CN102633237B - Method for producing liquid sulfur dioxide by using gypsum (CaSO4) - Google Patents
Method for producing liquid sulfur dioxide by using gypsum (CaSO4) Download PDFInfo
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Abstract
The invention relates to a method for producing liquid sulfur dioxide by using gypsum (CaSO4). Gas sulfur dioxide is firstly prepared by using the gypsum and coke as main raw materials, purified gas sulfur dioxide is then absorbed by using a sodium citrate lean solution, sulfur dioxide in the sodium citrate lean solution can be increased to obtain a sodium citrate pregnant solution, the sodium citrate pregnant solution is then subjected to heating, air stripping and resolution to produce saturated-steam-containing sulfur dioxide gas and a sodium citrate lean solution, and the liquid sulfur dioxide is obtained after the saturated-steam-containing sulfur dioxide gas is subjected to cooling, drying, compression and condensation; and the raw materials are subjected to calcination reaction in a rotary kiln during the process of the preparation of the gas sulfur dioxide, wherein the O2 content of the tail gas of the rotary kiln is controlled to be 0.05%-1.0%, and the CO content is controlled to be less than 0.4%, in terms of mass percentage. According to the method for producing the liquid sulfur dioxide by using the gypsum (CaSO4), provided by the invention, the decomposition reaction efficiency of the CaSO4 is high, and the sulfur loss is little; and the mass concentration of the obtained sulfur dioxide gas reaches 10%-13%, the liquid sulfur dioxide is prepared from the sulfur dioxide gas by adopting a sodium citrate method, and the sodium citrate solution is nontoxic and is difficult to burn, so that the production operation is safe.
Description
Technical field
The present invention relates to one utilizes gypsum to produce liquid SO
2production method, belong to Chemical Engineering Technology and industrial solid castoff comprehensive utilization of resources field.
Background technology
Traditional liquid SO
2production method be with sulphur burn or adopt sulfurous iron ore be raw material, produce SO
2gas, then adopt ammonium acid system, pure oxygen burning method, Citrate Buffer to produce liquid SO
2; And China's sulphur, ferro-sulphur ore scarcity need a large amount of imports to meet sulfuric acid and liquid SO every year
2production.China's plaster of paris and various chemical gypsum (phosphogypsum, desulfurated plaster etc.) resource is very abundant, especially pile up like a mountain for chemical gypsum, not only take also contaminate environment of a large amount of soils, active development utilizes gypsum to produce the product of sulfur dioxide liquid, turn waste into wealth, be profit in contemporary merit the cause in eternal lasting.
Adopt gypsum be raw material to prepare sulfur dioxide gas be take coke as reductive agent, the CaSO in reduction decomposition gypsum
4at high temperature produce following reaction: the first stage, temperature is CaSO in the time of 800～1000 ℃
4+ 2C----CaS+2CO
2, subordinate phase, temperature is 3CaSO in the time of 1000～1250 ℃
4+ CaS---4CaO+4SO
2decompose and produce SO
2gas, the CaO decompositing uses as material of construction.In the time utilizing all kinds of gypsum to produce the sulfur-bearing products such as sulfur dioxide liquid, due to the SO take all kinds of gypsum as raw material production
2unstripped gas concentration is too low, has lost economic worth, has been difficult to participate in market competition thereby prepare the products such as sulfur dioxide liquid, therefore produces sulfur dioxide liquid take cheap gypsum as primary industryization and is difficult to realize always.
Summary of the invention
The object of the present invention is to provide a kind of method take gypsum as raw material production sulfur dioxide liquid, adopt that the commodity sulfur dioxide liquid cost prepared of the method is low, remarkable in economical benefits.
The present invention seeks to be achieved through the following technical solutions:
A kind of gypsum is produced the method for sulfur dioxide liquid, it is characterized in that: first prepare gaseous sulfur dioxide take gypsum, coke as main raw material, again the sodium citrate solution for gaseous sulfur dioxide (lean solution) after purifying treatment is absorbed to the sulfurous gas making in sodium citrate solution and increase (rich solution), generate sulfur dioxide gas and Trisodium Citrate lean solution containing saturated steam with heating, air lift, parsing rich solution again, the described sulfur dioxide gas containing saturated steam obtains sulfur dioxide liquid after cooling, dry, compression, condensation; Described preparation gaseous sulfur dioxide process Raw is calcination reaction in rotary kiln, controls O in rotary kiln tail gas
2content 0.05%～1.0%, CO < 0.4%, in quality percentage composition.
