CN102303883A - Method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurated gypsum - Google Patents
Method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurated gypsum Download PDFInfo
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a method for preparing calcium oxide and sulfur by double-atmosphere fluidized roasting of desulfurated gypsum, belonging to the technical fields of solid pollutant treatment and in environmental protection chemical production. The method comprises the following steps: drying and dehydrating aged desulfurated gypsum, and then entering a multi-stage suspension heat exchanger for pre-heating; entering hot-state gypsum into a circulating fluidized bed decomposition furnace, and introducing primary and secondary air for decomposition; cooling discharged hot-state calcium oxide, wherein cooled hot-state calcium oxide is used as a desulfurizer for later use; entering discharged smoke containing sulfur dioxide into the multi-stage suspension heat exchanger; removing calcium oxide dust in cooled hot smoke through multi-stage dust removing equipment; and feeding the smoke without the dust into a high-temperature-resistant high-efficiency filter for further removing the dust, and feeding clean smoke into a sulfur recovery system; and preparing the sulfur product by the processes of hot reduction, catalytic reduction, Clause reaction and the like, and feeding Clause tail gas into a coal burning boiler in a power plant for combustion. The method has the advantages of good environmental protection benefits and strong economic benefits.
Description
Technical field
The invention belongs to solid pollutant in the environment protection and administer the technical field with Chemical Manufacture, be specifically related to the two atmosphere thermolysiss of a kind of desulfurated plaster and prepare quicklime and sulfurous gas, sulfurous gas restores the method for making sulphur.
Background technology
Lime/lime stone-gypsum method flue gas desulfurization technology is widely used in China, and thermal power plant's power unit total volume in the whole nation about 75% and most of coal firing boiler, steel works sintering machine adopt lime/lime stone-gypsum method to remove sulfur in smoke at present.The desulfurated plaster staple of sweetening process by-product is a terra alba, contains impurity such as calcium sulfite, quicklime, calcium hydroxide, lime carbonate and coal ash simultaneously.According to " the Ministry of Industry and Information Technology is about the instruction of industry by-product gypsum comprehensive utilization " of in February, 2011 issue, China's desulfurated plaster output was about 4,300 ten thousand tons/year in 2009, and whole nation accumulative total is stored up the desulfurated plaster amount above 5,000 ten thousand tons.At present China's desulfurated plaster comprehensive utilization ratio only 56%, still has quite a few desulfurated plaster simply to store up processing, both taken limited land resources, causes the secondary pollution problem again easily.According to instruction, to 2015 the end of the year China's desulfurated plaster comprehensive utilization ratio to reach 80%, therefore to desulfurated plaster in addition recycling meet national energy-saving and emission-reduction policy.
Existing desulfurated plaster comprehensive utilization technique mainly contains three types, and the one, desulfurated plaster is used as cement additire, the 2nd, desulfurated plaster is produced gypsum building material products such as terra alba, plasterboard, gypsum block, the 3rd, decompose desulfurated plaster system producing sulfuric acid and jointly cement.But because China's plaster of paris aboundresources and desulfurated plaster contain impurity such as coal ash, quicklime, calcium sulfite and calcium hydroxide, it is limited that cement additire and gypsum building material product consume the desulfurated plaster amount; And desulfurated plaster system producing sulfuric acid and jointly cement industry flow process is complicated, equipment is various, energy consumption is high, economic benefit is not high, and the accumulating of fluid sulphuric acid product is restricted, and therefore is badly in need of seeking a kind of method of more suitable desulfurated plaster recycling.Six ministries and commissions such as National Development and Reform Committee have issued " Chinese comprehensive utilization of resources technical policy outline " in July, 2010; Wherein propose to promote and reclaim sulphur resource production sulphur technology in the coal-fired plant flue gas; Its objective is to change sulfur in smoke into domestic sulfur product in short supply; Solid sulfur is easy to accumulating, added value is high, is to be fit to large sulfuration chemical product that power plant produces.For this reason, the contriver proposes a kind of the desulfurated plaster thermolysis to be prepared quicklime and sulphur new technology.
