer after by the waste heat boiler heat exchange; High-temperature flue gas enters the thionizer cooling section through MgSO
4The mother liquor spraying cooling, go upward to thionizer desulfurization section and doctor solution counter current contact, the SO in flue gas after flue gas is cooling
2Be desulfurized liquid and absorb, SO
2With Mg in doctor solution (OH)
2Reaction generates MgSO
3, the doctor solution that thionizer is discharged is from flowing to the doctor solution medial launder, and the doctor solution in the doctor solution medial launder is delivered to the thionizer circulation through recycle pump and is sprayed, and the partial desulfurization liquid in the doctor solution medial launder, from flowing to oxidation trough, blasts air, the MgSO in doctor solution in oxidation trough
3Oxidized generation MgSO
4A part of MgSO in oxidation trough
4Mother liquor is sent back to thionizer cooling section spraying cooling flue gas, a part of MgSO
4Mother liquor send vacuum crystallization device to extract MgSO
4Crystallization; MgSO at the bottom of thionizer
4Mother liquor by tower at the bottom of mother liquor be pumped to flash drum vacuum flashing and return to oxidation trough after cooling; Magnesium oxide mixes in slurry tank with water, passes into the steam heating slaking and obtains Mg (OH)
2Slurries, deliver to the doctor solution medial launder through slush pump.
2. according to claim 1 a kind ofly take sulphur slurry and magnesium oxide as the method for raw material production sal epsom, it is characterized in that, the main component during described sulphur is starched is sulphur, thiosulfuric acid ammonium salt, thiocyanate-and water, and wherein water content (wt%) is 30 ~ 60%.
3. according to claim 1 a kind ofly take sulphur slurry and magnesium oxide as the method for raw material production sal epsom, it is characterized in that, the coefficient of excess air in described roasting kiln is 1.2 ~ 1.5, and the interior temperature of roasting kiln is 1100 ~ 1200 ℃.
4. according to claim 1 a kind ofly take sulphur slurry and magnesium oxide as the method for raw material production sal epsom, it is characterized in that, after described waste heat boiler heat exchange, flue-gas temperature is 280 ~ 350 ℃.
5. a kind of method take sulphur slurry and magnesium oxide as raw material production sal epsom according to claim 1, it is characterized in that, the structure of described thionizer is two sections, and hypomere is cooling section, epimere is desulfurization section, and the below of thionizer top vent is provided with flutters the mist layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103303266A CN103387249A (en) | 2013-07-31 | 2013-07-31 | Method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103303266A CN103387249A (en) | 2013-07-31 | 2013-07-31 | Method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials |
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| CN103387249A true CN103387249A (en) | 2013-11-13 |
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|---|---|---|---|
| CN2013103303266A Pending CN103387249A (en) | 2013-07-31 | 2013-07-31 | Method for producing magnesium sulfate by using sulfur paste and magnesium oxide as raw materials |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058429A (en) * | 2014-07-04 | 2014-09-24 | 中节能六合天融环保科技有限公司 | Method for magnesium sulfate continuous crystallization |
| CN112090267A (en) * | 2020-09-23 | 2020-12-18 | 北京沃尔福环保科技有限公司 | Flue gas desulfurization process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762550A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Magnesium oxide flue gas desulfurization and outgrowth thick-slurry method oxidation reclaim process |
| CN101530725A (en) * | 2009-03-11 | 2009-09-16 | 清华大学 | Flue gas desulfurization by magnesia wet method and recovering process of automatic concentration of product |
| CN102806004A (en) * | 2011-05-30 | 2012-12-05 | 中国石油化工股份有限公司 | Magnesium desulfurization byproduct recovery process |
| CN102886199A (en) * | 2012-10-26 | 2013-01-23 | 煤炭工业济南设计研究院有限公司 | Flue gas desulfurization device and desulfurization method by magnesium oxide process |
| CN102951657A (en) * | 2012-12-10 | 2013-03-06 | 张卫东 | Process and equipment for producing ammonium sulfate by taking sulfur pulp and ammonia water as raw materials |
-
2013
- 2013-07-31 CN CN2013103303266A patent/CN103387249A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1762550A (en) * | 2005-09-09 | 2006-04-26 | 清华大学 | Magnesium oxide flue gas desulfurization and outgrowth thick-slurry method oxidation reclaim process |
| CN101530725A (en) * | 2009-03-11 | 2009-09-16 | 清华大学 | Flue gas desulfurization by magnesia wet method and recovering process of automatic concentration of product |
| CN102806004A (en) * | 2011-05-30 | 2012-12-05 | 中国石油化工股份有限公司 | Magnesium desulfurization byproduct recovery process |
| CN102886199A (en) * | 2012-10-26 | 2013-01-23 | 煤炭工业济南设计研究院有限公司 | Flue gas desulfurization device and desulfurization method by magnesium oxide process |
| CN102951657A (en) * | 2012-12-10 | 2013-03-06 | 张卫东 | Process and equipment for producing ammonium sulfate by taking sulfur pulp and ammonia water as raw materials |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058429A (en) * | 2014-07-04 | 2014-09-24 | 中节能六合天融环保科技有限公司 | Method for magnesium sulfate continuous crystallization |
| CN112090267A (en) * | 2020-09-23 | 2020-12-18 | 北京沃尔福环保科技有限公司 | Flue gas desulfurization process |
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Application publication date: 20131113 |