The decomposition of gypsum raw material in rotary kiln can follow side reaction to produce conventionally, generates sublimed sulphur and causes the loss of serious sulphur, and contriver finds in long-term experiment, when oxygen content there will be CaSO in gypsum higher than above-mentioned value range
4melting point depression, CaSO
4greatly affect its decomposition reaction efficiency thereby change in a large number molten state into, when oxygen content during lower than above-mentioned value range sublimed sulphur constantly generate, brought sulphur loss.O in control kiln exhaust gas of the present invention
2thereby effectively stop the appearance of sublimed sulphur, improved CaSO simultaneously in above-mentioned scope with the content of CO
4decomposition reaction efficiency, improved the concentration of gained sulfur dioxide gas.
Preferably, in above-mentioned preparation, control the kiln speed of rotary kiln at 1.5～2.5 revs/min; Air intake adopts secondary air, one time cool ambient air for elegance, assurance coal dust enter in kiln and burning equably, secondary air from kiln hood discharge to clinker cooling hot blast after treatment, primary air flow account for total blast volume 20～30%, secondary air flow accounts for 70～80% of total blast volume, in volumn concentration.
Gypsum raw material calcining and decomposing in rotary kiln, always some fails to decompose, remain in grog, thereby further improve the concentration of gained sulfur dioxide gas in order further to improve decomposition efficiency in gypsum, in the raw material of above-mentioned preparation gaseous sulfur dioxide, gypsum is selected CaSO
4gypsum, the coke of content>=85% are selected the coke containing fixed carbon>=75%, all in quality percentage composition; Wherein gypsum granularity is that 0.08 ㎜ tails over 15～20%, and coke size is that 0.2 ㎜ tails over < 20%.
Contriver finds in long-term experiment, if the improper coke that is prone to of the granularity control of reaction raw materials is at CaSO
4before not starting to decompose, just burnt, easily made CaSO
4not exclusively affect CaSO thereby decompose
4decomposition efficiency, each raw material granularity is rationally controlled to above-mentioned scope and has improved CaSO
4decomposition efficiency.
Thereby residually cause sulphur loss if C too much can cause CaS in final grog in above-mentioned raw materials, remain the concentration that C burning generation flue gas has also reduced sulfurous gas simultaneously, in order further to improve decomposition efficiency, to reduce sulphur loss, C/SO pressed by above-mentioned gypsum, coke raw material by the present invention
3mol ratio is controlled at 0.6～0.65:1.
Most preferably say, in order further to improve CaSO
4decomposition efficiency, reduce sulphur loss simultaneously, the present invention reacts in mixing raw material, by quality proportioning: gypsum 83～88%, coke 4～8%, yellow sand 3～5%, shale 2～5%, iron powder 1～2%; Gypsum is selected CaSO
4gypsum, the coke of content>=85% are selected the coke containing fixed carbon>=75%.
Further, contriver also finds that raw material is in rotary kiln in calcination reaction process, and the heat lost by radiation that the sensible heat that flue gas is taken away accounts for 27% left and right, the cylindrical shell of hear rate accounts for 20% left and right of hear rate, sensible heat that clinker discharging is taken away accounts for 10% of hear rate, and CaSO
4together with the gas that the flue gas that the sulfur dioxide gas of decomposition gained and rotary kiln coal produce and the decomposition of other raw materials produce, in kiln, discharge, the exhaust gas volumn that coal consumption is high, coal burning produces is larger, in kiln gas, the concentration of sulfur dioxide gas is lower, and hear rate is got over conference and greatly increased the coal consumption of reaction.
In order to reduce coal consumption, above-mentioned raw materials in calcination reaction process, takes insulation to process in rotary kiln, has specifically adopted one deck refractory brick at cylinder of rotary kiln internal surface, and described refractory brick preferably adopts the trapezoidal phosphoric acid salt refractory brick of 200 × 200 × 90 × 80cm.