Technology about gypsum thermolysis oxygenerating calcium (unslaked lime) is disclosed in following patent; Disclose among Chinese patent CN200910094110.8, CN200810068831.7, CN201010174513.6, CN201010131145.7, CN200810049430.7, the CN200910181251.3 and utilized phosphogypsum and desulfurated plaster oxygenerating calcium and vitriolic method, mentioned and use coke, high sulfur petroleum coke to be reductive agent reduction decomposition gypsum system vitriolic method in rotary kiln, suspended state decomposing furnace or fluidizing furnace.These patents exist following problem: a. with coke as reductive agent, decompose gypsum with decomposing kiln, the equipment hot working efficiency is not high, coke and coal-fired consume big, production cost is high, economy is not good, kiln gas (furnace gas) sulfur dioxide concentration is on the low side; B. with suspended state decomposing furnace or common fluidizing furnace reduction decomposition gypsum; Fail effectively to solve reducing atmosphere and the effective of oxidizing atmosphere separates; The intermediate product quicklime is easy to reduction and generates sulfurated lime and calcium sulfate; Influence the quality of final degradation production quicklime, it is unfavorable that the quicklime desulphurization circulating is used, and kiln gas (furnace gas) sulfur dioxide concentration is on the low side simultaneously; C. the sulfur dioxide flue gas that decomposes by-product is used to produce the fluid sulphuric acid product; Do not consider that power plant is actual; On the one hand power plant is not professional chemical enterprise, and chemical production line draws oversizely is unfavorable for the production operation management, and the added value of sulfuric acid product is low and be difficult for accumulating on the other hand; Need supporting logistics accumulating measure, the risk that exists the influence of sulfuric acid swell-warehouse to produce.
The technology of decomposing system sulphur about gypsum is disclosed in following patent; The method of utilizing sulfurous gas that gypsum decomposes or sulfurated lime reduction to prepare sulphur is disclosed among Chinese patent CN200710303450.8, the CN98101761.4; These patents exist following problem: a. directly with coal dust reduction sulfurous gas system hydrogen sulfide, and coal consumption is big, transformation efficiency is not high, side reaction is many; B. it is harsh that gypsum decomposes system sulfurated lime control condition, and the gypsum rate of decomposition is low, and the operational path of sulfurated lime system hydrogen sulfide is long, and there is big difficulty in industriallization; C. do not consider reaction end gas recycling and harmless handling problem, and fail to organically combine with the master of power plant technology.
Up to now, do not see as yet and desulfurated plaster is decomposed oxygenerating calcium, quicklime circulation desulfurization and sulfurous gas prepare reports such as patent of invention that sulphur organically combines and research document.
Summary of the invention
The objective of the invention is to have the not high problem of desulfurated plaster comprehensive utilization ratio now for solving, and a kind of method of utilizing the two atmosphere fluidized bed roastings of desulfurated plaster to prepare quicklime and sulphur that provides.
The quicklime of the inventive method preparation recycles as fume desulfurizing agent; Sulfurous gas finally changes sulfur product into; Through integrating lime-gypsum method flue gas desulfurization technique, gypsum system sulfurous gas and quicklime technology, sulfurous gas system sulphur technology; Realized sulphur, the utilization of calcium resource circulation, the maturation that possesses skills, less investment, advantage such as energy consumption is low, production cost is low are fit to power plant or Iron And Steel Plant's large-scale industrial production.
The present invention realizes by following technical scheme:
With the dry dehydration of the desulfurated plaster after the ageing, get into the preheating of multistage suspension heat exchange device, the hot gypsum after the preheating is sent in the circulating fluidized bed decomposing furnace;
The combustion air of fuel and preheating is that primary air is sent into said decomposing furnace, with unburnt mode reducing atmosphere is provided, and sends into secondary air oxidizing atmosphere is provided;
Said desulfurated plaster repeatedly through reduction zone and oxidation zone, relies on the stove outer circulation at said decomposing furnace internal recycle simultaneously, and said desulfurated plaster is decomposed fully;
Hot quicklime is from the slag-drip opening discharge of said decomposing furnace bottom, and after the cooling of heat material water cooler, it is subsequent use as sweetening agent with handling equipment the quicklime powder to be sent into the quicklime feed bin again;
The high temperature that comes out from said decomposing furnace top contains sulfur dioxide flue gas and gets into said multistage suspension heat exchange device, carries out multistage gas-solid attitude heat exchange with the cold conditions desulfurated plaster;
In said multistage suspension heat exchange device, said desulfurated plaster heat up whole free-waters and crystal water, concurrent first portion pyrolysis, the hot flue gas after the cooling removes quicklime dust wherein through multistage dust removal installation;
It is subsequent use that said quicklime dust is sent into said quicklime feed bin with handling equipment;
Flue gas after the said dedusting is sent into the high temperature high efficiency strainer and is further removed dust, and clean flue gas is sent into sulfur recovery system, prepares sulfur product through thermal reduction, catalytic reduction and claus reaction, and Claus tail gases send the coal-fired boiler in power plant burning disposal.