In order to reduce hear rate, realize the recycle of heat, the kiln gas that kiln tail is discharged carries out heat exchange by raw material, has effectively improved the pre-thermo-efficiency of raw material, also makes kiln tail kiln gas temperature effectively be reduced simultaneously.Grog is carried out to cooling process, adopt air girder grate cooler (commercially available equipment) to carry out grog cooling, make grog be cooled to 65 ℃ by original 200～300 ℃, also improved the secondary air temperature of entering kiln simultaneously, improved the efficiency of combustion of coal dust.
The most specifically, a kind of gypsum is produced the method for sulfur dioxide liquid, makes industrial SO 2 unstripped gas by the raw material of following mass percent calcination reaction in rotary kiln, gypsum 85%, coke 6%, yellow sand 3%, shale 4%, iron powder 2%, and gypsum is selected CaSO
4gypsum, the coke of content>=85% are selected the coke containing fixed carbon>=75%, and gypsum granularity is that 0.08 ㎜ tails over 18%, and coke size is that 0.2 ㎜ tails over < 20%; Wherein control O in rotary kiln tail gas
2content 0.05%～1.0%, CO < 0.4%, in quality percentage composition;
In described calcined by rotary kiln reaction process, control the kiln speed of rotary kiln at 1.5～2.5 revs/min; Air intake adopts secondary air, one time cool ambient air for elegance, assurance coal dust enter in kiln and burning equably, secondary air from kiln hood discharge to clinker cooling hot blast after treatment, primary air flow account for total blast volume 20～30%, secondary air flow accounts for 70～80% of total blast volume, in volumn concentration;
Described raw material in calcination reaction process, takes insulation to process in rotary kiln, specifically adopts one deck refractory brick at cylinder of rotary kiln internal surface, and described refractory brick adopts 200 × 200 × 90 × 80 trapezoidal phosphoric acid salt refractory brick; The kiln gas that kiln tail is discharged carries out heat exchange with the raw material of question response in level Four suspended preheater, then by gained kiln gas heat recovery and utilization; Grog is carried out to cooling process, adopt air girder grate cooler (commercially available equipment) to carry out grog cooling, make grog be cooled to 65 ℃ by original 200～300 ℃, simultaneously using the hot blast of generation as the secondary air of entering kiln;
After above-mentioned and raw material heat exchange, the kiln gas of gained obtains industrial SO 2 unstripped gas through dedusting, washing, purifying processing;
Industrial SO 2 unstripped gas obtained above adopts Citrate Buffer to prepare sulfur dioxide liquid, specifically the solid citric acid of purchase and solid sodium carbonate are mixed with to citric acid lean solution take mass ratio as 1:0.82, after adopting sodium citrate solution (lean solution) to absorb the sulfurous gas in kiln gas, make the sulfurous gas in sodium citrate solution increase (rich solution), again with heating, air lift, resolve rich solution and generate sulfur dioxide gas and the Trisodium Citrate lean solution containing saturated steam, the described sulfur dioxide gas containing saturated steam is through cooling, dry, compression, after condensation, obtain sulfur dioxide liquid product, net reaction is expressed as:
Ct
3 -represent Trisodium Citrate root.
The present invention has following beneficial effect:
CaSO in preparation method of the present invention
4rate of decomposition > 96%, CaS < 2.5wt%, SO in last gained grog
3< 1wt%, decomposition reaction efficiency is high, sulphur loss is little; The present invention has successfully realized and has utilized cheap, abundant gypsum to produce sulfur dioxide gas as main raw materials, gained sulfur dioxide gas mass concentration reaches 10%～13%, and the sulfur dioxide liquid product that adopts Citrate Buffer to prepare this sulfur dioxide gas meets national standard completely; Make absorption agent with sodium citrate solution, absorb the sulfurous gas in kiln gas, and thermal regeneration, obtain pure sulfurous gas compressed, the cooling liquid product that obtains again, it has utilized the damping characteristics of triprotic acid, increase the solubleness of sulfurous gas in solution, utilize the effect of its complexing sulfurous gas, minimizing inferior sulfate radical is oxidized to the side reaction of sulfate radical; Trisodium Citrate lean solution recycles after cooling, and Trisodium Citrate liquid is nontoxic, nonflammable, production operation safety; It is main material production that sulfur dioxide liquid preparation method of the present invention adopts cheapness, abundant gypsum, with low cost, be suitable for industrialization promotion.
Embodiment
Below by example, the present invention is specifically described; be necessary to be pointed out that at this; following instance is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to foregoing invention content.
Embodiment 1
Gypsum is produced a method for sulfur dioxide liquid, carries out according to the following steps:
1, raw material are equipped with: take the gypsum 85% of mass percent, coke 6%, yellow sand 3%, shale 4%, iron powder 2% as raw material, gypsum is CaSO
4the gypsum of content>=85%, coke are the coke containing fixed carbon>=75%, and gypsum granularity is that 0.08 ㎜ tails over 18%, and coke size is that 0.2 ㎜ tails over < 20%; Each material proportion is realized by measuring belt scale, and adding with metering screw of raw material adds, and accomplishes to feed in raw material even, smooth, can not occur fracture phenomenon, and accurate measurement, regulates freely;
2, calcination reaction in rotary kiln: the above-mentioned raw material that configure are added in rotary kiln and calcined, control the kiln speed of rotary kiln at 1.5 revs/min; Air intake adopts secondary air, elegance enters from coal spouting gun by cool ambient air, guarantee that coal dust enters in kiln and burning equably, primary air flow accounts for 30% of total blast volume, what secondary air was discharged from kiln hood air girder grate cooler accounts for 70% of total blast volume to clinker cooling hot blast after treatment, secondary air flow, in volumn concentration; To CO, O in kiln exhaust gas body
2, SO
2etc. composition on line analyzer is housed to guarantee O in kiln exhaust gas
2content is 0.05%～1.0% and CO < 0.4%, in quality percentage composition; Lay one deck refractory brick, the trapezoidal phosphoric acid salt refractory brick that described refractory brick is 200 × 200 × 90 × 80cm at cylinder of rotary kiln internal surface; Compound is calcined in rotary kiln, and rotary kiln provides thermal source by coal dust, and kiln gas amount and composition that decomposing and calcining gypsum produces are:
Kiln gas amount: 1.2～1.4N m
3/ kg; Compound; Water content: 6.27%; 350 ℃ of temperature <; Pressure :-2000Pa; Dust content < 3g/m
3; Kiln gas main component (butt leaks out containing kiln tail) SO
213%, O
20.06～0.08%, CO 0.20%, CO
218～20%, all by percentage to the quality;
3, after described calcined by rotary kiln reaction, the kiln gas that kiln tail is discharged carries out heat exchange with the raw material of question response in level Four suspended preheater, make kiln tail kiln gas temperature be reduced to 300 ℃ by 600 ℃ of original left and right, then gained is contained to the kiln gas heat recovery and utilization of sulfurous gas; The grog that calcination reaction is generated carries out cooling process, adopt air girder grate cooler (commercially available equipment) to carry out cooling to grog, make grog be cooled to 65 ℃ by original 200～300 ℃, improved the efficiency of combustion of coal dust simultaneously using the hot blast of generation as the secondary air recycle of entering kiln;
4, kiln gas purification processing: after above-mentioned and raw material heat exchange, the kiln gas of gained obtains industrial SO 2 unstripped gas, SO after the flow processs such as electric precipitator, dynamic wave scrubber, packing tower washer, electrostatic precipitator purify
2concentration can reach 13wt%, CaSO in preparation method of the present invention
4rate of decomposition is 99%, and in last gained grog, CaS only accounts for 0.8wt%, SO
3be only 0.2wt%.