Usually, the inventive method comprises following key step:
(a) said desulfurated plaster is sent in a hot air drying kiln or the steam dryer; Utilize the air of coal-fired heating or the back pressure steam that generates electricity as drying source; Deviate from most of crystal water and free-water in the said desulfurated plaster; 120 ~ 160 ℃ of control drying temperatures, the massfraction of water is 3% ~ 6% in the semi-hydrated gypsum of the dry back of control.Dried semi-hydrated gypsum itself is thin (mainly concentrating on 30 ~ 60 μ m), can directly use after breaing up.Dried cold conditions semi-hydrated gypsum is sent in the said multistage suspension heat exchange device.
(b) said multistage suspension heat exchange device heat exchange progression is preferred 4 ~ 5 grades; In said suspension heat exchange device; 950 ~ 1200 ℃ of abundant contact heat-exchangings of hot flue gas that said cold conditions semi-hydrated gypsum comes with said decomposing furnace in suspension cylinder and increase in pipeline; Said suspension heat exchange device temperature out is reduced to 400 ~ 600 ℃ flue gas and is sent into an air preheater and air heat exchange, gets into said multistage dust removal installation after flue-gas temperature is further reduced to 200 ~ 350 ℃.Preheated air divides two-way, and one the tunnel as said decomposing furnace combustion air, and another road is as the combustion air of reduction roasting kiln.Said gypsum pre-heating temperature elevation to 600 ~ 800 ℃, moisture is all deviate from the gypsum, and lime carbonate impurity begins to decompose.Hot dehydrated gyp-leaves said suspension heat exchange device and gets in the said decomposing furnace from the bottom feed mouth.
(c) said decomposing furnace is two atmosphere circulating fluidized bed decomposing furnaces of band cyclonic separator, and fuel port adds fuel from the bottom.Said fuel can be Sweet natural gas, common coal dust, high-sulfur coal dust or high sulfur petroleum coke powder etc., and preferred high-sulfur coal dust of power plant and high sulfur petroleum coke powder act as a fuel.Air after the said preheating divides two portions to add from said decomposing furnace bottom and middle part, and bottom primary air volume is into 70% ~ 90% of the total volume of air amount of stove, makes non-complete combustion of fuel to form the bottom reducing atmosphere, control mixed gas medium reduction potential (
p CO/
p CO2=0.15 ~ 0.25) operation; Middle part secondary air volume is into 10% ~ 30% of the total volume of air amount of stove, makes full combustion of fuel to form top oxidizing atmosphere.Repeatedly through reduction zone and oxidation zone, collected by cyclonic separator by the material that is decomposed simultaneously at said decomposing furnace internal recycle for desulfurated plaster, returns the decomposition that circulates of said decomposing furnace reduction zone again through sealing bore, and gypsum is almost completely decomposed.Service temperature all maintains 950 ~ 1200 ℃ in the stove, and operating gas velocity moves under 1 ~ 5m/s.
(d) flue-gas temperature that goes out said decomposing furnace is at 950 ~ 1200 ℃, the sulfur dioxide in flue gas volume(tric)fraction 12% ~ 15%, the oxysome integration is several 1.0% ~ 3.0%, flue gas also contains carbonic acid gas, nitrogen, oxygen, water vapour and a small amount of sulphur trioxide.Said multistage dust removal installation generally comprises the high-efficiency electric dust catcher of tornado dust collector and one 4 ~ 5 electric field.Flue gas after the dedusting gets at least one said high temperature high efficiency strainer, further removes dust in flue gas, filters the back clean flue gas and sends into sulfur recovery system.
(e) 900 ~ 1100 ℃ of hot quicklime powders of said decomposing furnace bottom slag-drip opening discharge are sent into said heat material water cooler; Through heating boiler water for cooling to 50 ~ 150 ℃; With handling equipment said quicklime powder is sent in the said quicklime feed bin subsequent usely again, said quicklime powder is sent into the power plant desulfurization system after metering and is joined stock tank and prepare lime slurry; Feedwater after the preheating send the generating of boiler of power plant producing steam.200 ~ 300 ℃ the dust that said tornado dust collector and electric precipitator are discharged is sent into said heat material water cooler internal cooling, and it is subsequent use to send into said quicklime feed bin with handling equipment again.