Be below the processing parameter of kiln gas purification technique:
(1), dynamic wave scrubber:
65 ℃ of 350 ℃ of outlet air temperature < of import temperature <
Recycle pump pressure: 0.2----0.3Mpa
Dilute acid concentration: 65 ℃ of 10----20% temperature <
Dynamic wave intake pressure :-0.1-----0.5Kpa resistance drop: 2.5----3.0Kpa
(2), packing tower washer:
36 ℃ of 65 ℃ of outlet air temperature < of import temperature <
Recycle pump pressure: 0.15----0.2Mpa
Dilute acid concentration: 35 ℃ of 5wt% temperature <
Packing tower intake pressure :-1.0-----2.0Kpa resistance drop: 0.6Kpa
(3), electrostatic precipitator:
36 ℃ of 36 ℃ of outlet air temperature < of import temperature <
Electricity demist intake pressure :-2.0-----3.0Kpa resistance drop: 0.2----0.4Kpa
Secondary voltage: 40----55KV secondary current: 150----280mA
(4), decontamination index:
Moisture < 0.1g/Nm
3acid mist < 0.03g/Nm
3dirt < 0.002g/Nm
3
5, liquid SO
2production process:
5.1, SO
2absorption
Gas flow process: above-mentioned from the SO after kiln system purification
2kiln gas enters SO
2device district, first enters fiber mist eliminator, send the first absorption tower after removing acid mist.From the SO of fiber mist eliminator
2kiln gas sprays reverse contact of sodium citrate solution (intermediate liquid) of getting off through the first bottom, absorption tower with tower top, and the sulfurous gas in kiln gas send second absorption tower through tower top wire mesh demister after being absorbed by sodium citrate solution.From the first top, absorption tower SO
2kiln gas sprays reverse contact of Trisodium Citrate liquid (lean solution) of getting off through second absorption tower bottom with tower top, and the sulfurous gas in kiln gas is further absorbed by sodium citrate solution, send tail gas absorber by tower top wire mesh demister.Contain a small amount of SO from second absorption tower top
2kiln gas enters tail gas absorber bottom and sprays with tower top that the alkali lye getting off is reverse to be contacted, and the sulfurous gas in kiln gas is further absorbed by alkali lye, by high altitude discharge.
Liquid flow: the sodium citrate solution after desorb enters lean solution groove; Send into by lean pump, interchanger reverse contact of kiln gas that second absorption tower top enters with bottom, the sulfurous gas in kiln gas flows in middle circulation groove after being absorbed by sodium citrate solution; Send into by middle liquid pump, interchanger reverse contact of kiln gas that the first top, absorption tower enters with bottom, the sulfurous gas in kiln gas flows into rich solution circulation groove after being absorbed by sodium citrate solution; After by the rich solution in rich solution circulation groove send resolve workshop section.
5.2 resolve
With rich solution pump by the rich solution in rich solution groove send into poor rich liquid heat exchanger heat exchange heat up after, send high temperature sulfur dioxide gas and the water vapour that Analytic Tower top spray and vaporizer heating and gasifying generate to conduct heat at Analytic Tower inner transmission matter, the sulfurous gas in rich solution is resolved out and send sulfur dioxide gas water cooler through resolving tower top.Rich solution becomes lean solution after resolving, and high-temperature barren liquor flash-pot flows out through poor rich liquid heat exchanger cooling inflow lean solution groove and recycles.
5.3 dry and compressions
From resolving the high temperature sulfur dioxide gas of tower top and water vapour through SO
2gas cooler is cooling, enter sulfuric acid tower bottom after foam removal sprays with tower top that the vitriol oil getting off is reverse to be contacted, the pure sulfur dioxide gas that moisture in sulfur dioxide gas obtains being dried after being absorbed by the vitriol oil send compressor compresses, the gas after compression through sulfurous gas condenser, cooling to be become from gas phase after liquid phase is sent scale tank metering enters SO
2basin.The sulfuric acid that absorbs moisture enters to be dried sour circulation groove by tower bottom flow, will be dried after acid cooler cooling is sent in acid and send the pouring of drying tower top spray to recycle with recycle pump.Dense with the dry acid of vitriol oil adjusting in sulfuric acid apparatus, according to the dry sulfuric acid of liquid level output.Gained sulfur dioxide liquid product meets GB requirement.