(f) said sulfur recovery system comprises preparation of intermediate product hydrogen sulfide and Clause method sulfur production operation.According to raw material condition; Can adopt the fuel reduction sulfurous gas that comprises Sweet natural gas, water-gas or coke-oven gas to prepare intermediate product hydrogen sulfide; Near do not have the power plant of Sweet natural gas or coke-oven gas supply to pay the utmost attention to a blue-gas generator is set to prepare water-gas, act as a fuel and hydrogen source with water-gas; Iron And Steel Plant can act as a fuel and hydrogen source with coke-oven gas.
(g) said clean flue gas gets into a reduction roasting kiln, adds said fuel and preheated air in the said reduction roasting kiln, reacts completely through high-temp combustion and removes oxygen and the sulphur trioxide in the flue gas.Said reduction roasting kiln outlet high-temperature flue gas component comprises sulfurous gas, carbonic acid gas, nitrogen, carbon monoxide, hydrogen, hydrogen sulfide, dithiocarbonic anhydride, carbonylsulfide, water vapour, sulfur vapor, and said high-temperature flue gas gets into a waste heat boiler recovery heat producing steam and send power plant's generating.The flue gas that said waste heat boiler comes out gets at least one high temperature resistant sulphur separator and removes the sulfur vapor in the flue gas; Flue gas gets into a catalytic reduction reactor subsequently, changes sulfur dioxide in flue gas, dithiocarbonic anhydride, carbonylsulfide and Determination of Trace Sulfur steam into hydrogen sulfide through hydrogenating reduction and hydrolysis reaction.Said catalytic reduction reactor outlet flue gas gets into a sulfur condenser and reclaims the sulphur in the flue gas; Flue gas gets into a claus reaction device subsequently; Change sulfur in smoke into sulphur through claus reaction; Said claus reaction device outlet flue gas gets into a sulfur condenser and at least one sulphur separator recovery sulier successively; Contain carbon monoxide, sulfurous gas, carbonic acid gas, nitrogen and a small amount of carbonylsulfide, dithiocarbonic anhydride, hydrogen, sulfur vapor in the tail gas of said sulphur separator outlet, said Claus tail gases is sent into coal-fired boiler in power plant carry out burning disposal.
(h) fuel such as said water-gas, Sweet natural gas or coke-oven gas are at first reducing the combustion chamber internal combustion of roasting kiln; Utilize fuel combustion heat that gaseous mixture is heated to 1100 ~ 1250 ℃, oxygen in the gaseous mixture and sulphur trioxide all change carbonic acid gas, water vapour and sulfurous gas into.Control said catalytic reduction reactor inlet gas temperature at 350 ~ 600 ℃, temperature out at 500 ~ 650 ℃; Through hot by-pass said catalytic reduction reactor part inlet gas is caused the outlet of said catalytic reduction reactor, the mol ratio of hydrogen sulfide and sulfurous gas maintains 2: 1 in the outlet mixed gas to regulate.Said catalytic reduction reactor adopts the titaniferous hydrolyst.
(i) said claus reaction device inlet temperature is controlled at 200 ~ 300 ℃, can said catalytic reduction reactor section port gas be caused the import of said claus reaction device if needed, to regulate the inlet gas temperature.Said claus reaction device adopts aluminium oxide catalyst.
The inventive method adopts multi-stage heat exchanger equipment retrieving arrangement heat energy such as multistage suspension heat exchange device, air preheater, waste heat boiler, heat material cooler in order to reduce plant energy consumption.Said multistage suspension heat exchange device and air preheater advance said decomposing furnace gypsum and air through heating, both can reduce bunker coal consumption, can improve the furnace gas sulfur dioxide concentration again.Said waste heat boiler adds the feedwater recovery heat energy that heat power plant provides with heat material cooler, and the hot water of generation or steam return the boiler of power plant power generation system.In addition, contain combustiblesubstances such as carbon monoxide, sulfur vapor, carbonylsulfide, dithiocarbonic anhydride, hydrogen in the said Claus tail gases, send the coal-fired boiler in power plant burning disposal it, both can the fuel saving consumption of coal, again can the harmless treatment Claus tail gases.