Embodiment 2
Gypsum is produced a method for sulfur dioxide liquid, carries out according to the following steps:
1, raw material are equipped with: take the gypsum 83% of mass percent, coke 8%, yellow sand 5%, shale 2%, iron powder 2% as raw material, gypsum is CaSO
4the gypsum of content>=85%, coke are the coke containing fixed carbon>=75%, and gypsum granularity is that 0.08 ㎜ tails over 15%, and coke size is that 0.2 ㎜ tails over < 20%; Each material proportion is realized by measuring belt scale, and adding with metering screw of raw material adds, and accomplishes to feed in raw material even, smooth, can not occur fracture phenomenon, and accurate measurement, regulates freely;
2, calcination reaction in rotary kiln: the above-mentioned raw material that configure are added in rotary kiln and calcined, control the kiln speed of rotary kiln at 2.5 revs/min; Air intake adopts secondary air, elegance enters from coal spouting gun by cool ambient air, guarantee that coal dust enters in kiln and burning equably, primary air flow accounts for 20% of total blast volume, what secondary air was discharged from kiln hood air girder grate cooler accounts for 80% of total blast volume to clinker cooling hot blast after treatment, secondary air flow, in volumn concentration; To CO, O in kiln exhaust gas body
2, SO
2etc. composition on line analyzer is housed to guarantee O in kiln exhaust gas
2content is 0.05%～1.0% and CO < 0.4%, in quality percentage composition; Lay one deck refractory brick, the trapezoidal phosphoric acid salt refractory brick that described refractory brick is 200 × 200 × 90 × 80cm at cylinder of rotary kiln internal surface; Compound is calcined in rotary kiln, and rotary kiln provides thermal source by coal dust, and kiln gas amount and composition that decomposing and calcining gypsum produces are:
Kiln gas amount: 1.5N m
3/ kg; Compound; Water content: 6.0%; 350 ℃ of temperature <; Pressure :-2000Pa; Dust content < 3g/m
3; Kiln gas main component (butt leaks out containing kiln tail) SO
211%, O
20.05%, CO 0.10%, CO
215～18%, all by percentage to the quality;
3, after described calcined by rotary kiln reaction, the kiln gas that kiln tail is discharged carries out heat exchange with the raw material of question response in level Four suspended preheater, make kiln tail kiln gas temperature be reduced to 280 ℃ by 600 ℃ of original left and right, then gained is contained to the kiln gas heat recovery and utilization of sulfurous gas; The grog that calcination reaction is generated carries out cooling process, adopt air girder grate cooler (commercially available equipment) to carry out cooling to grog, make grog be cooled to 65 ℃ by original 200～300 ℃, improved the efficiency of combustion of coal dust simultaneously using the hot blast of generation as the secondary air recycle of entering kiln;
4, kiln gas purification processing: after above-mentioned and raw material heat exchange, gained kiln gas obtains industrial SO 2 unstripped gas, SO after purifying
2concentration can reach 11wt%, CaSO in preparation method of the present invention
4rate of decomposition is 97.2%, and in last gained grog, CaS only accounts for 1.5wt%, SO
3be only 0.6wt%;
5, liquid SO
2production process: industrial SO 2 unstripped gas obtained above adopts Citrate Buffer to prepare sulfur dioxide liquid, specifically first citric acid and sodium carbonate are mixed with to Trisodium Citrate lean solution with mass ratio 1:0.82, after absorbing the sulfurous gas in kiln gas (45 ℃ of kiln gas temperature <) by Trisodium Citrate lean solution (40 ℃ of Trisodium Citrate lean solution temperature <), make the sulfurous gas increase in Trisodium Citrate lean solution obtain Trisodium Citrate rich solution, again with heating (heating kettle temperature: 103-108 ℃), air lift, resolve rich solution and generate sulfur dioxide gas (90 ℃-100 ℃ of this gas temperatures) and the Trisodium Citrate lean solution containing saturated steam, the described sulfur dioxide gas containing saturated steam is through cooling, dry, compression (40 ℃ of Compressor Inlet Temperature <, 135 ℃ of compressor exit temperature <, ), after condensation sulfur dioxide liquid product, its sulfurous gas (SO
2)>=99.99%, residue≤0.008%, moisture≤0.018%, meet GB requirement completely.
All the other are with embodiment 1.