Beneficial effect of the present invention: the development and use desulfurated plaster prepares quicklime and sulphur technology; Not only can solve the desulfurated plaster problem of complex utilization; Consider that power plant's Chemical Manufacture level is not high and coal feedstock abundant; Utilize domestic in short supply, the sulfur product that is easy to accumulating of by-product sulphur dioxide production, and technical process is simple, easy to operate.The quicklime of by-product both can or be produced material of construction, cement etc. as pavior; Also can combine with means of flue gas desulfurization of power plant; To substitute lime carbonate as sweetening agent through the quicklime of high-temperature activation; Can reduce the destruction of lime carbonate exploitation on the one hand, preserve the ecological environment, can reduce lime carbonate on the other hand and decompose the percent of greenhouse gases emission of carbon-dioxide massif and vegetation.Therefore, this technology has good and environmental benefit and stronger economic advantages.
Through simple material balance, utilize technology per minute according to the invention to separate 1 ton of desulfurated plaster (butt) and can produce 0.45 ton in quicklime, 0.2 ton in sulphur.By present coal in power plant
w(S) 0.7% ~ 1.0%; Annual 90000 tons of the desulfurated plaster (butt) of approximately discharging of 2 * 300MW power plant; If build the production line of 90,000 tons/year of gypsum treatment capacities, can produce 4.1 ten thousand tons in quicklime, 1.8 ten thousand tons in sulphur every year, by 250 yuan/ton of current unslaked lime prices, 1200 yuan/ton of sulphur prices, 500 yuan of/ton conversions of high-sulfur coal dust price; And consider depreciation and general facilities consumption, can obtain nearly 2,000,000 yuan of direct economic benefit every year in the time of the harmless treatment desulfurated plaster.Annual 300000 tons of the desulfurated plaster (butt) of discharging of 2 * 1000MW power plant if build the production line of 300,000 tons/year of gypsum treatment capacities, can produce 13.7 ten thousand tons in quicklime, 60,000 tons in sulphur every year.By current unslaked lime, sulphur, high-sulfur coal dust price accounting, and consider depreciation and general facilities consumption, can obtain nearly 6,200,000 yuan of direct economic benefit every year in the time of the harmless treatment desulfurated plaster.
Description of drawings
Fig. 1 prepares the method embodiment process flow diagram of quicklime and sulphur for the two atmosphere fluidized bed roastings of desulfurated plaster of the present invention.
Among the figure: 1 is hot air drying kiln or steam dryer, and 2 is multistage suspension heat exchange device, and 3 is air preheater, and 4 is tornado dust collector; 5,19 is the warm sludge water cooler, and 6 is electric precipitator, and 7 is the high temperature high efficiency strainer, and 8 are the reduction roasting kiln; 9 is waste heat boiler, and 10 is high temperature resistant sulphur separator, and 11 is catalytic reduction reactor, and 12,14 is sulfur condenser; 13 is the claus reaction device, and 15 is the sulphur separator, and 16 is the Molten sulphur storage tank, and 17 for joining stock tank; 18 is the quicklime feed bin, and 20 is sealing bore, and 21 is cyclonic separator, and 22 is circulating fluidized bed decomposing furnace.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is described further.
Describe the present invention with instance below, but the present invention is not limited to these instances, in these instances: the desulfurated plaster of handling according to method of the present invention contain following shown in component:
w(SO
3) 44.88%,
w(CaO) 33.30%,
w(SiO
2) 0.62%,
w(Al
2O
3) 0.23%,
w(Fe
2O
3) 0.17%,
w(MgO) 1.03%, crystal water (
w) 18.96%, other impurity (
w) 0.81%.
The embodiment of the invention adopts following technical process: equipment 1 drying and dehydrating that desulfurated plaster advances among Fig. 1 becomes semi-hydrated gypsum, sends into equipment 2 subsequently, and with the hot flue gas heat exchange from equipment 21, the gypsum after the preheating is from charging opening access arrangement 22.In equipment 22 gypsum with react from the preheated air of equipment 3 and the fuel of sending into (like coal dust); The sulfur dioxide flue gas that generates enters equipment 2,3,4 successively after equipment 21 gathers dust; 5 cooling dedustings, flue gas is sent into equipment 8 after advancing equipment 7 further dedustings again.In equipment 8 flue gas with react from the preheated air of equipment 3 and the fuel of sending into (like water-gas); The high-temperature flue gas that generates is access arrangement 10 after equipment 9 coolings; Remove sulfur vapor and remaining dust in the flue gas; Flue gas access arrangement 11 carries out catalytic reduction reaction afterwards, contains sulfurous gas and hydrogen sulfide flue gas access arrangement 12 subsequently and removes access arrangement 13 behind the sulfur vapor.Claus reaction takes place in equipment 13 generate elemental sulfur; Claus tail gases advances equipment 14 successively; 15 recovery sulier, the tail gas that contains carbon monoxide, sulfurous gas, carbonic acid gas, nitrogen and a small amount of carbonylsulfide, dithiocarbonic anhydride, hydrogen, sulfur vapor that equipment 15 comes out finally send the coal-fired boiler in power plant burning disposal.The quicklime powder that quicklime powder that equipment 22 is discharged and equipment 3,4,5 are discharged is sent into equipment 18 respectively after equipment 5 and 19 coolings subsequent use, sends into equipment 17 after the quicklime powder metering in the equipment 18 and join slurry and prepare lime slurry and be used for flue gas desulfurization.
Embodiment 1.Production line with 100,000 tons/year of a desulfurated plaster (butt) treatment capacities is an example, adopts the technical process like Fig. 1.Advance 600 ℃ of circulating fluidized bed decomposing furnace desulfurated plaster (butt) 12.5t/h, temperature, go into stove air capacity 9500m
3250 ℃ of/h, temperature, wherein primary air amount 7600m
3/ h, secondary air amount 1900m
3/ h (secondary air account for total air 20%).Go out 1200 ℃ of decomposing furnace gas temperatures, gypsum rate of decomposition 99.3%, furnace gas component are SO
2Volume(tric)fraction 12.4%, O
2Volume(tric)fraction 1.0%, CO
2Volume(tric)fraction 10.3%, N
2Volume(tric)fraction 76.3%.Decomposing furnace bed drain purge 5.7t/h, wherein the CaO massfraction is 90.5%, meets flue gas desulfurization and uses the quicklime quality index.The reduction roasting kiln acts as a fuel 1100 ℃ of temperature of combustion, sulfur recovery system sulfur recovery rate 88%, recovery sulier 2.45t/h, purity 99.5% with water-gas.
Embodiment 2.Production line with 100,000 tons/year of a desulfurated plaster (butt) treatment capacities is an example equally, adopts the technical process like Fig. 1.Advance 700 ℃ of circulating fluidized bed decomposing furnace desulfurated plaster (butt) 12.5t/h, temperature, go into stove air capacity 8500m
3300 ℃ of/h, temperature, wherein primary air amount 7000m
3/ h, secondary air amount 1500m
3/ h (secondary air account for total air 17.6%).Go out 1000 ℃ of decomposing furnace gas temperatures, gypsum rate of decomposition 99.1%, furnace gas component are SO
2Volume(tric)fraction 14.0%, O
2Volume(tric)fraction 1.0%, CO
2Volume(tric)fraction 10.1%, N
2Volume(tric)fraction 74.9%.Decomposing furnace bed drain purge 5.65t/h, wherein the CaO massfraction is 89.5%, meets flue gas desulfurization and uses the quicklime quality index.The reduction roasting kiln acts as a fuel 1200 ℃ of temperature of combustion, sulfur recovery system sulfur recovery rate 90%, recovery sulier 2.5t/h, purity 99.5% with water-gas.
Embodiment 3.Production line with 100,000 tons/year of a desulfurated plaster (butt) treatment capacities is an example equally, adopts the technical process like Fig. 1.Advance 700 ℃ of circulating fluidized bed decomposing furnace desulfurated plaster (butt) 12.5t/h, temperature, go into stove air capacity 8000m
3300 ℃ of/h, temperature, wherein primary air amount 6500m
3/ h, secondary air amount 1500m
3/ h (secondary air account for total air 18.75%).Go out 950 ℃ of decomposing furnace gas temperatures, gypsum rate of decomposition 99%, furnace gas component are SO
2Volume(tric)fraction 15.0%, O
2Volume(tric)fraction 1.0%, CO
2Volume(tric)fraction 9.0%, N
2Volume(tric)fraction 76.0%.Decomposing furnace bed drain purge 5.6t/h, wherein the CaO massfraction is 90.0%, meets flue gas desulfurization and uses the quicklime quality index.The reduction roasting kiln acts as a fuel 1250 ℃ of temperature of combustion, sulfur recovery system sulfur recovery rate 91%, recovery sulier 2.53t/h, purity 99.5% with water-gas.