Embodiment 3
Gypsum is produced a method for sulfur dioxide liquid, carries out according to the following steps:
1, raw material are equipped with: take the gypsum 88% of mass percent, coke 4%, yellow sand 3%, shale 4%, iron powder 1% as raw material, gypsum is CaSO
4the gypsum of content>=85%, coke are the coke containing fixed carbon>=75%, and gypsum granularity is that 0.08 ㎜ tails over 20%, and coke size is that 0.2 ㎜ tails over < 20%; Each material proportion is realized by measuring belt scale, and adding with metering screw of raw material adds, and accomplishes to feed in raw material even, smooth, can not occur fracture phenomenon, and accurate measurement, regulates freely;
2, calcination reaction in rotary kiln: the above-mentioned raw material that configure are added in rotary kiln and calcined, control the kiln speed of rotary kiln at 2.0 revs/min; Air intake adopts secondary air, elegance enters from coal spouting gun by cool ambient air, guarantee that coal dust enters in kiln and burning equably, primary air flow accounts for 40% of total blast volume, what secondary air was discharged from kiln hood air girder grate cooler accounts for 60% of total blast volume to clinker cooling hot blast after treatment, secondary air flow, in volumn concentration; To CO, O in kiln exhaust gas body
2, SO
2etc. composition on line analyzer is housed to guarantee O in kiln exhaust gas
2content is 0.05%～1.0% and CO < 0.4%, in quality percentage composition; Lay one deck refractory brick, the trapezoidal phosphoric acid salt refractory brick that described refractory brick is 200 × 200 × 90 × 80cm at cylinder of rotary kiln internal surface; Compound is calcined in rotary kiln, and rotary kiln provides thermal source by coal dust, and kiln gas amount and composition that decomposing and calcining gypsum produces are:
Kiln gas amount: 1.7N m
3/ kg; Compound; Water content: 6.42%; 350 ℃ of temperature <; Pressure :-2000Pa; Dust content < 3g/m
3; Kiln gas main component (butt leaks out containing kiln tail) SO
212%, O
20.07%, CO 0.30%, CO
217～21%, all by percentage to the quality;
3, after described calcined by rotary kiln reaction, the kiln gas that kiln tail is discharged carries out heat exchange with the raw material of question response in level Four suspended preheater, make kiln tail kiln gas temperature be reduced to 280 ℃ by 600 ℃ of original left and right, then gained is contained to the kiln gas heat recovery and utilization of sulfurous gas; The grog that calcination reaction is generated carries out cooling process, adopt air girder grate cooler (commercially available equipment) to carry out cooling to grog, make grog be cooled to 65 ℃ by original 200～300 ℃, improved the efficiency of combustion of coal dust simultaneously using the hot blast of generation as the secondary air recycle of entering kiln;
4, kiln gas purification processing: after above-mentioned and raw material heat exchange, gained kiln gas obtains industrial SO 2 unstripped gas, SO after purifying
2concentration can reach 12wt%, CaSO in preparation method of the present invention
4rate of decomposition is 98%, and in last gained grog, CaS only accounts for 1.1wt%, SO
3be only 0.4wt%;
5, liquid SO
2production process: industrial SO 2 unstripped gas obtained above adopts Citrate Buffer to prepare sulfur dioxide liquid, after specifically using sodium citrate solution (lean solution) to absorb the sulfurous gas in kiln gas, make the sulfurous gas in sodium citrate solution increase (rich solution), generate sulfur dioxide gas and Trisodium Citrate lean solution containing saturated steam with heating, air lift, parsing rich solution again, the described sulfur dioxide gas containing saturated steam obtains sulfur dioxide liquid product after cooling, dry, compression, condensation, meets GB requirement.
All the other are with embodiment 1.
Claims (4)
1. the method that gypsum is produced sulfur dioxide liquid, it is characterized in that: first prepare gaseous sulfur dioxide take gypsum, coke as main raw material, to absorb by Trisodium Citrate lean solution through purified gas sulfurous gas again, make the sulfurous gas increase in Trisodium Citrate lean solution obtain Trisodium Citrate rich solution, generate sulfur dioxide gas and Trisodium Citrate lean solution containing saturated steam with heating, air lift, parsing rich solution again, the described sulfur dioxide gas containing saturated steam obtains sulfur dioxide liquid after cooling, dry, compression, condensation; Described preparation gaseous sulfur dioxide process Raw is calcination reaction in rotary kiln, controls O in rotary kiln tail gas
2content 0.05%～1.0%, CO < 0.4%, in quality percentage composition; Control the kiln speed of rotary kiln at 1.5～2.5 revs/min; Air intake adopts secondary air, and one time cool ambient air for elegance, primary air flow account for 20～30% of total blast volume, and what secondary air was discharged from kiln tail accounts for 70～80% of total blast volume to clinker cooling hot blast after treatment, secondary air flow, in volumn concentration;
In described reaction raw materials, by quality proportioning: gypsum 83～88%, coke 4～8%, yellow sand 3～5%, shale 2～5%, iron powder 1～2%; Described gypsum is selected CaSO
4gypsum, the coke of content>=85% are selected the coke containing fixed carbon>=75%, all in quality percentage composition; Wherein gypsum granularity is that 0.08 ㎜ tails over 15～20%, and coke size is that 0.2 ㎜ tails over < 20%; Described gypsum, coke raw material are pressed C/SO
3mol ratio is controlled at 0.6～0.65:1.
2. production method as claimed in claim 1, it is characterized in that: in described calcination reaction process, take insulation to process, specifically adopted one deck refractory brick at cylinder of rotary kiln internal surface, described refractory brick adopts the trapezoidal phosphoric acid salt refractory brick of 200 × 200 × 90 × 80cm.
3. production method as claimed in claim 2, is characterized in that: after described calcined by rotary kiln reaction, the kiln gas of also kiln tail being discharged carries out heat exchange by raw material; The grog also described calcination reaction being produced carries out cooling process, specifically adopts air girder grate cooler to carry out grog cooling, makes grog be cooled to 65 ℃ by original 200～300 ℃, simultaneously using the hot blast after cooling process as the secondary air of entering kiln.
4. production method as claimed in claim 1, is characterized in that: take the gypsum 85% of mass percent, coke 6%, yellow sand 3%, shale 4%, iron powder 2% as raw material, gypsum is CaSO
4the gypsum of content>=85%, coke are the coke containing fixed carbon>=75%, and gypsum granularity is that 0.08 ㎜ tails over 18%, and coke size is that 0.2 ㎜ tails over < 20%; Wherein control O in rotary kiln tail gas
2content 0.05%～1.0%, CO < 0.4%, in quality percentage composition;
In described calcined by rotary kiln reaction process, control the kiln speed of rotary kiln at 1.5～2.5 revs/min; Air intake adopts secondary air, and one time cool ambient air for elegance, primary air flow account for 20～30% of total blast volume, and what secondary air was discharged from kiln hood accounts for 70～80% of total blast volume to clinker cooling hot blast after treatment, secondary air flow, in volumn concentration;
Described raw material in calcination reaction process, takes insulation to process in rotary kiln, specifically lays one deck refractory brick, the trapezoidal phosphoric acid salt refractory brick that described refractory brick is 200 × 200 × 90 × 80cm at cylinder of rotary kiln internal surface; After described calcined by rotary kiln reaction, the kiln gas of also kiln tail being discharged carries out heat exchange with the raw material of question response in level Four suspended preheater, then gained is contained to the kiln gas heat recovery and utilization of sulfurous gas; The grog also calcination reaction being generated carries out cooling process, adopts air girder grate cooler to carry out grog cooling, makes grog be cooled to 65 ℃ by original 200～300 ℃, simultaneously using the hot blast of generation as the secondary air of entering kiln;
After described and raw material heat exchange, the kiln gas of gained obtains industrial SO 2 unstripped gas after conventional dedusting, washing, purifying;
The described industrial SO 2 unstripped gas obtaining adopts Citrate Buffer to prepare sulfur dioxide liquid, specifically citric acid is reacted take mass ratio as 1:0.82 and is mixed with citric acid lean solution with sodium carbonate, make the sulfurous gas increase in sodium citrate solution obtain Trisodium Citrate rich solution with Trisodium Citrate lean solution sulfur dioxide absorption industrial raw material gas, again with heating, air lift, resolve rich solution and generate sulfur dioxide gas and the Trisodium Citrate lean solution containing saturated steam, the described sulfur dioxide gas containing saturated steam is through cooling, dry, compression, after condensation, obtain sulfur dioxide liquid product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101954233A (en) * | 2010-09-26 | 2011-01-26 | 西安建筑科技大学 | Desorbing method and device of absorption rich liquor for absorbing sulfur dioxide by using citrate solution |
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| CN101954233A (en) * | 2010-09-26 | 2011-01-26 | 西安建筑科技大学 | Desorbing method and device of absorption rich liquor for absorbing sulfur dioxide by using citrate solution |
Non-Patent Citations (4)
| Title |
|---|
| 单玉才.硫磺在空气中燃烧制液体SO2工艺探讨及三废处理.《安徽化工》.2007,第33卷(第2期),44、45. |
| 张松柏.柠檬酸钠法吸收二氧化硫制液体二氧化硫.《硫酸工业》.1985,1-4. |
| 柠檬酸钠法吸收二氧化硫制液体二氧化硫;张松柏;《硫酸工业》;19850401;1-4 * |
| 硫磺在空气中燃烧制液体SO2工艺探讨及三废处理;单玉才;《安徽化工》;20070430;第33卷(第2期);44、45 * |
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