In the embodiment of the invention, the desulfurated plaster rate of decomposition more than 99%, sulfur recovery rate is 88% ~ 91%, in the by-product quicklime CaO massfraction 89.5% ~ 90.5%, sulfur purity is 99.5%.The waste heat of fully recycling circulating fluidized bed decomposing furnace and reduction roasting kiln is used for power plant's generating, does not have waste water, waste sludge discharge in the production process basically, and sulfur-bearing tail gas then send the coal-fired boiler in power plant burning disposal.
What should explain at last is: above embodiment is only in order to explaining technical scheme of the present invention, but not to its restriction.Although with reference to previous embodiment detailed explanation has been carried out in invention, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of technical scheme break away from the spirit and the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the two atmosphere fluidized bed roastings of desulfurated plaster prepare the method for quicklime and sulphur, it is characterized in that, comprise following consecutive steps:
With the dry dehydration of the desulfurated plaster after the ageing, get into the preheating of multistage suspension heat exchange device, the hot gypsum after the preheating is sent in the circulating fluidized bed decomposing furnace;
The combustion air of fuel and preheating is that primary air is sent into said decomposing furnace, with unburnt mode reducing atmosphere is provided, and sends into secondary air oxidizing atmosphere is provided;
Said desulfurated plaster repeatedly through reduction zone and oxidation zone, relies on the stove outer circulation at said decomposing furnace internal recycle simultaneously, and said desulfurated plaster is decomposed fully;
Hot quicklime is from the slag-drip opening discharge of said decomposing furnace bottom, and after the cooling of heat material water cooler, it is subsequent use as sweetening agent with handling equipment the quicklime powder to be sent into the quicklime feed bin again;
The high temperature that comes out from said decomposing furnace top contains sulfur dioxide flue gas and gets into said multistage suspension heat exchange device, carries out multistage gas-solid attitude heat exchange with the cold conditions desulfurated plaster;
In said multistage suspension heat exchange device, said desulfurated plaster heat up whole free-waters and crystal water, concurrent first portion pyrolysis, the hot flue gas after the cooling removes quicklime dust wherein through multistage dust removal installation;
It is subsequent use that said quicklime dust is sent into said quicklime feed bin with handling equipment;
Flue gas after the said dedusting is sent into the high temperature high efficiency strainer and is further removed dust, and clean flue gas is sent into sulfur recovery system, prepares sulfur product through thermal reduction, catalytic reduction and claus reaction, and Claus tail gases send the coal-fired boiler in power plant burning disposal.
2. according to the method for claim 1, it is characterized in that said desulfurated plaster adopts hot air drying kiln or steam dryer to dewater to semi-hydrated gypsum, 120 ~ 160 ℃ of drying temperature controls, the massfraction of water is 3% ~ 6% in the semi-hydrated gypsum of the dry back of control.
3. according to the method for claim 1; It is characterized in that; Said multistage suspension heat exchange device heat exchange progression is 4 ~ 5 grades, in said suspension heat exchange device, and 950 ~ 1200 ℃ of abundant contact heat-exchangings of hot flue gas that said cold conditions semi-hydrated gypsum comes with said decomposing furnace in suspension cylinder and increase in pipeline; Said suspension heat exchange device outlet flue gas is sent into an air preheater and air heat exchange, flue-gas temperature is further reduced to 200 ~ 350 ℃ after the said multistage dust removal installation of entering; Preheated air divides two-way, and one the tunnel as said decomposing furnace combustion air, and another road is as the combustion air of reduction roasting kiln; Said hot dehydrated gyp-leaves said suspension heat exchange device and gets in the said decomposing furnace from the bottom feed mouth.
4. according to the method for claim 1, it is characterized in that said decomposing furnace is two atmosphere circulating fluidized bed decomposing furnaces of band cyclonic separator, fuel port adds fuel from the bottom; Said fuel is Sweet natural gas, common coal dust, high-sulfur coal dust or high sulfur petroleum coke powder; Air after the said preheating divides two portions to add from said decomposing furnace bottom and middle part, and bottom primary air volume is into 70% ~ 90% of the total volume of air amount of stove, makes non-complete combustion of fuel to form the bottom reducing atmosphere, and the control mixed gas is at medium reduction potential
p CO/
p CO2=0.15 ~ 0.25 operation; Middle part secondary air volume is into 10% ~ 30% of the total volume of air amount of stove, makes full combustion of fuel to form top oxidizing atmosphere; Repeatedly through reduction zone and oxidation zone, collected by cyclonic separator by the material that is decomposed simultaneously at said decomposing furnace internal recycle for desulfurated plaster, returns the decomposition that circulates of said decomposing furnace reduction zone again through sealing bore, and gypsum is decomposed fully; Service temperature all maintains 950 ~ 1200 ℃ in the stove, and operating gas velocity moves under 1 ~ 5m/s.
5. according to the method for claim 1, it is characterized in that said multistage dust removal installation comprises the high-efficiency electric dust catcher of tornado dust collector and one 4 ~ 5 electric field; Flue gas after the dedusting gets at least one said high temperature high efficiency strainer, further removes dust in flue gas, filters the back clean flue gas and sends into sulfur recovery system.
6. according to the method for claim 1; It is characterized in that; Said decomposing furnace bottom slag-drip opening is discharged 900 ~ 1100 ℃ of hot quicklime powders and is sent into said heat material water cooler; Through heating boiler water for cooling to 50 ~ 150 ℃, with handling equipment said quicklime powder to be sent in the said quicklime feed bin subsequent usely again, said quicklime powder is sent into the power plant desulfurization system after metering and is joined stock tank and prepare lime slurry; Feedwater after the preheating send the generating of boiler of power plant producing steam; 200 ~ 300 ℃ the dust that said tornado dust collector and electric precipitator are discharged is sent into said heat material water cooler internal cooling, and it is subsequent use to send into said quicklime feed bin with handling equipment again.
7. according to the method for claim 1, it is characterized in that said sulfur recovery system comprises preparation of intermediate product hydrogen sulfide and Clause method sulfur production operation; Employing comprises that the fuel reduction sulfurous gas of Sweet natural gas, water-gas or coke-oven gas prepares intermediate product hydrogen sulfide; Or a blue-gas generator is set prepares water-gas, act as a fuel and hydrogen source with water-gas; Iron And Steel Plant act as a fuel and hydrogen source with coke-oven gas.
8. according to the method for claim 1, it is characterized in that said clean flue gas gets into a reduction roasting kiln, add said fuel and preheated air in the said reduction roasting kiln, react completely through high-temp combustion and remove oxygen and the sulphur trioxide in the flue gas; Said reduction roasting kiln outlet high-temperature flue gas gets into a waste heat boiler recovery heat producing steam and send power plant's generating; The flue gas that said waste heat boiler comes out gets at least one high temperature resistant sulphur separator and removes the sulfur vapor in the flue gas; Flue gas gets into a catalytic reduction reactor subsequently, changes sulfur dioxide in flue gas, dithiocarbonic anhydride, carbonylsulfide and Determination of Trace Sulfur steam into hydrogen sulfide through hydrogenating reduction and hydrolysis reaction; Said catalytic reduction reactor outlet flue gas gets into a sulfur condenser and reclaims the sulphur in the flue gas, and flue gas gets into a claus reaction device subsequently, changes sulfur in smoke into sulphur through claus reaction; Said claus reaction device outlet flue gas gets into a sulfur condenser and at least one sulphur separator recovery sulier successively, and the Claus tail gases of said sulphur separator outlet is sent into coal-fired boiler in power plant and carried out burning disposal.
9. according to the method for claim 7 or 8; It is characterized in that; Said water-gas, Sweet natural gas or coke-oven gas fuel are at first reducing the combustion chamber internal combustion of roasting kiln; Utilize fuel combustion heat that gaseous mixture is heated to 1100 ~ 1250 ℃, oxygen in the gaseous mixture and sulphur trioxide all change carbonic acid gas, water vapour and sulfurous gas into; Control said catalytic reduction reactor inlet gas temperature at 350 ~ 600 ℃, temperature out at 500 ~ 650 ℃; Through hot by-pass said catalytic reduction reactor part inlet gas is caused the outlet of said catalytic reduction reactor, the mol ratio of hydrogen sulfide and sulfurous gas maintains 2: 1 in the outlet mixed gas to regulate; Said catalytic reduction reactor adopts the titaniferous hydrolyst.
10. according to the method for claim 1 or 8, it is characterized in that said claus reaction device inlet temperature is controlled at 200 ~ 300 ℃, said catalytic reduction reactor section port gas is caused the import of said claus reaction device, to regulate the inlet gas temperature; Said claus reaction device adopts aluminium oxide catalyst.
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